Classifications

• • A—HUMAN NECESSITIES
  • A62—LIFE-SAVING; FIRE-FIGHTING
  • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
  • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
  • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B25/00—Compositions containing a nitrated organic compound
  • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
  • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
  • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

• the present invention relates to ingredients for use in pyrotechnic gas generant compositions, and more specifically to fuels containing a high oxygen balance.
• the gas generant compositions are useful as gas generant propellants for air bag occupant restraint systems for automobiles, gun propellants, inflation and expulsion devices, flotation devices, ignition materials, pyrotechnics, fire suppression devices and smokeless and smoke producing rocket propellants.
• U.S. Patent No. 3,405,144 discloses a l-azido-N,N,N'- trifluoroformamidine that is useful in a propellant composition which exhibits a high specific impulse. Specifically, the said material is disclosed to be useful in rocket fuel compositions.
• Gas generant compositions have also been developed to include the addition of modifiers to lower flame temperatures and increase gas production. Further ingredients may be added such as binders, ignition aids, slag formers, scavengers, and catalysts to improve various features of the underlying propellant. The modifiers and additional ingredients often times, however, improve one aspect of the propellant composition while also contributing to the production of undesirable by-products and may increase the corrosiveness thereof. This is particularly disadvantageous in an automobile air bag environment.
• One major gas generating composition having desirable characteristics contains strontium nitrate and 5-aminotetrazole (SrN/5 ATZ) as major constituents.
• This formulation is relatively non-toxic when compared with sodium azide systems, has good ballistic properties and retains the majority of solid combustion products as a slag or clinker either in the combustion or filtration areas of, for instance, an air bag system for an automobile. These formulations also exhibit acceptable flame temperatures of 2250 °K to 2750 °K depending upon the stoichiometry of the formulation and the oxygen to fuel ratio.
• the strontium nitrate and 5-aminotetrazole formulations are relatively non-hygroscopic and the ingredients do not exhibit crystalline phase changes over the operating temperature range of the air bag system.
• propellants based on mixtures of potassium perchlorate and oxygenated fuels such as guanidine nitrate and aminoguanidine nitrate.
• These propellants are also relatively non- hygroscopic, provide excellent gas output, high burning rates and only about two thirds of the solid combustion products of the above-noted strontium nitrate and 5-aminotetrazole based propellants.
• the solid combustion products do not form clinkers or slags which deposit in the combustion or filtration area, but instead form very fine particulates in the gas stream which results in a smokey and dirty exhaust.
• Smoke or dirty exhaust combustion products are not commercially desirable, particularly, in automobile air bag systems since the production of such product may cause undue anxiety on the part of drivers and passengers involved in an automobile accident in which air bags are deployed.
• a propellant material or gas generant that exhibits high gas output upon combustion, but does not produce unwanted by-products upon combustion.
• the object of the present invention is to improve upon and to overcome the deficiencies of the prior art and to provide a substantially non-hygroscopic, substantially non-toxic gas producing pyrotechnic gas generant composition that upon combustion produces a high gas output and a high burn rate with limited non-gaseous combustion products.
• Another object of the present invention is to provide a pyrotechnic gas generant composition including a high oxygen balance fuel, preferably, azodiformamidine dinitrate, that produces the desirable high gas output at a low combustion temperature and reduced non-gaseous combustion products.
• a high oxygen balance fuel preferably, azodiformamidine dinitrate
• Still another object of the present invention is to provide a pyrotechnic gas generant composition including a high oxygen balance fuel, preferably, azodiformamidine dinitrate, with the capability of self- deflagration similar to a solid monopropellant.
• a pyrotechnic gas generant composition including a high oxygen balance fuel, preferably, azodiformamidine dinitrate, with the capability of self- deflagration similar to a solid monopropellant.
• Yet another object of the present invention is to provide a pyrotechnic gas generant composition including a high oxygen balance fuel which will auto-ignite in an inflator at acceptable but low enough temperatures to ensure that the inflator only rupture but does not fragment in a bonfire test.
• Still another object of the present invention is to provide a gas generating composition capable of producing a substantially high gas output upon combustion for use as an automobile air bag propellant.
