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WO2014197508A1 - Nitro aromatic substituted metal hydroxyl nitrates - Google Patents

Nitro aromatic substituted metal hydroxyl nitrates Download PDF

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Publication number
WO2014197508A1
WO2014197508A1 PCT/US2014/040752 US2014040752W WO2014197508A1 WO 2014197508 A1 WO2014197508 A1 WO 2014197508A1 US 2014040752 W US2014040752 W US 2014040752W WO 2014197508 A1 WO2014197508 A1 WO 2014197508A1
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WO
WIPO (PCT)
Prior art keywords
salts
nitrate
metal
derivatives
gas generating
Prior art date
Application number
PCT/US2014/040752
Other languages
French (fr)
Inventor
Sudhakar R. Ganta
Scott M. RAMBOW
Deborah L. Hordos
Original Assignee
Tk Holdings Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Tk Holdings Inc. filed Critical Tk Holdings Inc.
Priority to DE112014002656.5T priority Critical patent/DE112014002656T5/en
Publication of WO2014197508A1 publication Critical patent/WO2014197508A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B41/00—Compositions containing a nitrated metallo-organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention relates generally to gas generating systems, and to an improved gas generating compound that may constitute a monopropellant.
  • the present invention relates to vehicle occupant protection systems or other safety systems employing gas generators to actuate an inflatable cushion for example.
  • U.S. Patent Nos. 5,035,757, 5,872,329, 6,074,502, 6,210,505, 6,287,400, 7,959,749, 6, 189,927, 5,062,367, and 5,308,588 exemplify known pyrotechnic gas generating compositions and/or known gas generators and their operating environments, whereby each patent is herein incorporated by reference in its entirety.
  • the pyrotechnic means typically include an initiator or igniter, and a gas generating composition igniiable by the igniter once the actuator is activated.
  • a gas generating composition includes a compound that is produced from the substitution reaction of a nitro- arornatic compound and a metal hydroxy nitrate.
  • the reaction product may be selected from dimirobenzoic acid substituted basic copper nitrate, dinitrosalicylic acid substituted basic copper nitrate, potassium salt of dinitrosalicylic acid substituted basic copper nitrate, isophthaiic acid substituted basic copper nitrate, potassium salt of isophthaiic acid substituted basic copper nitrate, hydroxy pyridine substituted basic copper nitrate, and mixtures thereof;
  • An oxidizer may be selected from nonmeta! and metal nitrate salts; chlorate salts; metal and nonmetal perchlorate salts; metal and nonmeta! oxides; basic nitrate salts, and mixtures thereof.
  • a fuel may be selected from derivatives of bi$-(l(2)H- tetrazo 1-5-yl )-amrne; tetrazoles, triazoles, and azoles; metal and nonmetal salts of tetrazo!es, triazoies, and azoles; nitrate salts of tetrazoles, triazole, and azoles;
  • nitramine derivatives of tetrazoles, triazoies, and azoles metal and nonmetal salts of nitramine derivatives of azoles; salts and derivatives of guanidines; azoamides; nitrate salts of azoamides; and mixtures thereof.
  • the present invention relates to compounds formed by substitution reactions including a metal hydroxy! nitrate, such as basic copper nitrate, and a nitro aromatic, such as dinitrobenzoic acid, as reactants.
  • a metal hydroxy! nitrate contains at least one hydroxide km and at least one nitrate as a basic metal nitrate.
  • a ''nitro aromatic may be defined as a compound thai has nitro and aromatic character.
  • the term '"compound is given its normal meaning, which is to say that it means a single constituent such as a fuel, an oxidizer, or any other constituent of known gas generating compositions, for example.
  • composition is meant to convey a mixture of several compounds such as a fuel, an oxidizer, and any other constituent of known gas generating compositions, for example.
  • the compounds formed by nitro aromatic substitution of a metal hydroxy] nitraie are useful as gas generant constituents, and certain of these compounds may be used as a monoprope!lant thereby reducing the cost and complexity of manufacturing related gas generants.
  • manufacturing safety is enhanced because of the ability to use these novel compounds independent of any other typical gas generant constituents such as oxidizers, slag formers, coolants, and other known constituents.
  • the formation reactions may be generally stated as substituting metal hydroxy] nitrates with various nitro aromaiics.
  • the metal hydroxy! nitrates may be formed with transition metals, such as but not limited to, cobalt, zinc, manganese, iron, copper, and cerium.
  • An exemplary metal hydroxy! nitrate includes basic copper nitrate.
  • nitro aromaties may be selected from the group including, but not limited to, nitro benzo derivatives such as nitrobenzoic acid and dinitrobenzoic acid, derivatives thereof and metal and nonmetal salts thereof including 3,5-dinitrobenz house substituted basic copper nitrate; nitro salicylic derivatives such as di.notxosaiicylic acid and salts thereof such as the potassium salt of dinitrosalicylic acid, potassium 3,5 ⁇ dinitrosalicylate substituted basic copper nitrate, and 3,5-dinitrosaIicylate substituted basic copper nitrate; isophtha!ic acid and derivatives and salts thereof including the potassium salt of Isophf a!ic acid, 5- rntroisophthalate substituted basic copper nitrate, and. potassium isophihalate substituted
  • nitro-aromatic substituted metal hydroxy! nitrates are synthesized by reacting the metal hydroxy! nitrate (e.g. basic copper nitrate) with nitro aromatic acid in the presence of water to yield novel mtro-aromatic substituted metal hydroxy! nitrate molecules.
  • metal hydroxy! nitrate e.g. basic copper nitrate
  • nitro aromatic acid e.g. nitro aromatic acid
  • novel gas generating constituents such as, but not limited to the following, may be combined with the novel compounds described above, thereby forming novel gas generating compositions.
  • These constituents include: fuels selected from tetrazo!es, triazoies, triazines, and guamdines, and salts and derivatives of each type of fuel ; oxidizers selected from nonrnetal or metal (alkali, alkaline earth, and/or transitional metal) nitrates, nitrites, chlorates, perchiorates, and oxides; coolants, slag formers, and/or additives such as clay, tale, mica, silica, and so forth.
