KR100656304B1 - Fatigue Technique Gas Generator Compositions Containing High Oxygen Balanced Fuels - Google Patents

Abstract

The pyrotechnic gas generator composition comprises a high oxygen balance compound or a fuel, preferably azodiformamidine dinitrate, which is a reaction product obtained by the reaction of aminoguanidine nitrate with nitric acid. Specifically, the high oxygen balance compound or fuel of the present invention is the reaction product of an aminoguanidine salt, ie, aminoguanidine nitrate, aminoguanidine bicarbonate or aminoguanidine sulfate with nitric acid. Preferably, the aminoguanidine salt is aminoguanidine bicarbonate. The reaction product is a yellow precipitate that can be used alone or can self detonate quickly in combination with oxidants or other additives. In each example, the gas generating composition has a high amount of gas generation and a low amount of combustion products in the solid phase. In addition, the precipitate is relatively non-moisture resistant and has a high combustion rate. Gas generator compositions are useful as automotive airbag passenger restraint systems, firearm propellants, inflation and explosion devices, flotation devices, pyrotechnics, flame arresters and gas generators for smokeless, low smoke and flexible rocket propellers.

Description

Pyrotechnic gas generant composition including high oxygen balance fuel}

TECHNICAL FIELD The present invention relates to components used in a fatigue technique gas generator composition, and more particularly, to a fuel containing high oxygen balance. The gas generant composition can be used in the air bag occupant restraint system of automobiles, propellants of firearms, inflation and explosion devices, flotation devices, pyrotechnics, pyrotechnics, fire suppression devices and smokeless and smoke generating rocket propellers. It is usefully used as a gas generating propellant in the back.

There is a high demand for a pyrotechnic gas generator composition that has an acceptable burn rate upon combustion and provides a small amount of solid particulate material that can produce large quantities of gases and smoke that are substantially nontoxic at relatively low flame temperatures. It is also important that the solid by-products produced upon combustion of the gas generant composition are minimal and that the gaseous combustion products are substantially non-toxic and non-corrosive. Various gas generant compositions have been used in the past to obtain the desired properties as described above.

U. S. Patent No. 3,405, 144 discloses 1-azido-N, N, N'-trifluoroformamidine useful in propellant compositions that exhibit high specific impulse. In particular, this material is disclosed to be useful in rocket fuel compositions.

In addition, gas generator compositions have also been developed that add a modifier to lower the flame temperature and increase the amount of gas produced. Additional components, such as binders, ignition aids, slag formers, scavengers, and catalysts, may be added to improve various properties of the propellants described below. However, the addition of a denaturant and additional additives, on the one hand, improves the propellant composition, while on the other hand produces undesirable by-products and consequently increases corrosiveness. This is a particular disadvantage in the airbag environment of automobiles.

One of the gas generator compositions having desirable properties includes strontium nitrate and 5-aminotetrazole (SrN / 5ATZ) as main components. Such formulations are relatively non-toxic compared to sodium azide systems, have good ballistic properties and are responsible for the majority of solid combustion products, for example, slag or clinkers that occur in the combustion or filtration areas of automotive airbag systems. Occupies. In addition, these formulations show acceptable flame temperatures of 2250 ^o K to 2750 ^o K, depending on stoichiometry and oxygen to fuel ratio. In addition, the strontium nitrate and 5-aminotetrazole formulations are relatively non-moisturizing and the components do not show crystalline changes over the operating temperature range of the airbag system.

However, these formulations are problematic in terms of gas generation, particularly in volume-limited systems such as driver side airbags. This is because high concentrations of strontium nitrate are required to maintain an intermediate oxygen to fuel (O / F) balance. As the design of the inflator is increasingly limited in volume, the propellant must still have the desirable properties of the strontium nitrate / 5-aminotetrazole system while providing more gas evolution.

Attempts have been made to obtain a propellant that exhibits desirable characteristics as described above and has a low gas generation. As a result, propellants based on mixtures of potassium perchlorate with oxidizing fuels such as guanidine nitrate and aminoguanidine nitrate have been developed. This propellant is also relatively non-hygroscopic and offers excellent gas generation and high burn rates, with only about two-thirds the amount of solid combustion products compared to the propellants based on strontium nitrate / 5-aminotetrazole described above. Unfortunately, solid combustion products do not form clinkers or slags deposited in the combustion or filtration zones, but instead form very fine particulate matter that produces misty contaminated exhaust gases in the gas stream.

It is not commercially desirable to produce such combustion products, especially in automotive airbag systems, because the formation of fumed, contaminated exhaust combustion products may create unnecessary anxiety for drivers and passengers in an automobile accident in which the airbag is deployed. As a result, there is a need for a propellant material or gas generator composition that has a high rate of gas generation upon combustion but does not produce unwanted byproducts.

It is an object of the present invention to overcome the drawbacks of the prior art to produce a pyrotechnic gas which produces a substantially non-hygroscopic and substantially non-toxic gas which limits the non-gaseous combustion products while exhibiting a high gas generation rate and a good combustion rate upon combustion. It is providing a composition.

It is another object of the present invention to provide a pyrotechnic gas generator composition comprising a high oxygen balance fuel, which has a high gas generation rate and a low amount of non-gas combustion products at low temperatures.

Another object of the present invention is a pyrotechnic gas generator composition comprising a high oxygen balance fuel, preferably azodiformamidine dinitrate, having a self-deflagration ability similar to that of a solid propellant. To provide.

Another object of the present invention is a fatigue comprising a high oxygen balance fuel, which expands automatically in the inflator at an acceptable temperature while the inflator bursts in the bonefire test but is low enough not to break into pieces. It is to provide a technique gas generator composition.

Another object of the present invention is to provide a gas generator composition which can be used as an airbag propellant of an automobile by providing a substantially high amount of gas generation upon combustion. However, it can also be used to inflate firearms, pyrotechnics, ignition mixtures, flame arresters and rocket propellers, as well as air-expanded rafts or chutes for passenger evacuation of airplanes. From a practical point of view, the compositions of the present invention are additives that have been used with other gas generating compositions so far, such as oxidizers, gas shift catalysts, ballistic modifiers, slag formers, ignition aids, strong plasticizers and binders, not strong. Non-plasticizers, non-strong binders, mixing aids, and the like.

The above object of the present invention is a pyrotechnic gas comprising a high oxygen content compound or fuel, preferably azodiformamidine, which is a reaction product of aminoguanidine nitrate and nitric acid, usually prepared with or without potassium permanganate Achieved by the generator composition. Specifically, the reaction product is a yellow precipitate that can be ignited and used alone without oxidizing agents or other additives to self-detonate very quickly and nearly lead-free or burn into a mixture with oxidizing agents and / or other additives. . In each example, the gas generating composition has a large amount of gas generation during combustion and a small amount of decomposition products in the solid phase. The precipitate is also relatively non-moisture resistant and exhibits high combustion rates. As a result, the cartridge used to contain the gas generator composition has a conventional ammonium nitrate-based gas generator which shows a small amount of solid combustion products similar to that of the gas generator composition of the present invention, but has a low combustion rate and usually has moisture resistance. It is not necessary to have very high pressure resistance as in the case of the composition. Based on the general physical properties of the reaction products of the present invention described above, it is believed that this product is 1,1'-azodiformamidine dinitrate. However, the pyrotechnic gas generator composition of the present invention relates to both a method using a yellow reaction product obtained by the reaction of aminoguanidine nitrate with nitric acid and to 1,1'-azodiformamidine dinitrate.