• the composition of the present invention may also be employed to inflate such items as an inflatable raft or passenger escape chute of an airplane, as well as for gun propellants, pyrotechnics, ignition mixtures, fire suppression devices and rocket propellants.
• the composition of the present invention also may include additives heretofore used with other gas generant compositions, such as oxidizers, gas conversion catalysts, ballistic modifiers, slag formers, ignition aids, energetic plasticizers and binders, non-energetic binders, and compounding aids.
• a pyrotechnic gas generant composition including a high oxygen compound or fuel, preferably, azodiformamidine dinitrate, which is the resulting reaction product of aminoguanidine nitrate and nitric acid prepared with or without the use of potassium permanganate.
• the reaction product is a yellow precipitate that can be ignited and used alone, with no oxidizers or other additives, for very rapid and substantially smokeless self- deflagration or combusted in combination with oxidizers and/or other additives.
• the gas generant composition provides both high gas output and low production of solid decomposition products upon combustion.
• the precipitate is relatively non-hygroscopic and has a high burn rate.
• cartridges used to contain the gas generating composition are not required to withstand the extremely high pressures associated with prior art gas generating compositions, such as ammonium nitrate based compositions, that exhibit the similar low solid combustion product production as the gas generating composition of the present invention, but have low burn, rates and are generally hygroscopic.
• the product is believed to be 1,1 '-azodiformamidine dinitrate.
• the pyrotechnic gas generant composition of the present invention is directed separately to both the use of the yellow reaction product of aminoguanidine nitrate and nitric acid and to 1 , 1 '-azodiformamidine dinitrate.
• the azodiformamidine dinitrate may also be formed as the reaction product of nitric acid and other aminoguanidine salts, such as aminoguanidine bicarbonate, aminoguanidine sulfate, or any combination thereof.
• aminoguanidine salt is aminoguanidine bicarbonate.
• the use of such materials provide a cost effective means of producing the azodiformamidine dinitrate of the present invention.
• the gas generant composition of the present invention is generally prepared by the methods heretofore employed for prior art compositions and generally, but not exclusively, involve the dry or wet blending and compaction of the comminuted ingredients selected for combination.
• the generant has applications in automobile air bag systems, inflatable rafts or passenger escape chutes, gun propellants, pyrotechnics, ignition mixtures, fire suppression devices and rocket propellants.
• propellant(s) and gas generant(s) are used interchangeably.
• the reactions shown are with anhydrous components. The use of non-anhydrous components, however, is also contemplated.
• Figure 1 is a conventional passenger-side inflator that may be used with the composition of the present invention.
• Figure 2 is a conventional driver-side inflator that may be used with the composition of the present invention.
• Figure 3 is an infrared absorption spectra of the reaction product of embodiment 1 of the present invention.
• Figure 4 is a differential scannning calorimetry of the reaction product of embodiment 1 of the present invention.
• Figure 5 is a differential scanning calorimetry of the reaction product of embodiment 2 of the present invention.
• Figure 6 is a differential scanning calorimetry of the reaction product of embodiment 3 of the present invention.
• Figure 7 is an infrared absorption spectra of the reaction product of embodiment 1 of the present invention.
• Figure 8 is an infrared absorption spectra of the reaction product of embodiment 2 of the present invention.
• Figure 9 is an infrared absorption spectra of the reaction product of embodiment 3 of the present invention.
• Figures 10(a)-(d) are infrared absorption spectra of the reaction product of embodiments 4, 1, 2 and 3, respectively, of the present invention.
• Figure 11 is a prior art infrared absorption spectra for azodicarbamidine dinitrate.
• Figure 12 is a graph showing a representative firing of the reaction product of the present invention. DETAD ED DESCRD7TION OF THE PREFERRED EMBODIMENTS
• the invention provides for a pyrotechnic gas generant, preferably comprising azodiformamidine dinitrate, which when combusted provides high gas output and minimal solid combustion products and which is useful for various purposes. It has been found that the reaction of the high oxygen balance fuel of the present invention with an oxidizer produces a high gas output volume with very little solid combustion products.
• the fuel preferably azodiformamidine dinitrate, also exhibits a high burn rate and is a self-deflagrating monopropellant.