  • gas generating compositions of the present invention may contain a mtro-aromatic substituted metal hydroxyl nitrate as defined herein. More preferably, the nitro-aromatic substituted metal hydroxyl nitrate may be provided at about 3-15 weight percent of the total composition. Yet further, the nitro-aromatic substituted metal hydroxyl nitrate may be provided at about 5-15 weight percent of the total composition.
  • the first oxidizer is generally provided at about 0.1 -SO wt% of the gas generant composition, and more preferably at about 10-70 wt%.
  • gas generating compositions formed in accordance with the present invention may contain a secondary fuel selected from the group containing derivatives of bis-(l (2)H-tetrazol-5-yl )-amine (BTA), including its anhydrous acid and its acid monohydrate.
  • BTA bis-(l (2)H-tetrazol-5-yl )-amine
  • azoles such as 5 ⁇ aminot.etrazole; metal salts of azoles such as potassium 5-aininotetrazole; nonmetal salts of azoles such as mono-or di- ammonium salt of 5, S'-bis-l H-tetrazole; nitrate salts of azoles such as 5- aminotetrazoie nitrate; nitramine derivatives of azoles such as 5-nitraminotetrazoie; metal salts of nitramine derivatives of azoles such as dipotassium 5- nitraminotetrazole; nonmetal salts of nitramine derivatives of azoles such as mono- or di -am
  • nitroguanidine azoamides such as azodicarbonamide; nitrate salts of azoamides such as azodi.carbonamidi.ne dinitrate; and mixtures thereof and is generally provided at about 0. ⁇ -50 wt%, more preferably 0.1 -30 wt%.
  • the gas generating compositions of the present invention may be mixed in a known manner.
  • the primary fuel formed by the substitution reaction of the nitro aromatic and the metal hydroxyl nitrate may be mixed with an oxidizer, and any other desired constituent, such as a secondary foe! described above.
  • Other gas generating constituents known in the art, such as coolants, slag formers, desiccants, and so forth, may also be provided in known effective amounts.
  • a gas generating compositions of the present invention may also contain an optional additive selected from the group including silicone compounds; elemental silicon; silicon dioxide; famed silica: silicones such as
  • the optional additive is generally provided at about 0.1-10%, and more preferably at about 0.1-5%.
  • An optional binder may be included in the gas generant composition and is selected from the group of cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, carhoxyrnethyceliulose, salts of carboxymethylcel ose,
  • carboxymethyl cellulose acetate butyrate silicone; polvalkene carbonates such as polypropylene carbonate and polyethylene carbonate: and mixtures thereof, and when included is generally provided at abou 0.1-10%, and more preferably at about 0,1-
  • the substitutio reactants and the various typical gas generant constituents described herein may be provided by companies such as Aldrich Chemical Company or Fisher, for example.
  • Various exemplary salts were manufactured by basic acid'base chemistry resulting in salts ofnit.ro aromatics as described herein.
  • the novel nitro-aromatic substituted metal hydroxy! nitrates of the present invention may he dry-mixed or wet-mixed with the oxidizers, secondary fuels, and other constituents of the gas generating compositions described herein to form a un form or homogeneous mixture of the gas generating composition containing the novel compounds.
  • the following examples illustrate the present invention, but not by way of limitation.
  • the examples illustrate the unexpected and surprising results of adding a nitro-aromatic substituted metal hydroxy! nitrate to compositions containing an oxidizer such as a basic metal nitrate, and a fuel such as a guanidirje-based derivative,
  • BCN Basic copper nitrate
  • ADNSA ammonium dmitrosalieylic acid
  • the mixture was mixed, for example with a planetary mixer, for about 1 -5 minutes, at a nominal speed setting of 400 rpms. Water, in an amount of 500 ml, was added as a rinse.
  • GN Guanidme nitrate
  • the mixture was maintained at I05C and stirred (at about 400 rpm) for about ten minutes while adding an additional 500 ml of water as a second rinse. A uniform or homogeneously mixed precipitate formed. The precipitate was dried for about 90 minutes in a temperature range of 90C to 105C.
  • a composition containing 46.6 grams of basic copper nitrate and 53.4 grams of guanidine nitrate was mixed and formed as described in Example 1.
  • the composition was compacted and formed as a tablet.
  • the chamber pressure peaked at about 21.5 MPa at about .003 seconds.
  • a pressure trough was presented in the combustion profile from 0,02 to 0.025 seconds wherein the chamber pressure measured about 3.5 to 4.0 MPa.
  • the chamber pressure then increased slightly from 4.0 to about 5.25 MPa from about 0.025 to about 0.035 seconds. Thereafter, the chamber pressure iinearly decreased over time to a chamber pressure of about 2.5 at 0.1 seconds of combustion.
  • Example 2 A A sample of the composition formed as described in Example 2 A and loaded in the same type ofinflator as 2 A, was inserted in a 60 L lank., wherein combustion of the composition was initiated and conducted over a period of 0, 1 seconds.
  • the combustion profile exhibited a slight combustion lag or trough from about 0.01 to about 0.03 seconds.
  • the combustion profile then exhibited substantially linear growth to a maximum tank pressure of about 120 kPa at 0.1 seconds.
  • the bum rate of the composition of Example 2A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the burn rate of the sample was about. 0.275 inches per second (ips). At 20 MPa, the bum rate of the sample was about 0.500 ips. At about 36 MPa, the bum rate of the sample was about 0.675 ips.
  • a composition containing 46.2 grams of basic copper nitrate, 43.5 grams of guanidine nitrate, and 10.3 grams dinitrobenzoic acid substituted basic copper nitrate (BCN- DNBA) (formed from the substitution reaction of basic copper nitrate (metal hydroxy! nitrate) and dinitrobenzoic acid (DNBA, niiro aromatic) as described herein), was mixed and formed as described in Example 1.
  • the composition was compacted and formed as a tablet, A gas generator as described in Example 2A was loaded with 283 grams of this composition. Upon combustion, over a period of 0.3 seconds of combustion time, the chamber pressure peaked at about 20.5 Pa at about .003 seconds.