Azodiformamidine dinitrate can also be produced as a reaction product of nitric acid with other aminoguanidine salts, such as aminoguanidine bicarbonate, aminoguanidine sulfate or combinations thereof. Preferably, the aminoguanidine salt is aminoguanidine bicarbonate. The use of such materials provides a low cost means of generating the azodiformamidine dinitrates of the present invention.

The gas generant composition of the present invention is typically prepared according to the methods used in the preparation of conventional compositions and typically, but not always, comprises dry or wet blending and compacting the milled components selected for combustion. In view of the useful properties of the gas generator composition of the present invention, namely high gas generation rate, low solid combustion products and high combustion rate, etc., this gas generator is used for automobile airbag systems, air inflated rafts and passenger transport for passenger evacuation. Applied in applications such as devices, gun propellers, pyrotechnics, ignition mixtures, flame arresters and rocket propellers.

For the purposes of the present invention, the terms 'propellant' and 'gas generator' are used interchangeably. In addition, the reactions disclosed for the purposes of the present invention are reactions with anhydrous components. However, consideration should also be given to the use of non-anhydrous ingredients.

1 is a typical passenger seat inflator that may be used with the composition of the present invention.

2 is a conventional driver's seat inflator that may be used with the compositions of the present invention.

3 is an infrared absorption spectrum of the reaction product of Embodiment 1 of the present invention.

4 is a differential scanning calorimetry result of the reaction product of Embodiment 1 of the present invention.

5 is a differential scanning calorimetry result of the reaction product of Embodiment 2 of the present invention.

6 is a differential scanning calorimetry result of the reaction product of Embodiment 3 of the present invention.

7 is an infrared absorption spectrum of the reaction product of Embodiment 1 of the present invention.

8 is an infrared absorption spectrum of the reaction product of Embodiment 2 of the present invention.

9 is an infrared absorption spectrum of the reaction product of Embodiment 3 of the present invention.

10 (a)-(d) are infrared absorption spectra of the reaction products of embodiments 4, 1, 2 and 3, respectively, of the present invention.

11 is an infrared absorption spectrum of conventional azodicarbamidine dinitrate.

12 is a graph showing representative ignition characteristics of the reaction product of the present invention.

Detailed description of preferred embodiments

The present invention provides a pyrotechnic gas generator comprising azodiformamidine dinitrate, which preferably contains azodiformamidine dinitrate, which has a large amount of gas generated during combustion, a small amount of solid combustion products, and which can be usefully used for various purposes. It has been found that the reaction of the high oxygen balance fuel according to the invention with the oxidant produces a very small amount of solid phase combustion products with high gas emissions. In addition, this fuel, preferably azodiformamidine dinitrate, is a one-way propellant that exhibits high combustion rates and self-detonates. As a result, the gas-generating composition of the present invention comprises a single component auto-ignition pill (AIP); Solid propellant; High balance fuel used in all pyro systems; Additives for improving combustion rate; And components used in conventional oxidative hybrid expansion systems. The gas generators of the present invention are particularly useful for automotive airbag propellants, but are also used for firearm propellants, flotation gas generators, propellants, fatigue techniques, gas generators, ignition mixtures, flame suppressors and rocket propellers.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which is a simplified description of preferred embodiments of the invention, including the best mode of carrying out the invention. The invention may be other alternative embodiments, and its various details may be various obvious modifications without departing from the scope of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive of the invention.

More specifically, the gas generator composition of the present invention comprises a high oxygen balanced fuel prepared from the reaction of nitric acid with aminoguanidine nitrate. The inventors also refer to azodiformamidine dinitrate (azodicarbamidine dinitrate, azobicarbamidine dinitrate, and azobi forformamidine dinitrate, in which the fuel exhibits the following structure): I think.

However, the present invention is not limited to azodiformamidine nitrate, whether crystalline or recrystallized, but also relates to a product obtained from the reaction of nitric acid and aminoguanidine nitrate as provided below.

The gas generant composition of the present invention may be produced from the reaction of nitric acid with other aminoguanidine salts, namely aminoguanidine bicarbonate (AGB) or aminoguanidine sulfate (AGS). Preferably this aminoguanidine salt is AGB. The product from the reaction of the salts with nitric acid gives rise to a solid light yellow substance which is thought to be azodiformamidine dinitrate as described above for the reaction of nitric acid with aminoguanidine nitrate.

Regarding azodiformamidine dinitrate, reference is made to J. Chem. Thiele, Ann. 270, 39, 1892), which is described herein as azodicarbonamidinnitrat. This conventional synthesis has been done in connection with the study of powerful wool dyes / pigments.

In addition, conventional synthesis methods involve the addition of a solution of a metallic oxidant compound (potassium permanganate) to form a yellow reaction product, and no heat is applied from an external heat source during the reaction. As will be described later, the method of the present invention is preferred because the reaction occurs quickly without the need to add a metal oxidant by applying heat. By not using a metal oxidant compound during the preparation of the yellow reaction product, there is no generation of solid particulates from outside or the possibility of forming metallic oxide particles, thereby generating a gas comprising a high oxygen balance fuel according to the present invention. Agents can be prepared. Thus, gas generators using the high oxygen balance fuel of the present invention can be made free of metal-containing contaminants.

According to the present invention, if nitric acid and aminoguanidine nitrate are decomposed over an extended period of time, a reaction may occur that forms azodiformamidine nitrate with or without external heat and with or without potassium permanganate at ambient temperature. . This method is also applicable to the use of the other salts described above, namely aminoguanidine bicarbonate (AGB) and aminoguanidine sulfate (AGS).

Other High Oxygen Balance Fuel Hydrazodicarbonamidine, Diazoguanidine, Formamidine, Bisporamidine, and Guanyl Azide Nitrate, Diazoguanidine Nitrate, Azobisnitroformamidine and 1,1 Azobisformamidine derivative fuels, such as' -azodiformamidine diprecate, are also useful as gas generating components according to the present invention. Also hydrazodicarbonamidines having formamidine, guanyl azide, diazoguanidine, or oxidizing groups such as (NO ₂ ), (NO ₃ ), (ClO ₄ ), (ClO ₃ ) or mixtures thereof Groups, or mixtures of different hydrazodicarbonamidines, guanyl azides, diazoguanidines, formamidines, bisporamidines, and azobisporamimidine compounds with oxidant groups with suitable precautions Other derivatives and fuels are also useful in propellant compositions.