• the gas generant composition of the present invention can be a single ingredient auto-ignition pill (AIP); a solid monopropellant; a high oxygen balance fuel in all pyro systems; a burning rate enhancing additive; and an ingredient in conventional and oxygenated hybrid inflation systems.
• AIP auto-ignition pill
• the gas generant of the present invention is particularly useful as an automobile air bag propellant, but also has applications as a gun propellant, flotation device gas generant, propellant, pyrotechnic, gas generator, ignition mixture, fire suppression device and rocket propellant. Additional objects and advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description wherein the preferred embodiments of the invention are shown and described simply by way of illustration of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of other and different embodiments and its several details are capable of modifications of various obvious respects, all without departing from the invention. Accordingly, the figures and description are to be regarded as illustrative in nature and not as restrictive.
• the gas generant composition of the present invention includes a high oxygen balance formamidine-type fuel prepared from the reaction of nitric acid and aminoguanidine nitrate.
• a high oxygen balance formamidine-type fuel prepared from the reaction of nitric acid and aminoguanidine nitrate.
• the inventors believe the fuel to be azodiformamidine dinitrate (also called azodicarbamidine dinitrate, azobicarbamidine dinitrate, and azobisformamidine dinitrate) .shown structurally as follows:
• This invention is not limited, however, to only azodiformamidine dinitrate, both crystallized and recrystalhzed, but instead is also directed to the product from the reaction of nitric acid and aminoguanidine nitrate as provided in detail below.
• the gas generant composition of the present invention may also be formed from the reaction of nitric acid and other aminoguanidine salts, such as aminoguanidine bicarbonate (AGB) or aminoguanidine sulfate (AGS).
• the aminoguanidine salt is AGB.
• the product from the reaction of these salts with nitric acid similarly produces a solid, bright yellow colored material believed to be azodiformamidine dinitrate as noted above with respect to the reaction of nitric acid and aminoguanidine nitrate.
• the prior synthesis involved the addition of a solution of a metallic oxidizing compound (potassium permanganate) to form a yellow reaction product and did not add heat from an external source during the process.
• a metallic oxidizing compound potassium permanganate
• the method of the present invention is preferred because by adding heat, the reaction occurs rapidly without requiring the addition of a metal oxidizing compound.
• the high oxygen fuel gas generant of the present invention can be prepared free of foreign solid minute particles or without the potential for formation of metallic oxide particles.
• gas generants using the high oxygen balance fuel of the present invention can be prepared without metal-containing contaminants.
• the reaction to form azodiformamidine dinitrate will also occur without external heat and with or without the use of potassium permanganate at ambient temperature if nitric acid and aminoguanidine mtrate are allowed to digest over a longer period of time.
• additional salts namely, aminoguanidine bicarbonate (AGB) and aminoguanidine sulfate (AGS).
• hydrazodicarbonamidine diazoguanidine, formamidine, bisformamidine, and azobisformamidine derivative fuels such as guanyl azide nitrate, diazoguanidine nitrate, azobisnitroformamidine, and 1,1 '-azodiformamidine dipicrate are also useful gas generator ingredients in accordance with the present invention.
• other derivatives and fuels containing a formamidine, guanyl azide, diazoguanidine, or hydrazodicarbonamidine group with an oxidizing group e.g.
• Prior art propellants such as those containing ammonium nitrate, produce very little solid combustion products, but have a number of other properties that make them less desirable.
• Ammonium nitrate for instance, is hygroscopic.
• gas generant/propellant compositions its use results in a low burn rate and a high pressure exponent at operating pressures of 1000-2000 psi. Consequently, a propellant composition including ammonium nitrate as the principal oxidizer must be burned at very high pressures, e.g. 4000-6000 psi, and sealed to prevent moisture from contacting the composition.
• ammonium nitrate typically requires the use of phase stabilizers, such as potassium compounds, which generate solid combustion products.
• the high oxygen balance fuel of the present invention overcomes a number of the above-noted, less than desirable characteristics. Specifically, a gas generant/propellant composition including the high oxygen balance fuel of the present invention exhibits a high gas output with no or little resulting solid combustion product or ash, while also being relatively non-hygroscopic, having a high burn rate and providing a more desirable pressure exponent. As a result, the composition of the present invention does not have to be held in such a high pressure and moisture sealed container, since the operating pressures required for achieving burning rates are much lower than for the above-noted ammonium nitrate gas generant propellant compositions.