  • the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 1.5 MPa, The chamber pressure from 0.01 - 0.03 seconds ranged from about 12.5 MPa to about 5.5 MPa,
  • Example 3 A A sample of the composition ionised as described in Example 3 A (28.3 grams) and loaded in the same type of infiator as 2A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0.3 seconds, The combustion profile exhibited a progressive logarithmic growth to a maximum tank pressure of about 127 kPa at 0.1 seconds.
  • the burn rate of the composition of Example 3 A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the bum rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0.335 inches per second (ips). At 20 MPa, the burn rate of the sample was about 0.570 ips. At about 36 MPa, the burn rate of the sample was about 0.725 ips.
  • a composition containing 45,7 grams of basic copper nitrate, 44.8 grams of guanidine nitrate, and 9.2 grams ofd Urosa!icyiic acid substituted basic copper nitrate (BCN- DNSA) (formed from the substitution reaction of basic copper nitrate (metal hydroxvl nitrate) and ammonium dinitrosaiicyiic acid (nitro aromatic) a.s described herein), was mixed and formed as described in Example 1.
  • the composition was compacted and formed as a tablet.
  • a gas generator as described in Example 2A was loaded with 27,9 grams of this composition. U on combustion, over a period of 0, 1 seconds of combustion time, the chamber pressure peaked at about 23.0 Pa at about .003 seconds.
  • the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0, 1 seconds was about 1.0 MPa.
  • the chamber pressure from 0.01 ⁇ 0.03 seconds ranged from about 14.8 MPa to about 7,4 MPa.
  • Example 4A A sample of the composition formed as described in Example 4A (27.9 grams) and loaded in the same type of infiator as 2 A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0,1 seconds.
  • the combustion profile exhibited a progressive logarithmic growth to about 145 kPa at 0.3 seconds.
  • the maximum tank pressure was about .146 kPa at about 0.09 seconds.
  • the bum rate of the composition of Example 4A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0.325 inches per second (ips). At 20 MPa, the burn rate of the sample was about 0.615 ips. At about 36 MPa, the burn rate of the sample was about 0.8(H) ips.
  • the composition was compacted and formed as a tablet.
  • a gas generator as described in Example 2A was loaded with 28.0 grams of this composition. Upon combustion, over period of 0.1 seconds of combustion rime, the chamber pressure peaked at about 21.5 MPa at about .003 seconds.
  • the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 0.5 MPa.
  • the chamber pressure from 0.01 - 0.03 seconds ranged from about 13.0 MPa to about 5.0 MPa.
  • Example 5 A sample of the composition formed as described in Example 5 A (28.0 grams) and loaded in the same type of inflator as 2 A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0.1 seconds.
  • the combustion profile exhibited a progressive logarithmic growth to about 153 kPa at 0.1 seconds, The maximum tank pressure was about. 160 kP at about 0.062 seconds.
  • E mrmleJC 8010 The burn rate of the composition of Example 5 A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except, for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0,335 inches per second (ips). At 20 MPa. the bum rate of the sample was about 0.600 ips. At about 36 MPa, the hum rate of the sample was about 0.780 ips.
  • BCN- DNBA dinitrobenzoic acid substituted basic copper nitrate
  • KDNBA potassium dinitrobenzoic acid
  • the combustion profile After peak, combustion, the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 0,5 MPa.
  • the chamber pressure from 0.01 ⁇ 0,03 seconds ranged from about 12.0 MPa to about 4,8 MPa.
  • Example 6A A sample of the composition formed as described in Example 6A (28.3 grams) and loaded in the same type of inflator as 2A, was inserted in a 60 L tank wherein combustion of the composition was initiated and conducted over a period of 0, 1 seconds, The combustion profile exhibited a progressive logarithmic growth to about 1 6 kPa at 0.1 seconds. The maximum tank pressure was about 150 kPa at about 0.060 seconds.
  • the bum rate of the composition of Example 6A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample w as then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the burn rale of the sample was about 0.300 inches per second (ips). At 20 MPa, the bum rate of the sample was about 0.520 ips. At about 36 MPa, the bum rate of the sample was about 0.680 ips.
  • an exemplary inflator utilizing the compounds of the present in vention incorporates a d ual chamber design to tailor the force of deployment of an associated airbag.
  • an inflator containing a booster composition 12 formed as known in the art may be provided, and may be manufactured as known in the art.
  • a primary gas generating compound or composition 14 as described herein is also provided as shown in FIG. 1 .
  • U.S. Patent Nos. 6,422,601 , 6,805,377, 6,659,500, 6,749,219, and 6,752,421 exemplify typical airbag inflator designs and are each incorporated herein by reference in their entirety.
  • Airbag system 200 includes at least one airbag 202 and an inflator 1 containing a gas generating composition 14 in accordance with the present invention, coupled to airbag 202 so as to enable fluid communication with an interior of the airbag.
  • Airbag system 200 may also include tor be in communication with) a crash event sensor 210.
  • Crash event sensor 210 includes a known crash sensor algorithm that signals actuation of airbag system 200 via, for example, activation of airbag inflaior 10 in the event of a collision.
  • FIG. 2 shows a schematic diagram of one exemplary embodiment of such a restraint system.
  • Safety belt assembly 150 includes a safety belt housing 152 and a safety belt 100 extending from housing 152,
  • a safety belt retractor mechanism 154 (for example, a spring-loaded mechanrsm) may be coupled to an end portion of the belt.
  • a safety belt pretensioner 156 containing gas generating composition 14 may be coupled to belt retractor mechanism 154 to actuate the retractor mechanism in the event of a collision.
  • Typical seat belt retractor mechanisms which may he used in conjunction with the safety belt embodiments of the present invention are described in U.S. Pat. os. 5,743,480, 5,553,803, 5,667,161 , 5,451,008, 4,558,832 and 4,597,546, each incorporated herein by reference.