Conventional propellants, such as those containing ammonium nitrate, generate very small amounts of solid combustion products, but there are some other properties that make them undesirable. Ammonium nitrate, for example, exhibits moisture content. In addition, the use of ammonium nitrate in gas generator / propellant compositions results in low combustion rates and high pressure indices at operating pressures of 1000-2000 psi. In conclusion, propellant compositions comprising ammonium nitrate as the main oxidant should be combusted at high pressures such as 4000-6000 psi and should be sealed to prevent moisture from contacting the composition. In addition, ammonium nitrate must use phase stabilizers that generate solid combustion products, such as potassium compounds.

The high oxygen balance fuel of the present invention overcomes several of the aforementioned undesirable problems. In particular, the gas generator / propellant composition comprising the high balance fuel according to the present invention has a large amount of gas generation and a very small amount even if no solid combustion products are produced or produced, and relatively non-moisturizing and excellent combustion rate. Indicates a more preferable pressure index. As a result, the composition of the present invention does not need to be stored in a high pressure and moisture barrier container because the operating pressure required to achieve the burn rate is much lower than that of the ammonium nitrate gas generating propellant compositions described above.

The gas generator composition of the present invention may act as a self-deflatable one-way propellant or may include an oxidant as described above alone. Other materials can be added to the composition to facilitate processing, ignite easily, improve ballistic properties, improve heat aging and safety, improve hazardous properties, reduce particulate matter, bind and undesirable Gaseous combustion products can be removed.

One or several oxidants can be mixed with the high oxygen balance fuel according to the present invention to provide additional oxygen to achieve the desired oxygen to fuel balance (O / F) during combustion. The high oxygen balance fuel according to the present invention has a higher oxygen content than conventional gas generator compositions, so the amount of oxidant must be small in order to provide the desired oxygen to fuel (O / F) balance. Suitable metallic and nonmetallic oxidants are known in the field of the present invention, which typically includes nitrites, nitrates, chlorites, chlorates, chlorates, perchlorates of base metals, alkali metals, alkaline earth metals, transition metals and transition metal complexes and mixtures thereof. And oxides, hydroxides, peroxides, persulfates, chromates and dichromates. Preferred oxidants include ammonium perchlorate, tripotassium perchlorate, strontium nitrate, potassium nitrate, sodium nitrate, barium nitrate, potassium chlorate and mixtures thereof.

In order to maintain the useful properties of the high oxygen balance fuel according to the present invention, the preferred oxidant should be non-moisture. Preferred oxidants are usually used at a concentration of about 0 to 98% by weight, preferably 5 to 50% by weight, based on the gas generator composition.

Scavengers may be preferably used to control the production of corrosive combustion products. For example, when using nonmetallic oxidants such as ammonium perchlorate, hydrochloric acid can be obtained as a reaction product, which is clearly undesirable. To prevent the production of hydrochloric acid, a scavenger such as sodium nitrate may be used to form sodium chloride instead of hydrochloric acid. Other corrosive / toxic gas scavengers may be used.

Combustion of the high oxygen balance fuel according to the present invention can be controlled by the addition of ballistic modifiers and can include combustion rate catalysts that affect temperature sensitivity, pressure index and propellant burn rate. Such ballistic modifiers have been developed primarily for solid rocket propellers, but have also been found to be useful as gas generators for expansion devices. Examples of ballistic modifiers that may be usefully used in the compositions of the present invention include oxides and halogen compounds of Group 4 to Group 12 elements of the Periodic Table of the Elements (developed by IUPAC, published by CRC Press (1989)); Sulfur and metal sulfides; Transition metal salts including copper, chromium, cobalt, nickel and mixtures thereof; And borohydrides of alkali metals and alkaline earth metals. Guanidine borohydride and triaminoguanidine borohydride can also be used as ballistic modifiers. Examples of organometallic ballistic modifiers include, but are not limited to, metal chelates, oxalates, metallocenes, ferrocenes, metal acetyl acetonates. Examples of other ballistic modifiers include dicyanamide, nitroguanidine, guanidine chromate, guanidine dichromate, guanidine trichromate, and guanidine perchromate. Ballistic modifiers are typically used at a concentration of about 0.1 to 25% by weight, based on the total amount of the gas generator composition. Due to the self deflagration and high burn rate characteristics of the high oxygen balance fuel according to the invention, the fuel can also be used as a ballistic modifier of other gas generator compositions at low concentrations of 0.1-25%.

The formation of filterable slag is improved by adding slag formers. However, considering that the amount of solid phase fuel product produced is limited, such slag formers are not necessary. If desired, suitable slag forming agents can be used, examples include lime, borosilicate, bicore glass, bentonite clay, silica, alumina, silicate, aluminate, transition metal oxides, alkaline earth metal compounds, lanthanum compounds, and Mixtures thereof.

Other additives known to facilitate handling of gas generant compositions and thereby promote combustion temperatures are ignition aids. Ignition aids include finely ground elemental sulfur, boron, boron potassium nitrate (BKNO ₃ ), carbon, magnesium, aluminum, and Group 4 transition metals, transition metal oxides, hydroxides and sulfides, 3-nitro-1,2,4 Hydrazine salts of -triazol-5-one and mixtures thereof. Ignition aids are usually used in concentrations of from 0.1 to 15% by weight, based on the total amount of the gas generator composition.

It is preferable to add a mixing aid to facilitate mixing to obtain a homogeneous mixture. Suitable binders and processing or mixing aids include molybdenum disulfide, graphite, boronated boron, alkali metals, alkaline earth metals and transition metal stearates, various solvents such as water, methanol, ethyl ether, acetone, isopropanol, methylene chloride, polyethylene glycol , Polyacetal, polyvinyl acetate, polyvinyl alcohol, polycarbonates such as Q-PAC, cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose nitrate (CN), TEFLON Commercially available fluoropolymers, and silicones. The mixing aid is usually used at a concentration of about 0.1 to 15% by weight, based on the total amount of the gas generating composition.

In addition to the additives described above, the high oxygen balance fuel according to the present invention may be mixed with other fuels and / or strong nitro and / or nitroto plasticizers and / or strong plasticizers and inefficient binders to provide a gas generator / propellant composition. have. Suitable fuels that can be mixed with the fuels according to the invention include azido, hydrazine, guanidine, tetrazole, triazole, triazine, polyamine, nitramine (linear and cyclic), and derivatives thereof. Mixtures may be exemplified, but are not limited thereto. Suitable examples of strong plasticizers include butanetriol trinitrate (BTTN), nitroglycerin (NG), triethyleneglycol dinitrate (TEGDN), trimethylolethane trinitrate (trimethylolethane trinitrate) TMETN) and mixtures thereof, but is not limited to these. An example of a strong binder is glycidyl azide polymer (GAP).