• the gas generant composition of the present invention can function alone as a self-deflagrating monopropellant, as noted above, or include an oxidizer.
• Other materials may be added to the composition for processing, aiding ignition, enhancing ballistics, improving thermal aging and stability, improving hazardous properties, reducing particulates, binding, and scavenging undesirable gaseous combustion products.
• a single oxidizer or multiple oxidizers may be combined with the high oxygen balance fuel of the present invention to supply additional oxygen for achieving the desired oxygen to fuel balance (O/F) during combustion. Since the high oxygen balance fuel of the present invention includes a larger amount of oxygen than prior gas generating compositions, a smaller amount of oxidizer for providing a desirable oxygen to fuel (O/F) balance is necessary.
• Suitable metallic and non-metallic oxidizers are known in the art and generally comprise nitrites, nitrates, chlorites, chlorates, perchlorates, oxides, hydroxides, peroxides, persulfates, chromates and perchromates of non-metals, alkali metals, alkaline earth metals, transition metals and transition metal complexes and mixtures thereof.
• Preferred oxidizers include ammonium perchlorate, potassium perchlorate, strontium nitrate., potassium nitrate, sodium nitrate, barium nitrate, potassium chlorate, and mixtures thereof.
• Preferred oxidizers are non-hygroscopic in order to preserve the advantageous characteristic of the high oxygen balance fuel of the present invention.
• the preferred oxidizers are generally employed in a concentration of about 0% to 98% by weight of the total gas generant composition and preferably in a concentration of 5 to 50% by weight of the total gas generant composition.
• Scavengers may be desirable to control the production of corrosive combustion products. For example, if a non-metal oxidizer is used, such as ammonium perchlorate, hydrogen chloride (HC1) can be produced as a resulting reaction product, which is clearly undesirable. To prevent the production of HC1, a scavenger such as sodium nitrate can be used to form sodium chloride (NaCl) instead. Other corrosive/toxic gas scavengers may also be employed.
• the combustion of the high oxygen balance fuel of the present invention may also be controlled by the addition of ballistic modifiers and include burning rate catalysts which influence the temperature sensitivity, pressure exponent and rate at which the propellant burns.
• ballistic modifiers were primarily developed for solid rocket propellants, but have also been found useful in gas generants for inflatable devices.
• Examples of ballistic modifiers useful with the composition of the present invention include oxides and halides of Group 4 to 12 of the Periodic Table of Elements (as developed by IUPAC and published by the CRC Press, 1989); sulfur and metal sulfides; transition metal salts containing copper, chromium, cobalt, nickel and mixtures thereof; and alkali metal and alkaline earth metal borohydrides.
• Guanidine borohydrides and triaminoguanidine borohydrides have also been used as ballistic modifiers.
• Organometallic ballistic modifiers include, but are not limited to, metal chelates, oxalates, metallocenes, ferrocenes and metal acetyl acetonates.
• Other ballistic modifiers include salts of dicyanamide, nitroguanidine, guanidine chromate, guanidine dichromate, guanidine trichromate, and guanidine perchromate.
• the ballistic modifiers are generally employed in concentrations varying from about 0.1 to 25 % by weight of the total gas generant composition.
• slag former may not, however, be necessary in the present invention in view of the limited amount of solid combustion product produced.
• Suitable slag formers include lime, borosilicates, vycor glasses, bentonite clay, silica, alumina, silicates, aluminates, transition metal oxides, alkaline earth compounds, lanthanide compounds, and mixtures thereof.
• Ignition aids include finely divided elemental sulfur, boron, boron- potassium nitrate (BKN0 3 ), carbon, magnesium, aluminum, and Group 4 transition metals, transition metal oxides, hydrides and sulfides, the hydrazine salt of 3-nitro-l,2,4-triazole-5-one and mixtures thereof.
• the ignition aids are normally employed in concentrations of 0.1 to 15% by weight of the total gas generant composition. It may be desirable to add compounding agents to facilitate compounding and obtain homogeneous mixtures.