  • Illustrative examples of typical pretens oners with which the safety belt embodiments of the present invention may be combined are described in U.S. Pat. Nos. 6,505,790 and 6,419,177, incorporated herein by- reference ,
  • Safety belt assembly 1 50 may also include (or be in communication with) a crash event sensor 158 (for example, an inertia sensor or an accelerometer) including a known crash sensor algorithm that signals actuation of belt pretensioner 156 via, for example, activation of a pyrotechnic igniter (not shown) incorporated into the pretensioner.
  • a crash event sensor 158 for example, an inertia sensor or an accelerometer
  • U.S. Patent Nos. 6,505,790 and 6,419,177 previously incorporated herein by reference, provide illustrative examples of pretensioners actuated in such a manner.
  • safety belt assembly 150, airbag system 200, and more broadly, vehicle occupant protection system 180 exemplify but do not limit gas generating systems contemplated in accordance with the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

The reaction product of a nitro aromatic and a metal hydroxyl nitrate is presented. Gas generating compositions containing the reaction product are also presented. Gas generators (10) and vehicle occupant protection systems (200) containing the reaction product are also presented. The metal hydroxyl nitrate can be basic copper nitrate. The nitro aromatic can be nitro benzo derivative; nitro salicylic derivative; isophthalic acid derivative or pyridine derivative.

Description

fJTRO AROMATIC SUiiSTITIJTED METAL HYDROXYL NITRATES
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application Serial No. 61/830,616 filed on June 3, 2013.
TECHNICAL FIELD
The present invention relates generally to gas generating systems, and to an improved gas generating compound that may constitute a monopropellant.
BACKGROUND OF T . VENTION
The present invention relates to vehicle occupant protection systems or other safety systems employing gas generators to actuate an inflatable cushion for example. U.S. Patent Nos. 5,035,757, 5,872,329, 6,074,502, 6,210,505, 6,287,400, 7,959,749, 6, 189,927, 5,062,367, and 5,308,588 exemplify known pyrotechnic gas generating compositions and/or known gas generators and their operating environments, whereby each patent is herein incorporated by reference in its entirety. The pyrotechnic means typically include an initiator or igniter, and a gas generating composition igniiable by the igniter once the actuator is activated.
There is an ongoing initiative to provide gas generating compositions that improve upon the amount of gas produced per gram of gas generating composition, while maintaining or improving the burn rate of the gas generating composition at ambient or other operating pressures.
SUMMARY OF THE INVENTION
In accordance with the present invention, a gas generating composition includes a compound that is produced from the substitution reaction of a nitro- arornatic compound and a metal hydroxy nitrate. The reaction product may be selected from dimirobenzoic acid substituted basic copper nitrate, dinitrosalicylic acid substituted basic copper nitrate, potassium salt of dinitrosalicylic acid substituted basic copper nitrate, isophthaiic acid substituted basic copper nitrate, potassium salt of isophthaiic acid substituted basic copper nitrate, hydroxy pyridine substituted basic copper nitrate, and mixtures thereof;
An oxidizer may be selected from nonmeta! and metal nitrate salts; chlorate salts; metal and nonmetal perchlorate salts; metal and nonmeta! oxides; basic nitrate salts, and mixtures thereof. Finally, a fuel may be selected from derivatives of bi$-(l(2)H- tetrazo 1-5-yl )-amrne; tetrazoles, triazoles, and azoles; metal and nonmetal salts of tetrazo!es, triazoies, and azoles; nitrate salts of tetrazoles, triazole, and azoles;
nitramine derivatives of tetrazoles, triazoies, and azoles; metal and nonmetal salts of nitramine derivatives of azoles; salts and derivatives of guanidines; azoamides; nitrate salts of azoamides; and mixtures thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to compounds formed by substitution reactions including a metal hydroxy! nitrate, such as basic copper nitrate, and a nitro aromatic, such as dinitrobenzoic acid, as reactants. When used herein, a metal hydroxy! nitrate contains at least one hydroxide km and at least one nitrate as a basic metal nitrate. When used herein, a ''nitro aromatic" may be defined as a compound thai has nitro and aromatic character. When used herein, the term '"compound" is given its normal meaning, which is to say that it means a single constituent such as a fuel, an oxidizer, or any other constituent of known gas generating compositions, for example. When used herein, the term "composition" is meant to convey a mixture of several compounds such as a fuel, an oxidizer, and any other constituent of known gas generating compositions, for example. The compounds formed by nitro aromatic substitution of a metal hydroxy] nitraie are useful as gas generant constituents, and certain of these compounds may be used as a monoprope!lant thereby reducing the cost and complexity of manufacturing related gas generants. Furthermore, manufacturing safety is enhanced because of the ability to use these novel compounds independent of any other typical gas generant constituents such as oxidizers, slag formers, coolants, and other known constituents.
The formation reactions may be generally stated as substituting metal hydroxy] nitrates with various nitro aromaiics. 'The metal hydroxy! nitrates may be formed with transition metals, such as but not limited to, cobalt, zinc, manganese, iron, copper, and cerium. An exemplary metal hydroxy! nitrate includes basic copper nitrate. The nitro aromaties may be selected from the group including, but not limited to, nitro benzo derivatives such as nitrobenzoic acid and dinitrobenzoic acid, derivatives thereof and metal and nonmetal salts thereof including 3,5-dinitrobenzoaie substituted basic copper nitrate; nitro salicylic derivatives such as di.notxosaiicylic acid and salts thereof such as the potassium salt of dinitrosalicylic acid, potassium 3,5~dinitrosalicylate substituted basic copper nitrate, and 3,5-dinitrosaIicylate substituted basic copper nitrate; isophtha!ic acid and derivatives and salts thereof including the potassium salt of Isophf a!ic acid, 5- rntroisophthalate substituted basic copper nitrate, and. potassium isophihalate substituted
basic copper nitrate; and pyridine and derivatives thereof such as nitro pynd e(s),
hydroxy! pyridine(s), and 3,5-dinitro hydroxy! pyridine substituted basic copper nitrate.
The following examples of various species within the broader groups describai
above exemplify or blueprint various substitution reactions within the broader group. In
general, stoichiometric amounts of the metal hydroxy! nitrate, such as basic copper
nitrate, combined with the desired niiro-aromatic such as dimtrohenzoic acid yield the
novel substituted metal hydroxy! nitrates.