A method of mixing and blending the components of the gas generator composition according to the present invention, provided that a homogeneous mixture is obtained without structural damage, and mixing is carried out under conditions that are not unnecessarily dangerous and do not cause decomposition of the component elements used; and The order is not that important. For example, the materials may be wet mixed in an aqueous or non-aqueous liquid, or dry mixed in a ball mill or paint shake in the form of a "RED DEVIL" in the presence or absence of a binder or processing aid, followed by compression molding to extrude and Molded, castable or compression molded into single crystal granules. The materials are ground either in a fluid energy mill, a "SWECO" vibroerengy mill, or a bantam micro-pulverizer, or with a binder and / or other additives, respectively. They may be ground together or without them, then mixed and extruded, or further mixed and extruded in a v-blender.

The various components described above used with the novel fuel according to the present invention with high oxygen balance can also be used in other gas generator compositions up to now. References relating to gas generating compositions for various additives are described in US Pat. No. 5,0357,57; 5,084,118; 5,139,588; 4,948,439; 4,909,549; And 4,370,181. As will be apparent to those skilled in the art and skilled in the art, additives having two or more functions in one composition may be mixed. Thus alkaline earth metal salts of tetrazole, bitetrazole and triazole not only act as gas generator components but also as slag formers. It is also known that, for example, strontium nitrate not only acts as an oxidant and slag former, but is also effective as a ballistic modifier, a ignition aid, a densifier and a processing aid.

The high oxygen balance furnace according to the present invention may utilize conventional gas generator mechanisms as in the prior art. Such a mechanism is mentioned in US Pat. No. 4,369,079, which is incorporated herein by reference. In general, conventional methods involve the use of hermetically sealed metallic cartridges containing gas generant compositions. Itrazodicarbonamidine, diazoguanidine, formamidine, bisporamidine, and azobisformamidine based fuels according to the present invention can be used in such devices. Specifically, the sealing mechanism ruptures when the firecracker is lit and combusted. This causes gas to flow out of the combustion chamber through several holes. Of course, also in using the gas generating composition which concerns on this invention, another gas generating mechanism can be employ | adopted similarly.

Referring to the vehicle airbag environment, FIG. 1 illustrates a typical passenger passenger side hybrid inflator capable of using a high oxygen balance fuel in accordance with the present invention. In practice, the initiator 1 ignites in response to a sensor (not shown) that detects a collision, which is a rapid deceleration indication. The initiator provides a hot gas to ignite the ignition charge 2, which burns the main generator chage 8 to heat and further pressurize the expansion gas mixture 3. When the pressure of the inflation gas mixture increases to a predetermined value, the seal disc 6 ruptures and the gas mixture passes through the manifold 4 through the outlet 5 to inflate the airbag. The generator container 9 holds the main generator differential 8. All charges in the inflation gas mixture are contained in the pressure tank 7.

2 shows all fatigue technique gas generators that can be used in the present invention. The device is smaller than the corresponding hybrid inflator because neither part of the inflator has a storage capacity. In this figure, an initiator combusts in response to a signal from a sensor (not shown) resulting, for example, from changes in conditions such as excessive temperature rise or sudden deceleration (meaning a collision) of a vehicle equipped with an inflator. There is (11). The initiator 11 emits a hot gas to ignite the main generator cage 16, and the main generator charge is burned while generating an expansion gas mixture. This mixture exits manifold 14 through discharge port 15. If the gas generating propellant is to be ignited at a temperature lower than the auto ignition temperature (T _ig ) and the temperature at which the materials composing the hardware begin to weaken, suitably ignite the ignition charge 12 and then ignite the propellant 16. It will be required automatic igniting the propellant (AIP, 13) having a lower T _ig.

Since the high oxygen balance fuel according to the invention shows a high burning rate at medium to low operating pressures, the invention can also be used in the physical form of monocrystalline granules.

The use of a high oxygen balance fuel according to the invention preferably provides a self deflagration capability similar to that of the solid phase one-way propellant. In addition, the high oxygen dissipation fuel according to the invention makes it possible to use even lower concentrations of the oxidant component and generates much lower concentrations of solid phase combustion products and higher amounts of gas, which is particularly true in volume-limited systems. It is advantageous. As a result, the high oxygen balance fuel according to the present invention is applied to both the systems described above as well as to the systems generally shown in FIGS. 1 and 2.

Yellow solid reaction product obtained by reaction of aminoguanidine nitrate with nitric acid and yellow solid reaction product by reaction of nitric acid with other aminoguanidine salts such as aminoguanidine bicarbonate and / or aminoguanidine sulfate It is assumed to be din dinitrate (azobisporamidine dinitrate), but the present invention is not limited to this specific high oxygen balance fuel. The present invention also specifically relates to azodiformamidine dinitrate (azobisformamidine dinitrate). However, for convenience, the term AZODN will be used below for both the reaction product and the azodiformamidine dinitrate in the anhydrous and aqueous phase unless otherwise indicated.

Comparing the high oxygen balance fuel, AZODN, according to the present invention with other fuels with high oxygen balance (HOB and CAPS), as shown in Table 1, the AZODN is more effective for carbon dioxide and water than any other fuel with high oxygen balance. It can be seen that it has a high oxygen balance.

The oxygen balance of the AZODN according to the present invention is superior to other fuels with high oxygen balance, such as guanidine nitrate, which can result in lower oxidant use concentrations and thus the desired oxygen-to-fuel (O / F) The balance can be maintained between 0.90 / 1 and 1.1 / 1. However, if a gas generator is desired that does not include all or part of the solid phase combustion product, an oxidant such as ammonium nitrate, which is phase stabilized or not phase stabilized, may be used with the high oxygen balance fuel according to the present invention. In this case, the fuel of the present invention is present at 40-60% by weight relative to the total amount of gas generator composition. The use of the AZODN of the present invention in the form of the reaction product of aminoguanidine nitrate and nitric acid or specifically azobisporamimidine dinitrate results in high gas generation and low solid phase combustion products.

As shown in Table 2 below, conventional fuels such as 5-aminotetrazole (5ATZ: previously discussed in the background of the present invention), guanidine nitrate (GN), and ethylenediaminedinite (EDDN) In this case, a higher amount of strontium nitrate (SrN) is required to achieve an oxygen to fuel (O / F) balance of .95 / 1. Moreover, the gas generator composition comprising such a fuel has a smaller amount of gas generation and more solid phase combustion products than the gas generator composition comprising the AZODN according to the present invention.

As explained from the results listed in Table 2, a composition comprising EDDN, GN and 5ATZ was found to have a higher O / F ratio of 0.95 / 1 than a composition comprising a high oxygen balance fuel (AZODN) according to the present invention. It requires much more than SrN by weight. Although 5ATZ exhibits a similar flame temperature as in the present invention, the amount of gas generated is significantly lower than the composition comprising AZODN and the content of solid phase combustion products is more than twice that of the composition comprising 5AZT.