• Suitable binders and processing or compounding aids include molybdenum disulfide, graphite, boron nitride, alkali metal, alkaline earth and transition metal stearates, various solvents, such as water, methanol, ethanol, ethyl ether, acetone, isopropanol, methylene chloride, etc, polyethylene glycols, polyacetals, polyvinyl acetates, polyvinyl alcohols, polycarbonates such as Q-PAC, cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose nitrate (CN), fluoropolymers commercially available under the tradename TEFLON, and silicones.
• the compounding aids are typically, but not universally, employed in concentrations of about 0.1 to 15% by weight of the total gas generant composition.
• the high balance fuel of the present invention may also be combined with other fuels and/or energetic nitro and/or nitrato plasticizers and/or energetic and non-energetic binders to provide a gas generant/propellant composition.
• Suitable fuels for such combination with the fuel of the present invention include but are not limited to the families of azido, hydrazine, guanidine, tetrazole, triazole, triazine, polyamine, nitramine (linear and cyclic), and derivatives of these families of fuels, as well as mixtures thereof.
• Suitable energetic plasticizers include but are not limited to butanetriol trinitrate (BTTN), nitroglycerine (NG), triethyleneglycol dinitrate (TEGDN), trimethylolethane trinitrate (TMETN) and mixtures thereof.
• BTTN butanetriol trinitrate
• NG nitroglycerine
• TMGDN triethyleneglycol dinitrate
• TMETN trimethylolethane trinitrate
• GAP glycidyl azide polymer
• the manner and order in which the components of the gas generant composition of the present invention are combined and compounded are not critical so long as an intimate, uniform mixture with good structural integrity is obtained and the compounding is carried out under conditions which are not unduly hazardous, and, which do not cause decomposition of the components employed.
• the materials may be wet blended in aqueous or nonaqueous liquids, or dry blended, with or without binders or processing aids, in a ball mill or "RED DEVIL” type paint shaker and then extruded, pelletized by compression molding, or formed into a castable or compression molded monolithic grain.
• the materials may also be ground separately or together with or without binders and/or other additives in a fluid energy mill, "SWECO" vibroenergy mill, or bantam micro-pulverizer and then blended or further blended in a v-blender prior to compaction.
• the high oxygen balance fuel of the present invention can utilize conventional gas generator mechanisms of the prior art. These are 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 a gas generant composition.
• Hydrazodicarbonamidine, diazoguanidine, formamidine, bisformamidine, and azobisformamidine type fuels of the present invention can be used in such devices. Specifically, upon initiation of combustion by the firing of a squib, the sealing mechanism ruptures. This allows gas to flow out of the combustion chamber through several orifices. Of course, other gas generator mechanisms may equally be employed for use with the gas generant composition of the present invention.
• Figure 1 depicts a conventional passenger-side hybrid inflator for an automobile in which the high oxygen balance fuel of the present invention may be used.
• the initiator 1 ignites in response to a sensor (not shown) that senses rapid deceleration indicative of a collision.
• the initiator gives off hot gases that ignite the ignition charge 2 which causes the main generant charge 8 to combust,thereby heating and further pressurizing the inflation gas mixture 3.
• the seal disk 6 ruptures, permitting the gas mixture to exit the manifold 4 through the outlet portions 5 and inflate an air bag.
• the generant container 9 holds the main generant charge 8. All the charges in the inflation gas mixture are enclosed in the pressure tank 7.
• FIG. 2 illustrates an all pyrotechnic gas generator in which the instant invention may be employed. Since no part of the inflator is reserved for storage capacity, the device is smaller than its counterpart hybrid inflator.
• an initiator 11 that will combust in response to a signal from a sensor (not shown), that generates a signal as a result of a change in conditions, e.g. , an excessive increase in temperature or a sudden deceleration of a vehicle (indicative of a crash), in which the inflator is installed.
• the initiator 11 gives off hot gases that ignite the main generant charge 16, which combusts, generating an inflation gas mixture.
• the mixture exits the manifold 14 through the exit ports 15.
• an auto- ignition propellant (AIP) 13 having a suitably low T ig may be needed to ignite the ignition charge 12, which then ignites the propellant 16. Because of the high burning rates exhibited by the high oxygen balance fuel of the present invention at moderate to low operating pressures, the invention may also be utilized in the physical form of a monolithic grain.