EXAMPLES
1 ) Dinitrobenzoic acid substituted Basic copper nitrate:
3Cu(OH)2 .C {N(¼)2 v 2 C7H4N206 J.!.20 f R i&~ 2Cu{OH)∑ .Cu(C7H,N206)2 .Cu(NOj)2 2.H20
2) Dinitrosalieylic acid substituted Basic copper nitrate:
3Cu{OH)2 .Cu( 03)2 2 C7H4N;07 mo 1 2Cu(OH)2 .Cu{C?H?,N207)2 -Cu(NO,)2 + 2.¾0
Potassium salt of dinitrosalicvlic acid substituted Basic copper nitrate C»(OH>, .Co(NO,}2 -r 2 -C7H3N,G7 1120 / R , 2Cu(OH)2 .Cxi{K-C7H2N207)2 .Cu(N03)2 - 2.H20 ) Isophihalicacid substituted Basic copper nitrate:
3C«(OH)2 .CiJ(NO, !2 + 2 <¼Η,Ν06 JH2I L- 2Co{OH)2 .Ca(CsH4N06)2 .C«{N03)2 + 2 2Q
Potassium salt of Isophihalicacid substituted Basic copper nitrate
Cu(GH)2 .Cu{N<¾}2 + 2 K-C*H4N<¾ H2Q / RT^ 2Cu(OH}2 .Cu( -C8H3N06)2 .Ca(N03)2 + 2.1¾0 } Hydroxy pyridine substituted Basic copper iiitrate:
Cu(OH)2 ,Ctt(N03}2 + 2 CsH3N305 H2Q m^ 2Cu(OH)2 .CuiC^^O- ,Cu(NG3)2 + 2.H20 )
Figure imgf000006_0001
H>0
Figure imgf000006_0002
As exemplified in the examples, nitro-aromatic substituted metal hydroxy! nitrates are synthesized by reacting the metal hydroxy! nitrate (e.g. basic copper nitrate) with nitro aromatic acid in the presence of water to yield novel mtro-aromatic substituted metal hydroxy! nitrate molecules.
It is contemplated that if desired, other typical gas generating constituents such as, but not limited to the following, may be combined with the novel compounds described above, thereby forming novel gas generating compositions. These constituents include: fuels selected from tetrazo!es, triazoies, triazines, and guamdines, and salts and derivatives of each type of fuel ; oxidizers selected from nonrnetal or metal (alkali, alkaline earth, and/or transitional metal) nitrates, nitrites, chlorates, perchiorates, and oxides; coolants, slag formers, and/or additives such as clay, tale, mica, silica, and so forth.
For example, gas generating compositions of the present invention may contain a mtro-aromatic substituted metal hydroxyl nitrate as defined herein. More preferably, the nitro-aromatic substituted metal hydroxyl nitrate may be provided at about 3-15 weight percent of the total composition. Yet further, the nitro-aromatic substituted metal hydroxyl nitrate may be provided at about 5-15 weight percent of the total composition. A first oxidizer selected from the group including nonmetal an metal nitrate salts such as ammonium nitrate, phase-stabilized ammonium nitrate, potassium nitrate, strontium nitrate; nitrite salts such as potassium nitrite; chlorate salts such as potassium chlorate; metal and nonmetal perchlorate salts such as potassium or ammonium perchlorate; oxides such as iron oxide and copper oxide; basic nitrate salts such as basic copper nitrate and basic iron nitrate, and mixtures thereof is provided. The first oxidizer is generally provided at about 0.1 -SO wt% of the gas generant composition, and more preferably at about 10-70 wt%. further, gas generating compositions formed in accordance with the present invention may contain a secondary fuel selected from the group containing derivatives of bis-(l (2)H-tetrazol-5-yl )-amine (BTA), including its anhydrous acid and its acid monohydrate. mono-ammonium salt of his-(l (2)H-tetrazoh5-yl)-amine, metal salts of bis-(l (2)H-tetrazol-5~yl)-amine including the potassium, sodium, strontium, copper, and zinc salts of BTA, and complexes thereof; azoles such as 5~aminot.etrazole; metal salts of azoles such as potassium 5-aininotetrazole; nonmetal salts of azoles such as mono-or di- ammonium salt of 5, S'-bis-l H-tetrazole; nitrate salts of azoles such as 5- aminotetrazoie nitrate; nitramine derivatives of azoles such as 5-nitraminotetrazoie; metal salts of nitramine derivatives of azoles such as dipotassium 5- nitraminotetrazole; nonmetal salts of nitramine derivatives of azoles such as mono- or di -ammonium 5-nitraminotetrazole and; guanidraes such as dicyandi amide; salts of guanidines such as guanid ne nitrate; nitro derivatives guanidines such as
nitroguanidine; azoamides such as azodicarbonamide; nitrate salts of azoamides such as azodi.carbonamidi.ne dinitrate; and mixtures thereof and is generally provided at about 0. } -50 wt%, more preferably 0.1 -30 wt%.
The gas generating compositions of the present invention may be mixed in a known manner. For example, the primary fuel formed by the substitution reaction of the nitro aromatic and the metal hydroxyl nitrate may be mixed with an oxidizer, and any other desired constituent, such as a secondary foe! described above. Other gas generating constituents known in the art, such as coolants, slag formers, desiccants, and so forth, may also be provided in known effective amounts.
For example, a gas generating compositions of the present invention may also contain an optional additive selected from the group including silicone compounds; elemental silicon; silicon dioxide; famed silica: silicones such as
po!ydimethylsi!oxane; silicates such as potassium silicates; natural minerals such as talc and clay; lubricants such as graphite powder or fibers, magnesium stearate, boron nitride, molybdenum sulfide; famed alumina; polyethylene; paraffin: and mixtures thereof. When included, the optional additive is generally provided at about 0.1-10%, and more preferably at about 0.1-5%.