If ballistic composition is expected, some of the strontium nitrate can be replaced with potassium perchlorate. Under these conditions, the formation of solid phase combustion products is further reduced, as shown in Table 3.

However, compositions comprising EDDN and GN as fuel require significantly higher amounts of potassium perchlorate and strontium nitrate compared to compositions comprising AZODN. Although the gas generation amounts of the three types of compositions are similar to each other, the amount of solid phase combustion products generated is much lower in the compositions using AZODN. In conclusion, gas generators of the present invention comprising AZODN are preferred for fatigue technique gas generation systems such as those disclosed in FIGS. 1 and 2.

A composition comprising a high oxygen balance fuel (AZODN) and an oxidant according to the present invention is shown in Tables 4-7 below, which shows preferred O / F balances of 0.90 / 1 to 1.1 / 1. Specifically, compositions comprising AZODN and ammonium nitrate (AN) are shown in Table 4; Compositions comprising AZODN, ammonium perchlorate (AP) and strontium nitrate (SrN) are shown in Table 5; Compositions comprising AZODN, ammonium perchlorate (AP) and sodium nitrate (SN) are shown in Table 6; Compositions comprising AZODN, ammonium perchlorate (AP) and potassium nitrate (KN) are shown in Table 7. It should be remembered that the compositions in Table 4 are moist, but there is still very little production of solid phase combustion products. It is also preferred to use phase stabilized ammonium nitrate.

       AZDON, Ammonium Perchlorate and Potassium Nitrate Compositions AZDON (% by weight)   AP (% by weight)   SN (% by weight)   O / F Balance    82.6    9.3    8.1    .9 / 1    77.8   11.9   10.3    .95 / 1    77.3   14.3   12.4   1.0 / 1    69.2   16.5   14.3   1.05 / 1    65.3   18.6   16.1   1.1 / 1

In order to better understand the function of the high oxygen balance fuel according to the invention an example of the theoretical reaction of AZODN according to the invention is shown below, where the structural formula of AZODN is as follows:

In addition, the molecular formula of AZODN is C ₂ H ₈ N ₈ O ₆ .

(1) Pure AZODN as one-way propellant used in hybrid or ignition systems:

Total gas generation 100.0% by weight

Total gas generation (moles) 4.167 moles / 100 g

Total Solid Phase Combustion Product Weight 0%

(2) AZODN and (usually or phase stabilized) ammonium nitrate:

Total gas generation 100.0% by weight (O / F = 1.00) 100% by weight (O / F = 0.95)

Total gas generation (moles) 4.04 moles / 100 g

Total Solid Phase Combustion Product Weight 0%

(3) AZODN and lithium nitrate and ammonium perchlorate:

Total gas generation 94.7% by weight (O / F = 1.00) 95.6% by weight (O / F = 0.95)

Total gas generation amount (mol) 3.69 mol / 100 g

5.3% by weight of total solid phase combustion products (O / F = 1.00) 4.4% by weight (O / F = 0.95)

(4) AZODN and ammonium nitrate and ammonium perchlorate:

Total gas generation 92.8% by weight (O / F = 1.00) 93.8% by weight (O / F = 0.95)

Total gas generation (mol) 3.50 mol / 100 g

7.2% by weight total solid phase combustion products (O / F = 1.00) 6.2% by weight (O / F = 0.95)

(5) AZODN and potassium nitrate and ammonium perchlorate:

Total gas generation 91.0 wt% (O / F = 1.00) 92.0 wt% (O / F = 0.95)

Total gas generation amount (mol) 3.42 mol / 100 g

Total solid phase combustion products 9.0 wt% (O / F = 1.00) 8.0 wt% (O / F = 0.95)

(6) AZODN and strontium nitrate and ammonium perchlorate:

Total gas generation 90.5% by weight (O / F = 1.00) 92.0% by weight (O / F = 0.95)

Total gas generation (mol) 3.405 mol / 100 g

9.5% by weight total solid phase combustion products (O / F = 1.00) 8.0% by weight (O / F = 0.95)

(7) AZODN and lithium carbonate coolant and ammonium perchlorate:

Total gas generation 91.79% by weight (O / F = 1.00) 92.00% by weight (O / F = 0.95)

Total gas generation (mol) 3.51 mol / 100 g 3.73 mol / 100 g

Total solid phase combustion products 8.20% by weight (O / F = 1.00) 8.00% by weight (O / F = 0.95)

(8) AZODN and scandium nitrate and ammonium perchlorate:

Total gas generation 94.0% by weight (O / F = 1.00)

Total gas generation (mol) 3.51 mol / 100 g (O / F = 1.00)

6.0 wt% of total solid phase combustion products (O / F = 1.00)

(9) AZODN and Sodium Nitrate:

Total gas generation 92.0 wt% (O / F = 1.00) 93.0 wt% (O / F = 0.95)

Total gas generation (mol) 3.38 mol / 100 g

Total solid phase combustion products 8.0% by weight (O / F = 1.00) 7.00% by weight (O / F = 0.95)

(10) AZODN and Strontium Nitrate:

Total gas generation 87.2 wt% (O / F = 1.00) 89.3 wt% (O / F = 0.95)

Total gas generation (mol) 3.20 mol / 100 g

Total solid phase combustion products 12.8 wt% (O / F = 1.00) 10.7 wt% (O / F = 0.95)

(11) AZODN and Potassium Perchlorate:

Total gas generation 88.03 wt% (O / F = 1.00) 89.90 wt% (O / F = 0.95)

Total gas generation (mol) 3.24 mol / 100 g 3.56 mol / 100 g

Total solid phase combustion products 11.97 wt% (O / F = 1.00) 10.10 wt% (O / F = 0.95)

(12) AZODN and aminoguanidine hexanitratocerate:

Total gas generation 87.54%

Total solid phase combustion products 12.46%

(13) AZODN and aminoguanidine hexanitratoscandate

Total gas generation 94.01%

5.99% of total solid phase combustion products

As provided by the theoretical reaction of AZODN, significant amounts of gas may be generated using the fuel of the present invention. In most cases, the amount of gas generated exceeds 90% by weight. The gas generating agent of the present invention using AZODN has a smaller amount of formation than a conventional gas generating composition even though the amount of solid combustion products is high.

The specific procedure for obtaining the reaction product of the present invention resulting from the reaction of aminoguanidine with nitric acid is provided below. In addition, this reaction product is also used with various additives to show its benefits. As a result, the term AZDON Example 1, used in Examples 1-12 below, refers to the actual yellow precipitate. As noted above, the reaction product of nitric acid with other aminoguanidine salts, namely amimoguanidine bicarbonate or aminoguanidine sulfate, will provide substantially the same results as the AZODN used in the following examples. This is confirmed by additional tests performed to prove that the reaction product of nitric acid and these other salts has the same properties as the AZODN of Example 1.