• the high oxygen balance fuel of the present invention desirably provides the capability of self-deflagration similar to a solid monopropellant.
• the high oxygen balance fuel of the present invention permits the use of much lower concentrations of oxidizer components and results in a much lower concentration of solid combustion products and greater gas output, which is particularly advantageous for volume limited systems.
• the high oxygen balance fuel of the present invention has applications in both of the systems set forth above and illustrated generally in Figures 1 and 2.
• yellow colored solid reaction product of aminoguanidine nitrate and nitric acid as well as the yellow colored solid reaction product of nitric acid and other aminoguanidine salts, such as aminoguanidine bicarbonate and/or aminoguanidine sulfate, is assumed to be azodiformamidine dinitrate (azobisformamidine dinitrate), this invention is not limited only to this specific high oxygen balance fuel. The invention is also directed specifically to azodiformamidine dinitrate (azobisformamidine dinitrate). However, for simplicity, use of the term
• AZODN refers both to the reaction product and azodiformamidine dinitrate in anhydrous and hydrous versions, unless specifically indicated otherwise. Similar results would also be obtained by utilizing the azodiformamidine dinitrate formed from the reaction of nitric acid and aminoguanidine bicarbonate and/or aminoguanidine sulfate.
• HOB and CAPS high oxygen balance fuels
• Ethylenediamine dinitrate (EDDN), C 2 H 10 N 4 O 6 -25.8%
• AZODN of the present invention permits the use of a lower concentration of oxidizer to maintain a desired .90/1 to
• a gas generant that is totally or essentially free of solid combustion product
• an oxidizer such as either phase stabilized or non-phase stabilized ammonium nitrate
• the fuel of the present invention should be present as 40-60 wt% of the total gas generant composition.
• AZODN of the present invention in either the form of the reaction product of aminoguanidine nitrate and nitric acid or, specifically, azobisformamidine dinitrate, produces higher gas outputs and less solid combustion products.
• the compositions including EDDN, GN and 5ATZ required greater than 10% by weight more SrN than the composition including the high oxygen balance fuel (AZODN) of the present invention to provide the given 0.95/1 O/F ratio.
• AZODN high oxygen balance fuel
• KP potassium perchlorate
• compositions including EDDN and GN as fuel required significantly more potassium perchlorate and strontium nitrate than in the composition including AZODN.
• gas output for all three of the above compositions were similar to one another, the solid combustion products production for the composition utilizing AZODN was much lower. Consequently, the gas generant of the present invention including AZODN is preferred for pyrotechnic gas generator systems as illustrated in Figures 1 and 2.
• compositions including the high oxygen balance fuel of the present invention (AZODN) and oxidizers are provided below in Tables 4-7 for accomplishing the desired O/F balance of 0.90/1 to 1.1/1.
• AZODN and ammonium nitrate (AN) are provided in Table 4;
• AP ammonium perchlorate
• phase stabilized ammonium mtrate is preferred.
• Neat AZODN as a monopropellant for use in hybrid or ignition systems:
• Total Gas Output 100.0 Wt.% Total Gas Output (Moles): 4.167 Moles/100 Gms.
• AZODN with lithium carbonate coolant and ammonium perchlorate 14C 2 H g N 8 0 6 + 9NH 4 C10 4 + 5Li 2 C0 3 ⁇ > 9LiCl+ V 2 U 2 0+ 74H 2 0+ 27C0 2 + 6CO+ 60'/N 2 + VA0 2
• AZODN as used in Examples 1-12 provided below refers to the actual yellow precipitate of Example 1.
• the reaction product of nitric acid and other aminoguanidine salts such as aminoguanidine bicarbonate or aminoguanidine sulfate, would provide substantially the same results as the AZODN utilized in the following examples. This is substantiated by the additional tests conducted to demonstrate that the product resulting from the reaction of nitric acid and these additional salts has the same characteristics as the AZODN of Example 1.
• the high oxygen balance fuel of the present invention was prepared by the following method. First, 10 grams of aminoguanidine nitrate (AGN) was weighed into a 400 ml glass beaker. Then, water, preferably distilled, up to about 20-25 ml volume was added whereupon a slurry of AGN/water resulted. A dispersion was formed by slowly pouring 150 ml of reagent grade nitric acid (70%), while stirring, into the AGN/water slurry, which brought the total volume up to about 170-175 ml. A 10 degree temperature rise occurred as the acid was first added. As the acid was continually added, the temperature came back down. The dispersion was then heated to 55-65°C with moderate stirring on a hot plate.