An optional binder may be included in the gas generant composition and is selected from the group of cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, carhoxyrnethyceliulose, salts of carboxymethylcel ose,
carboxymethyl cellulose acetate butyrate; silicone; polvalkene carbonates such as polypropylene carbonate and polyethylene carbonate: and mixtures thereof, and when included is generally provided at abou 0.1-10%, and more preferably at about 0,1-
370 ,
The substitutio reactants and the various typical gas generant constituents described herein, may be provided by companies such as Aldrich Chemical Company or Fisher, for example. Various exemplary salts were manufactured by basic acid'base chemistry resulting in salts ofnit.ro aromatics as described herein. In accordance with the present invention, the novel nitro-aromatic substituted metal hydroxy! nitrates of the present invention may he dry-mixed or wet-mixed with the oxidizers, secondary fuels, and other constituents of the gas generating compositions described herein to form a un form or homogeneous mixture of the gas generating composition containing the novel compounds. The following examples illustrate the present invention, but not by way of limitation. More specifically, the examples illustrate the unexpected and surprising results of adding a nitro-aromatic substituted metal hydroxy! nitrate to compositions containing an oxidizer such as a basic metal nitrate, and a fuel such as a guanidirje-based derivative,
EXAMPLES
Example 1 -Mixing and Manufacturing Method
A mixing vessel containing 2000 ml of distilled water, heated to 105C, was provided. Gas generating constituents were provided that collectively weighed 5000 grams, Basic copper nitrate (BCN) ai about 2520.40 grams (50.41 weight percent of the total constituents) and ammonium dmitrosalieylic acid (ADNSA) at about 250.00 grams (5.00 weight percent of the total constituents) were both added to the mixing vessel. The mixture was mixed, for example with a planetary mixer, for about 1 -5 minutes, at a nominal speed setting of 400 rpms. Water, in an amount of 500 ml, was added as a rinse. Guanidme nitrate (GN) at about 2229.60 (44.59 weight percent of the total constituents) was then added to the mixture. The mixture was maintained at I05C and stirred (at about 400 rpm) for about ten minutes while adding an additional 500 ml of water as a second rinse. A uniform or homogeneously mixed precipitate formed. The precipitate was dried for about 90 minutes in a temperature range of 90C to 105C.
Example 2 A-Comparative Example 8001
A composition containing 46.6 grams of basic copper nitrate and 53.4 grams of guanidine nitrate was mixed and formed as described in Example 1. The composition was compacted and formed as a tablet. A gas generator formed as described in U.S. Patent No. 7,537,241, herein incorporated by reference in its entirety, was loaded with 26.3 grams of the composition. Upon combustion, over a period of 0.1 seconds of combustion time, the chamber pressure peaked at about 21.5 MPa at about .003 seconds. A pressure trough was presented in the combustion profile from 0,02 to 0.025 seconds wherein the chamber pressure measured about 3.5 to 4.0 MPa. The chamber pressure then increased slightly from 4.0 to about 5.25 MPa from about 0.025 to about 0.035 seconds. Thereafter, the chamber pressure iinearly decreased over time to a chamber pressure of about 2.5 at 0.1 seconds of combustion.
Example 2B-Comparative Example SO0I
A sample of the composition formed as described in Example 2 A and loaded in the same type ofinflator as 2 A, was inserted in a 60 L lank., wherein combustion of the composition was initiated and conducted over a period of 0, 1 seconds. The combustion profile exhibited a slight combustion lag or trough from about 0.01 to about 0.03 seconds. The combustion profile then exhibited substantially linear growth to a maximum tank pressure of about 120 kPa at 0.1 seconds.
Exek c sooi.
The bum rate of the composition of Example 2A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the burn rate of the sample was about. 0.275 inches per second (ips). At 20 MPa, the bum rate of the sample was about 0.500 ips. At about 36 MPa, the bum rate of the sample was about 0.675 ips.
Example 3 A 8000
A composition containing 46.2 grams of basic copper nitrate, 43.5 grams of guanidine nitrate, and 10.3 grams dinitrobenzoic acid substituted basic copper nitrate (BCN- DNBA) (formed from the substitution reaction of basic copper nitrate (metal hydroxy! nitrate) and dinitrobenzoic acid (DNBA, niiro aromatic) as described herein), was mixed and formed as described in Example 1. The composition was compacted and formed as a tablet, A gas generator as described in Example 2A was loaded with 283 grams of this composition. Upon combustion, over a period of 0.3 seconds of combustion time, the chamber pressure peaked at about 20.5 Pa at about .003 seconds. After peak combustion, the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 1.5 MPa, The chamber pressure from 0.01 - 0.03 seconds ranged from about 12.5 MPa to about 5.5 MPa,
Example 3B 8000
A sample of the composition ionised as described in Example 3 A (28.3 grams) and loaded in the same type of infiator as 2A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0.3 seconds, The combustion profile exhibited a progressive logarithmic growth to a maximum tank pressure of about 127 kPa at 0.1 seconds.
The burn rate of the composition of Example 3 A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the bum rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0.335 inches per second (ips). At 20 MPa, the burn rate of the sample was about 0.570 ips. At about 36 MPa, the burn rate of the sample was about 0.725 ips. Example 4 A 8004
A composition containing 45,7 grams of basic copper nitrate, 44.8 grams of guanidine nitrate, and 9.2 grams ofd Urosa!icyiic acid substituted basic copper nitrate (BCN- DNSA) (formed from the substitution reaction of basic copper nitrate (metal hydroxvl nitrate) and ammonium dinitrosaiicyiic acid (nitro aromatic) a.s described herein), was mixed and formed as described in Example 1. The composition was compacted and formed as a tablet. A gas generator as described in Example 2A was loaded with 27,9 grams of this composition. U on combustion, over a period of 0, 1 seconds of combustion time, the chamber pressure peaked at about 23.0 Pa at about .003 seconds. After peak combustion, the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0, 1 seconds was about 1.0 MPa. The chamber pressure from 0.01■■■ 0.03 seconds ranged from about 14.8 MPa to about 7,4 MPa.
E am|rieJB 8004
A sample of the composition formed as described in Example 4A (27.9 grams) and loaded in the same type of infiator as 2 A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0,1 seconds. The combustion profile exhibited a progressive logarithmic growth to about 145 kPa at 0.3 seconds. The maximum tank pressure was about .146 kPa at about 0.09 seconds.