EXAMPLE 1

The high oxygen balance fuel according to the invention was prepared according to the following method. First, 10 g of aminoguanidine nitrate (AGN) was weighed and placed in a 400 ml glass beaker. Then, about 20-25 mL of water, preferably distilled water, was added to obtain a slurry of AGN / water. Under stirring, 150 mL of reagent grade nitric acid (70%) was slowly added to the AGN / water slurry to form a dispersion with a total volume of about 170-175 mL. When the acid was first added, the temperature rose by 10 degrees. The acid was added continuously and the temperature dropped again. This dispersion was then placed on a hot plate and heated to 55-65 ° C. with gentle stirring. This will leave any AGN in solution.

The solution was subsequently heated to 55-65 ° C. while the color of the solution changed from clear colorless to straw color to full pale yellow (similar to the color of potassium dichromate solution). [I strongly suggest using a hood and ready ice bath]. In addition, the reaction temperature should be limited to a maximum of 65 ° C. It should be noted that this solution turns dark yellow just before exotherm.

The beer was then placed in an ice bath to cool the contents and sink while bubbling. The reaction mixture was maintained in an ice bath of about 0-5 ° C. and then a yellow precipitate appeared as the temperature dropped below 12 ° C. The yellow precipitate was vacuum filtered and washed several times with distilled water. The precipitate was then washed several times with ethanol and then dried at 62 ° C.

EXAMPLE 2

Infrared absorption spectra for reaction products formed according to the method disclosed in Example 1 were measured and shown in FIG. 3. This absorption spectrum is described in Anal. Chem. 23, 1594 (1951)] and infrared absorption spectra of azodicarbamidine dinitrate found. Comparing FIG. 3 with a control spectrum (FIG. 11), the azobisformamidine-based reaction product synthesized according to the present invention is 1.1'-azodiformamidine dinitrate (azodicarbamidine dinitrate). It is thought to be.

EXAMPLE 3

Differential scanning calorimetry (DSC) was used to compare the thermal stability of the washed reaction product obtained in Example 1 with the heat-aged reaction product (17 days at 107 ° C.). The DSC plot of the washed reaction product and the DSC slot of the heat-aged reaction product show that the exothermic peak of the material and the exothermic initiation point of the material are slightly different by aging. Specifically, the exothermic onset point changed from 160.82 ° C. to 170.21 ° C. and the exothermic peak changed from 183.32 ° C. to 185.47 ° C. In conclusion, the AZODN fuel of the present invention exhibits good aging characteristics.

EXAMPLE 4

Pure AZODN powder, produced according to the method of Example 1 and containing no oxidizing agents or other additives, spontaneously detonated very rapidly when fired at ambient temperature and pressure. Specifically, a small amount (1/2 g) of high oxygen balance fuel obtained in Example 1 was stacked in the center of the watch glass, and a spark of sparked splint was applied to the sample. The sample fired immediately and burned rapidly and cleanly, similar to the lead-free rifle powder. This rapid self deflagration allows the AZODN fuel of the present invention to be very beneficial for use in heterogeneous inflators and / or hybrid inflators or auto-ignition pills (AIP) and all fatigue gas generating systems.

[Example 5]

0.269 g of the AZODN of the invention was placed in a pre-weighed aluminum pan and fired with a lit splint. The pan was reweighed after firing. 0.005 g of tan residue was obtained with 1.84% by weight of combustion residue in the initial AZODN reaction product.

Other tests were conducted on small batches of propellant comprising the AZODN reaction product according to the present invention to assess sensitivity, heat aging, weight loss and ballistic properties. The density of the product and the propellant made from this product was determined from the weight and size measurements of the propellant and was at least 1.66 g / cc.

EXAMPLE 6

When pellets (1/4 inch x 5/8 inch) obtained by compressing pure AZODN according to the present invention are burned in a strand bomb without addition of any oxidizing agent or other additives, 100, 500 And burn rates of 0.122, 0.342 and 0.428 inches / sec (ips) at 750 psi, respectively. This burn rate provided a burn rate index of 0.63.

EXAMPLE 7

A propellant (Batch # 11899) comprising 10.60% of an oxidant and scavenger, sodium nitrate (SN), 14.59% of ammonium perchlorate (AP), and 74.81% of the AZODN of the present invention was formulated at an O / F ratio of 1.0 for combustion. Based on 100 g of the sample composition, 7% solid phase combustion product and 3.7 moles of almost non-toxic gas were provided. This formulation exhibited a burn rate of 0.32 and 0.46 ips at 500 and 750 psi, respectively. This burn rate gave a pressure index of 0.90.

EXAMPLE 8

Another propellant (Batch # 11900) comprising 22.05% sodium nitrate (SN) oxidant and 77.92% of the AZODN of the present invention was formulated to yield 8% solid phase combustion products and 3.4 moles of nearly nontoxic gas per 100 g of composition upon combustion. Was provided. The ballistic properties were tested for 1/4 x 5/8 inch pellets and the burn rates at 250, 500, 750, 1000 and 1250 psi were 0.17, 0.32, 0.47, 0.59 and 0.73 ips, respectively. This burn rate gave a pressure index of 0.90.

EXAMPLE 9

Other propellants (Batch # 11901) including scavenger and coolant lithium carbonate (LC) 7.74%, AP oxidant 22.01%, and AZODN 70.25% according to the present invention provided a burn rate of 0.34 ips at 500 psi, but at 107 ° C. A significant weight loss of 5.9% occurred after 24 hours at. DSC results for this formulation showed an onset temperature of 146 ° C and an exothermic peak of 179 ° C.

EXAMPLE 10

A propellant (Batch # 11903) comprising 12.35% by weight of potassium nitrate (KN), 14.3% by weight of ammonium perchlorate (AP), and 73.35% by weight of AZODN according to the present invention, O / F of 1.0 Formulation at rain provided a solid phase combustion product theoretical concentration of 9% and 3.6 moles of nearly nontoxic gas for 100 g of composition upon combustion. Compressed into 1/4 x 5/8 inch pellets and tested for ballistic properties, providing burn rates of 0.40 and 0.52 ips at 500 and 750 psi, respectively, and a pressure index of 0.56.

EXAMPLE 11

Another propellant (Batch # 11905) comprising 12.89% strontium nitrate (SrN), 14.21% AP, and 72.90% AZODN according to the present invention was formulated at an O / F ratio of 1.0 (SrN is Clinker / Scavenger / Served as an oxidant) upon combustion gave a solid phase combustion product concentration of 9.5% and 3.5 moles of nearly nontoxic gas for 100 g of the composition. This mixture provided combustion rates of 0.34 and 0.61 ips at 500 and 100 psi, respectively, and a pressure index of 0.85.

Initiation temperatures and exothermic peaks for the various propellants provided above are shown in Table 8. This temperature was obtained from the DSC plots performed for each of the above batches.                 

Pressurized burn rates for the AZODN propellants listed in the above examples are shown in Table 9 below.