• AGN aminoguanidine nitrate
• DSC Differential scanning calorimetry
• Neat AZODN powder produced by the method of Example 1, containing no oxidizers or other additives, self-deflagrated very rapidly when ignited at ambient temperature and pressure. Specifically, a small quantity (1/2 gram) of the high oxygen balance fuel of Example 1 was placed in a heap in the center of a watch glass and the flame of a burning splint was impinged on the sample. The sample immediately ignited and combusted very rapidly and cleanly similar to smokeless rifle powder.
• Example 5 A 0.269 gram quantity of AZODN of the present invention was placed in a pre-weighed aluminum pan and ignited with a burning splint. The pan was reweighed after igniting. Of the initial AZODN reaction product 0.005 grams of a tan residue remained, leaving a burn residual of 1.84% by weight. Additional tests were performed on small propellant batches containing the AZODN reaction product of the present invention for determining sensitivity, thermal aging, weight loss, and ballistics properties. The density of the product and propellants made from the product was determined from the weight and pellet dimension measurements to be 1.66 g/cc or greater.
• a propellant (Batch #11899) containing 10.60% sodium nitrate (SN) as an oxidizer and scavenger, 14.59% ammonium perchlorate (AP), and
• AZODN of the present invention was formulated at an O/F ratio of 1.0 to provide, when combusted, 7% solid combustion products and 3.7 moles of substantially non-toxic gas per 100 grams of composition product. This formulation gave burning rates of 0.32 and 0.46 ips, respectively, at 500 and 750 psi. These rates yielded a pressure exponent of 0.90.
• Another propellant (Batch #11900) containing 22.05% sodium nitrate (SN) oxidizer and 71.92% AZODN of the present invention was formulated to provide, when combusted, an 8% solid combustion products level and 3.4 moles of substantially non-toxic gas per 100 grams of composition.
• Example 9 Another propellant (Batch #11901) containing 7.74% lithium carbonate (LC) scavenger and coolant, 22.01%) AP oxidizer, and 70.25% AZODN of the present invention provided a burning rate of 0.34 ips at 500 psi but suffered severe weight loss of 5.9% after 24 hours at 107°C.
• the DSC for this formulation provided an onset temperature of 146°C and an exotherm peak at 179°C.
• Example 10 Example 10
• a propellant (Batch #11903) containing weight percents of 12.35% potassium nitrate (KN) acting as a scavenger/oxidizer, 14.3% ammonium perchlorate (AP), and 7335% AZODN of the present invention was formulated at an O/F ratio of 1.0 to provide on combustion, a theoretical solid combustion products level of 9% and 3.6 moles of substantially nontoxic gas per 100 grams of composition. When pressed into 1/4 x 5/8 inch pellets and tested for ballistic properties, the formulation gave a burning rate of 0.40 and 0.52 ips at 500 and 750 psi, respectively, with a pressure exponent of 0.56.
• KN potassium nitrate
• AP ammonium perchlorate
• 7335% AZODN of the present invention was formulated at an O/F ratio of 1.0 to provide on combustion, a theoretical solid combustion products level of 9% and 3.6 moles of substantially nontoxic gas per 100 grams of composition. When pressed into 1/4 x 5/8 inch pellets and tested for
• Weight loss during aging is presented in Table 10 for the various AZODN formulations provided above.
• Reformulation of the above propellant batches at an O/F ratio of 0.90 and 0.95 resulted in solid combustion products levels in the range of 6 to 7 1 / 2%.
• Substitution of SN for a KN scavenger and oxidizer in AP/AZODN systems resulted in solid combustion products levels of 6 and 4! 2 % at O/F ratios of 0.95 and 0.90, respectively.
• DSC Differential scanning calorimetry
• the high oxygen balance fuel of the present invention was prepared by the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine bicarbonate was combined with nitric acid to provide an embodiment 2 of the high oxygen balance fuel of the present invention.