Example 4C 8004
The bum rate of the composition of Example 4A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0.325 inches per second (ips). At 20 MPa, the burn rate of the sample was about 0.615 ips. At about 36 MPa, the burn rate of the sample was about 0.8(H) ips.
Example 5 A 8010
A composition containing 45.7 grams of basic copper nitrate, 45.1 grams of guanidine nitrate, and 9.2 grams of dinitrosalicylic acid substituted basic copper nitrate (BCN- D SA) (formed from the substitution reaction of basic copper nitrate (metal hydroxy! nitrate) and potassium dinitrosalicylic acid (nitro aromatic) as described herein), was mixed and formed as described in Example 1. The composition was compacted and formed as a tablet. A gas generator as described in Example 2A was loaded with 28.0 grams of this composition. Upon combustion, over period of 0.1 seconds of combustion rime, the chamber pressure peaked at about 21.5 MPa at about .003 seconds. After peak combustion, the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 0.5 MPa. The chamber pressure from 0.01 - 0.03 seconds ranged from about 13.0 MPa to about 5.0 MPa.
E ffi*}£!e 5B 8010
A. sample of the composition formed as described in Example 5 A (28.0 grams) and loaded in the same type of inflator as 2 A, was inserted in a 60 L tank, wherein combustion of the composition was initiated and conducted over a period of 0.1 seconds. The combustion profile exhibited a progressive logarithmic growth to about 153 kPa at 0.1 seconds, The maximum tank pressure was about. 160 kP at about 0.062 seconds.
E mrmleJC 8010 The burn rate of the composition of Example 5 A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except, for a top portion. The sample was then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the bum rate of the sample was about 0,335 inches per second (ips). At 20 MPa. the bum rate of the sample was about 0.600 ips. At about 36 MPa, the hum rate of the sample was about 0.780 ips.
A composition containing 46.2 grams of basic copper nitrate, 45.3 grams of guanidine nitrate, and 10.3 grams of dinitrobenzoic acid substituted basic copper nitrate (BCN- DNBA) (formed from the substitution reaction of basic copper nitrate (metal hydroxy! nitrate) and potassium dinitrobenzoic acid (KDNBA, nitro aromatic) as described herein), was mixed and formed as described in Example 1. The composition was compacted and formed as a tablet. A gas generator as described in Example 2A was loaded with 28.3 grains of this composition. Upon combustion, over a period of 0.1 seconds of combustion time, the chamber pressure peaked at about 18.0 MPa at about ,003 seconds. After peak, combustion, the combustion profile exhibited a regressive logarithmic curve throughout the combustion time of 0.1 seconds wherein the terminal chamber pressure at 0.1 seconds was about 0,5 MPa. The chamber pressure from 0.01 ···· 0,03 seconds ranged from about 12.0 MPa to about 4,8 MPa.
Example 6B 801.1
A sample of the composition formed as described in Example 6A (28.3 grams) and loaded in the same type of inflator as 2A, was inserted in a 60 L tank wherein combustion of the composition was initiated and conducted over a period of 0, 1 seconds, The combustion profile exhibited a progressive logarithmic growth to about 1 6 kPa at 0.1 seconds. The maximum tank pressure was about 150 kPa at about 0.060 seconds.
Example 6C 8011
The bum rate of the composition of Example 6A was evaluated by coating a 2.5 gram cylinder of the composition with epoxy except for a top portion. The sample w as then placed within a pressurized container and upon ignition, the burn rate and pressure were monitored over time. At 5 MPa, the burn rale of the sample was about 0.300 inches per second (ips). At 20 MPa, the bum rate of the sample was about 0.520 ips. At about 36 MPa, the bum rate of the sample was about 0.680 ips.
As shown in FIG. 1 , an exemplary inflator utilizing the compounds of the present in vention incorporates a d ual chamber design to tailor the force of deployment of an associated airbag. In general, an inflator containing a booster composition 12 formed as known in the art may be provided, and may be manufactured as known in the art. A primary gas generating compound or composition 14 as described herein is also provided as shown in FIG. 1 . U.S. Patent Nos. 6,422,601 , 6,805,377, 6,659,500, 6,749,219, and 6,752,421 exemplify typical airbag inflator designs and are each incorporated herein by reference in their entirety.
Referring now to FIG. 2, the exemplary inflator 10 described above may also be incorporated into an airbag system 200. Airbag system 200 includes at least one airbag 202 and an inflator 1 containing a gas generating composition 14 in accordance with the present invention, coupled to airbag 202 so as to enable fluid communication with an interior of the airbag. Airbag system 200 may also include tor be in communication with) a crash event sensor 210. Crash event sensor 210 includes a known crash sensor algorithm that signals actuation of airbag system 200 via, for example, activation of airbag inflaior 10 in the event of a collision.
Referring again to PIG. 2, airbag system 200 may also be incorporated into a broader, more comprehensive vehicle occupant restraint system 1 SO including additional elements such as a safety belt assembly 150. FIG. 2 shows a schematic diagram of one exemplary embodiment of such a restraint system. Safety belt assembly 150 includes a safety belt housing 152 and a safety belt 100 extending from housing 152, A safety belt retractor mechanism 154 (for example, a spring-loaded mechanrsm) may be coupled to an end portion of the belt. In addition, a safety belt pretensioner 156 containing gas generating composition 14 may be coupled to belt retractor mechanism 154 to actuate the retractor mechanism in the event of a collision. Typical seat belt retractor mechanisms which may he used in conjunction with the safety belt embodiments of the present invention are described in U.S. Pat. os. 5,743,480, 5,553,803, 5,667,161 , 5,451,008, 4,558,832 and 4,597,546, each incorporated herein by reference. Illustrative examples of typical pretens oners with which the safety belt embodiments of the present invention may be combined are described in U.S. Pat. Nos. 6,505,790 and 6,419,177, incorporated herein by- reference ,
Safety belt assembly 1 50 may also include (or be in communication with) a crash event sensor 158 (for example, an inertia sensor or an accelerometer) including a known crash sensor algorithm that signals actuation of belt pretensioner 156 via, for example, activation of a pyrotechnic igniter (not shown) incorporated into the pretensioner. U.S. Patent Nos. 6,505,790 and 6,419,177, previously incorporated herein by reference, provide illustrative examples of pretensioners actuated in such a manner. should be appreciated that safety belt assembly 150, airbag system 200, and more broadly, vehicle occupant protection system 180 exemplify but do not limit gas generating systems contemplated in accordance with the present invention.