The weight loss during aging for the various AZODN formulations provided above is shown in Table 10.                 

Each of the compositions used in the above examples was filtered and washed and then dried, but AZODN was not recrystallized. Table 10 shows that the weight loss that occurred during accelerated ripening at temperatures of 107 ° C. and 90 ° C. was very small. The pellets (1/2 inch diameter x 1/2 inch high) were dried at 62 ° C. before being placed in the aging oven. Some weight loss occurred during the first day (24 hours), presumably due to the aqueous or non-aqueous volatile content.

EXAMPLE 12

The propellant batch was re-formulated at an O / F ratio of 0.90 and 0.95, resulting in a concentration of 6-7½% of solid phase combustion product. In the AP / AZODN system, replacing KN with SN, the scavenger and oxidant, resulted in solid phase combustion product concentrations of 6 and 4½% at O / F ratios of 0.95 and 0.90, respectively (if the scavenger inhibited the formation of hydrogen chloride). Indicated.

All propellant batches using pure AZODN as well as the high oxygen balance fuel according to the present invention show an acceptable risk for impact, friction, and electrostatic sensitivity exerted on the powder during testing. The impact test results for the propellant showed negative reaction all 10 times at 2.5 kg, 50 cm (100 kg-cm). Subsequent tests with the dried component showed an acceptable risk. However, after the impact test from the test result after this, it showed a somewhat large sensitivity, for example, 50 kg-cm. All electrostatic discharge tests showed negative reactions at 10 Joules and 6 Joules. All friction tests (type ABL) showed negative reactions 10 times at 300 psi-90 ° and all negative reactions at 1800 psi-90 ° for LC, SN and KN propellants (see Example below). .

Thermal stabilization studies such as differential scanning calorimetry (DSC) and high speed aging at high temperatures were conducted on several batches containing a high oxygen balance product, believed to be AZODN, prepared in Example 1. DSC plots of the propellant comprising strontium nitrate (SrN), ammonium perchlorate (AP) and unrecrystallized AZODN 12.9, 14.2 and 72.9 wt%, respectively, showed an exothermic onset temperature of 161 ° C and a main decomposition temperature of 184.5 ° C.

Analysis of the differential scanning calorimetry showed that all propellants had an exothermic decomposition initiation temperature of about 160 ° C. This means that in the case of a high oxygen balance fuel or a propellant comprising AZODN according to the invention an automatic ignition fill (AIP) is not necessary. Pure AZODN and propellant comprising AZODN have an acceptable pressure index associated with low but acceptable auto-ignition temperatures and high burn rates at low operating pressures, so the present invention is intended for use in inflator hardware with limited volume and reduced weight. Very effective. In addition, if the inflator using the propellant of the present invention is fabricated using aluminum, high performance plastics or low gauge steel components, the inflator will more easily pass the Bonfire test, which must burst without breakage.

EXAMPLE 13

A high oxygen balance fuel according to the present invention is prepared according to the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine bicarbonate is mixed with nitric acid to give embodiment 2 of the high oxygen balance fuel according to the present invention. Provided.

EXAMPLE 14

A high oxygen balance fuel according to the present invention is prepared according to the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine sulfate is mixed with nitric acid to provide embodiment 3 of the high oxygen balance fuel according to the present invention. It was.

EXAMPLE 15

A high oxygen balance fuel according to the invention was prepared according to the method of Example 1, but instead of aminoguanidine nitrate, aminoguanidine sulfate was mixed with nitric acid. In addition, embodiment 4 of the present invention was provided using the acid used in the method of Example 1 as the nitric acid component. As a result, the nitric acid can be reused after recovering the fuel of the present invention to improve the yield of the final product. The nitric acid used in one reaction can be used in subsequent reactions regardless of which aminoguanidine salt is used in the initial or subsequent reactions.

4 shows an additional DSC graph of the AZODN of Example 1. FIG. As can be seen from this figure, exothermic onset occurs at about 160 ^° C. and major degradation occurs at 185.1 ^° C. FIG. 5 is a DSC graph of the fuel produced by Example 13 (embodiment 2), showing that the exothermic initiation occurs at 157.69 ^° C. and the main decomposition occurs at 184.98 ^° C. FIG. As a result, the fuel of Example 13 using aminoguanidine bicarbonate is substantially the same as the fuel of Example 1. Thus it is azodiformamidine dinitrate. It is preferred in the present invention to use aminoguanidine bicarbonate as the aminoguanidine salt.

Figure 6 is a DSC Example 14 Grafton heating start of the fuel produced by the (embodiment 3) and the main decomposition at 150.39 ^o C is shown to occur at 182.44 C ^o. As a result, the fuel of Example 14 using aminoguanidine sulfate is also substantially the same as the fuel of Example 1. Thus, it is azodiformamidine dinitrate.

7, 8, and 9 are infrared spectra of the fuels of Examples 1, 13, and 14, respectively. 10 (a)-(d) are also infrared spectra of the fuels of Examples 15, 1, 13 and 14, respectively. These spectra were analyzed in Analytical Chemistry, Vol 23, p. Compared with the infrared spectra taken in 1594 (1951), the fuel of high oxygen balance according to the invention using the guaaminoguanidine salts comprising aminoguanidine nitrate, aminoguanidine bicarbonate, and aminoguanidine sulfate It can be seen that zodiformamidine dinitrate is generated. The same is true for the acid recovered in Example 15.

Tables 11-14 are provided to show the use of representative AZODNs prepared with aminoguanidine nitrate, aminoguanidine bicarbonate, aminoguanidine sulfate, or combinations thereof. As can be seen from the results in Table 11, the total ash production is low, the flame temperature is acceptable, and the risk tester is acceptable as "green." Specifically, Table 11 shows the AZODN propellant properties seen by five different formulations without using a binder.

Table 12 shows an evaluation of the use of binders in AZODN propellant compositions, in particular QPAC-40 binder (polycarbonate) manufactured by PAC Polymers, Inc. and CAB (cellulose-acetate butyrate) manufactured by Eastman Chemical, Inc. ) Is used for comparison. In general, this table shows that as the binder content increases, the initial compressive strength of the AZODN propellant composition increases.

Tables 13 and 14 show the effects of quenching time and fine particle size on the compressive strength and burn rate of the AZODN propellant compositions used with or without the QPAC-40 binder.                 