• the high oxygen balance fuel of the present invention was prepared by the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine sulfate was combined with nitric acid to provide an embodiment 3 of the high oxygen balance fuel of the present invention.
• the high oxygen balance fuel of the present invention was prepared by the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine sulfate was combined with nitric acid. Further, the acid utilized in the method of Example 1 was used as the nitric acid component to provide an embodiment 4 of the present invention. Consequently, the nitric acid can be recycled ⁇ after the fuel of the present invention is recovered to improve the yield of the final product.
• the nitric acid used in one reaction can be used in a subsequent reaction no matter which aminoguanidine salt is used in the initial reaction or the subsequent reaction.
• Figure 4 provides an additional DSC plot of the AZODN of Example 1.
• the exothermic onset occurred at approximately 160°C with major decomposition at 185.1°C.
• Figure 5 shows a DSC plot of the fuel produced by Example 13 (Embodiment 2) with an exothermic onset occurring at 157.69°C and major decomposition at 184.98°C. Consequently, the fuel of Example 13 utilizing aminoguanidine bicarbonate is the substantially the same as the fuel of Example 1 and, thus, is azodiformamidine dinitrate. Use of aminoguanidine bicarbonate at the aminoguanidine salt is preferred in the present invention.
• Figure 6 shows a DSC plot of the fuel produced by Example 14 (Embodiment 3) with an exothermic onset occurring at 150.39°C and major decomposition at 182.44°C. Consequently, the fuel of Example 14 utilizing aminoguanidine sulfate is also the substantially the same as the fuel of Example 1 and, thus, is azodiformamidine dinitrate.
• Figures 7, 8 and 9 are IR spectras of the fuel of Examples 1, 13 and 14, respectively.
• Figures 10(a)-(d) are also IR spectra of the fuel of Examples 15, 1, 13 and 14, respectively.
• the high oxygen balance fuel of the present invention utilizing aminoguanidine salt, including aminoguanidine nitrate, aminoguanidine bicarbonate, and aminoguanidine sulfate, produces azodiformamidine dinitrate.
• Tables 11-14 are provided to show the use of representative AZODN made from aminoguanidine .
• Table 12 is an evaluation of the use of binders in AZODN propellant compositions and particularly comparing the use of QPAC-40 binder (polycarbonate) made by PAC Polymers, Inc. and CAB (cellulose-acetate butyrate) made by Eastman Chemical, Inc. This table generally shows that an increase in binder content increases the initial crush strength of the AZODN propellant composition.
• QPAC-40 binder polycarbonate
• CAB cellulose-acetate butyrate
• Tables 13 and 14 demonstrate the effect of annealing time and fine particle size on the crush strength and burning rate of various AZODN propellant compositions with and without a QPAC-40 binder.
• Table 15 shows the amount of insoluble and soluble decomposition product produced during an unfiltered inflator test of the gas generator propellant composition of the present invention made from the reaction of nitric acid and aminoguanidine salt, such as aminoguanidine nitrate, aminoguanidine sulfate, or the preferred salt, aminoguanidine bicarbonate.
• the test involved a PD-67 full size heavy weight test hardware inflator firing unit without any filter collection system. The sample propellant was fired in a 60 liter tank and then rinsed to measure the amount of solid decomposition product in the tank. The pH of the resulting solid decomposition product was also obtained.
• the pH of the decomposition product is relatively neutral which is important to prevent harm to passengers of an automobile in which the propellant of the present invention is utilized during a collision in an air bag unit. Further, the amount of unfiltered insoluble and soluble decomposition product is relatively low.
• the high oxygen balance fuel of the present invention preferably, azodiformamidine dinitrate, exhibits attractive propellant attributes and should be useful in a large number of pyrotechnic gas generant environments.

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• 1999
  • 1999-05-17 EP EP99951356A patent/EP1093422A2/de not_active Withdrawn
  • 1999-05-17 JP JP2000556939A patent/JP2002519278A/ja not_active Withdrawn
  • 1999-05-17 WO PCT/US1999/007049 patent/WO2000000365A2/en active IP Right Grant
  • 1999-05-17 CA CA002333942A patent/CA2333942A1/en not_active Abandoned
  • 1999-05-17 KR KR1020007013924A patent/KR100656304B1/ko not_active IP Right Cessation

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