The present description is for illustrative purposes only, and should not be construed to limit the breadth of the present invention in any way. Thus, those skilled in the art will appreciate that, various modifications coald be made to the presently disclosed embodiments without departing from the scope of the present invention as defined in the appended claims.

Claims

WHAT IS CLAIMED IS:
I , A gas generating compound comprising; the reaction product of a metal hydroxyi nitrate compound reacted with a nitro aromatic compound in an aqueous solution.
2. The gas generating compound of claim 1 wherein the metal hydroxyi nitrate is selected from basic metal nitrates containing at least one metal selected from copper, zinc, cobalt, manganese, iron, cerium, and nickel.
3. The gas generating compound of claim 1 wherein the metal hydroxyi nitrate contains a metal selected from copper, cobalt, zinc, manganese, iron, nickel, and cerium.
4. The gas generating compound of claim 1 wherein the metal hydroxyi nitrate contains a transitional metal.
5. The gas generating compound of claim I wherein the nitro aromatic is selected from nitro benzo derivatives; nitro salicylic derivatives; isophthalic acid and derivatives and salts thereof; and pyridine and derivatives thereof.
6. The gas generating composition of claim I wherein the reaction product is selected from dinitrobenzoic acid substituted baste copper nitrate,
dim rosalieylic acid substituted basic copper nitrate, potassium salt of dinttrosalicy!ic acid substituted basic copper nitrate, isophthalic acid substituted basic copper nitrate, potassium salt of isophthalic acid substituted basic copper nitrate, hydroxy pyridine substituted basic copper nitrate, and mixtures thereof,
7, The gas generating composition, of cl im 1 wherein the reaction product is represented by the formula:
Figure imgf000020_0001
8. A gas generating composition containing the compound of claim 1.
9. A vehicle occupant protection system containing the compound of claim 1.
10. A gas generator containing the compound of claim 1 ,
1 1 , A gas generating composition consisting of the compound of claim 1.
12. The gas generating composition of claim 6 further composing an oxidizer selected from nonmetal and metal nitrate salts; nitrite salts; chlorate salts; metal and nonmetal perchlorate salts; metal oxides; basic metal nitrate salts; and mixtures thereof.
13. The gas generating composition of claim 6 further comprising a fuel selected from derivatives of bis-( 1 (2)H-tetrazol-5-yl)-ainine; azoles and derivatives thereon triazines and derivatives thereof; tetrazoles and derivatives thereof; iriazoles and derivatives thereof; rjitrate salts of azoles; nonmeta! salts of nitramine derivatives of fizoles; salts of guanidin.es; nitro derivatives of guamdines; azoamides; nitrate salts of azoamides; and mixtures thereof.
14. A gas generating composition comprising: the reaction prod uct of a metal hydroxy! nitrate compound reacted with a nitro aromatic compound in an aqueous solution,
15. The gas generating composition of claim 12 further comprising: an oxidizer selected from nonmeta! and metal nitrate salts; chlorate salts; metal and nonmeta! perchiorate salts; metal and nonmetal oxides; basic metal nitrate salts, and mixtures thereof,
16. The gas generating composition of claim 12 further comprising; a fuel selected from derivatives of bis-( 1 (2)H-tetrazol-5-y!)-amine; tetrazoles, triazoles, and azoles; metal and nonmetal salts of tetrazoles, triazoles, and azoles; nitrate salts of tetrazoles, iriazole, and azoles: triazines and derivatives thereof; nitramine derivatives of tetrazoles, triazoles, and azoles: metal and nonmetal salts of nitramine derivatives of azoles; salts and derivatives of guarridines; azoamides; nitrate salts of azoamides; and mixtures thereof.
17. The gas generating composition of claim 16 wherein said salts and derivatives of guanidines are .selected from guanidine nitrate and nitroguanidine.
18. A gas generating composition comprising: a compound selected from dinitrobenzoic acid substituted basic copper nitrate, diniirosalicylic acid substituted basic copper nitrate, potassium salt of dmitrosalicy!ic acid substituted basic copper nitrate, isophthalic acid substituted basic copper nitrate, potassium salt of isophthalic acid substituted basic copper nitrate, hydroxy pyridine substituted basic copper nitrate, and mixtures thereof; an oxidizer selected from nonmetai and metal nitrate salts; chlorate salts; metal and nonmetai perchlorate salts; metal and nonmetai oxides; basic metal nitrate salts, and mixtures thereof; and a fuel selected ixom derivatives of bis-(1 (2)H-tetrazol-5-yl)-amine; tetrazoles, triazoles, and azoies; metal and nonmetai sails of tetrazoles, triazoles, and azoies; nitrate salts of tetrazoles, triazole, and azoies; nitramme derivatives of tetrazoles, triazoles, and azoies: metal and nonmetai salts of nitramine derivatives of azoies; salts and derivatives of guanidines; azoamides; nitrate salts of azoamides; and mixtures thereof.
19. The gas generating composition of claim 12 further comprising: a fuel selected from derivatives of bis-(i{2)H-tetrazol~5-yl)-araine; tetrazoles, triazoles, and azoies; triazines and derivatives thereof; metal and nonmetai salts of tetrazoles, triazoles, and azoies; nitrate salts of tetrazoles, triazole, and azoies; nitramine derivatives of tetrazoles, triazoles, and azoies; metal and nonmetai salts of nitramine derivatives of azoles; sails and derivatives of guanidines; azoaraides; nitrate salts of azoamides: and mixtures thereof.
20. The composition of claim ] 8 wherein said composition contains a fuel selected from guanidine nitrate and nitroguamdine, and basic copper nitrate.
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