                  AZODN promoter without binder   Formulation number                High Rb composition Very High Rb NL-021698-1  AA-106A  AA-106B  B12020 12020/12019     AZODN   78.0   79.10   39.00   37.15   81.25     GN   --.--   --.--   31.00   33.15   --.--     AP   11.70   12.01   15.85   16.42   --.--     KP   --.--   --.--   --.--   --.--   18.75     KN   10.30   --.--   14.15    7.08   --.--     SN   --.--    8.80   --.--    6.02   --.-- Ash total amount (%)    7.5    6.0   10.0    9.0   10.1 Flame temperature, K    2777    2779   2563   2563   2809 Mall / gas / 100 g    3.7    3.7   3.7    3.8   3.5 Ballistic Characteristics R _b @ 500 psi, ips     .35    .37   .31   --.--    .58 R _b @ 1000psi, ips     .57    .67   .46     .43   1.02  Exponent, n     .70    .82   .62   --.--    .67 400 hours of aging @ 107 ^o C Fracture Strength (Mature @ 107 ^o C)    2038    3211   4114   2534   3351 Risk test    green    green   green   green   green

        Evaluation of Binders Used in AZODN Propellant ARCAIR-106: Comparison of QPAC-40 and CAB Formulation number AA-106AQ1 AA-106AQ2 AA-106AQ3 AA-106AQ5 AA-106AC! AA2-106AC3 AA-106AC5  AZODN   74.58   71.36   68.15   61.73   74.05   66.57   59.10  AP, 3μ   12.94   14.12   15.29   17.63   13.22   16.13   19.03  KN, -40 mesh   11.48   12.52   13.56   15.64   11.73   14.30   16.87  QPAC40    1.00    2.00    3.00    5.00   --.--   --.--   --.--  CAB   --.--   --.--   --.--   --.--    1.00    3.00    5.00 Ash total amount (%)    8.5    9.2   10.0   11.5    8.6   10.5   12.6 Flame temperature, ^o K   2794   2785   2777   2759   2796   2783   2771 Mole, Gas / 100g    3.6    3.6    3.6    3.5    3.6    3.6    3.5 Breaking Strength (Initial)   2732   3589   4872   6447   2728   3963   5354

Effect of Quenching Time and Fine Particle Size on Fracture Strength and Burn Rate of AZODN Propellant Compositions Used with or Without QPAC-40 Binder Formulation AA106 AWOB AA106 BWOB AA106 AQ1F AA106 BQ1F AA106 AQ2F AA106 BQ2F AA106 AQ3F AA106 BQ3F AA106N AA106NQ3 AA106 CWOB AA106 CQ1F AZODN 78.00 79.10 74.58 76.02 71.36 72.93 68.15 69.85 100. 97.0 81.25 72.65 GN --.-- --.- --.- --.- --.- --.- --.- --.- --.- --.- --.- --.- AP, 3μ 11.70 12.01 12.94 13.33 14.12 14.54 15.29 15.75 --.- --.- --.- --.- KN, 20μ 10.30 --.- 11.48 --.- 12.52 --.- 13.56 --.- --.- --.- --.- --.- SN, 20μ --.-- 8.80 --.- 9.65 --.- 10.53 --.- 11.40 --.- --.- --.- --.- QPAC-40 --.-- --.- 1.00 1.00 2.00 2.00 3.00 3.00 --.- 3.00 --.- 3.00 KP --.-- --.- --.- --.- --.- --.- --.- --.- --.- --.- 18.75 24.35 SrN --.-- --.- --.- --.- --.- --.- --.- --.- --.- --.- --.- --.- % Reload 7.5 6.0 8.5 6.7 9.2 7.2 10.0 7.8 Ignore Ignore 10.1 13.0 Flame temperature ^o K 2777 2779 2794 2804 2785 2796 2777 2796 2480 2341 2809 2860 Mole, Gas / 100g 1.7 1.7 3.6 1.7 1.6 1.7 1.6 1.7 4.2 4.2 1.5 3.4 Aging cycle Breakdown Strength (psi, Initial) 1999 1940 2388 3643 3769 3393 3963 ¹ 8694 ² 4918 7759 ² 2279 ---- 2003 6727 ³ Fracture Strength (Mature 400 Hours @ 107 ^o C) ---- ---- ---- ---- ---- ---- 3461 6166 ² 6616 ² 2267 ---- 3351 ---- -40 to 107 cycling (100 cycles) ---- 1832 2388 3342 4708 4214 2929 5294 ---- ---- ---- ---- -40 to 107 cycling (200 cycles) ----  935 ---- 3294 ---- 4004 3345 4457 ---- ---- ---- ---- Ballistic Characteristics  Rb @ 500psi .350 .355 --.-- .287 --.-- .295 --.-- .269 .34 .33 .58 .51  Rb @ 1000psi .570 .633 --.-- .461 --.-- .509 .542 .491 .56 .55 1.02 .85  Rb @ 2000psi --.-- --.-- --.-- --.-- --.-- .897 1.07 .897 --.- .86 --.- 1.39  Rb @ 4000psi --.-- --.-- --.-- --.-- --.-- --.-- 1.72 --.-- --.- --.- --.- --.-  Exponent, n .70 .81 --.-- .68 --.-- .82 .68 ³ .86 .63 .68 .67 .73

1: using -40 mesh KN

2: Quench for 3 days at 135 ^o F instead of overnight

3. n = .68 @ 2000-4000 psi; n=1.0@1000-2000 psi                 

  Comparison of AZODN Propellant Composition ARCAIR-106B with and without QPAC-40 Formulation number Without AA-106B Binder   AA-106BQ1   AA-106BQ2   AA-106BQ3   AZODN   79.10   76.02   72.93   69.85   AP, 3μ   12.10   13.33   14.54   15.75   SN, powder    8.80    9.65   10.53   11.40  QPAC40   --.--    1.00    2.00    3.00 Ash total%    6.05    6.74    7.24    7.84 Flame temperature, ^o K   2826   2803   2796   2796 Mole, Gas / 100g    3.7    3.7    3.7    3.7 Breaking Strength (Initial)   2076   3643   3393   4918 Burn rate (ips @ 1000psi)     .67     .46     .51     .49

 Sample ID Flame temperature ^o F Poorly soluble weight  Soluble weight   pH  B12020      70   0.83593 g 3.4670 g / -131 mg    7.0  AA-106A      70   1.23137 g 1.5675g / + 9mg    7.5  AA-106A      70   1.30119 g 1.5931g / -55mg    6.0  AA-106A      70   0.61248 g 0.7523 g / -27 mg    5.5  12020/12019      70   0.56786 g 2.7353 g / -65 mg    6.1  AA-106A     -40   0.49002g 1.5558 g / -33 mg    6.0  AA-106A (inside)     -40   0.49058 g    9.0  AA-106A     -40   0.44710 g 0.9576 g    6.0  AA-106B     -40   0.54327 g 1.3217 g    5.5

Table 15 shows the poor solubility produced during the inflator test without filtration of the gas generator propellant compositions of the present invention obtained from the reaction of aminoguanidine salts with nitric acid, such as aminoguanidine nitrate, aminoguanidine sulfate or the preferred salt aminoguanidine bicarbonate. And the amount of soluble degradation product. Specifically, the test relates to PD-67 sized multi-quantity test hardware expander firing without any filter integrated system attached. The sample propellant was ignited in a 60 liter tank and washed to weigh the solid decomposition products in the tank. The pH of the resulting solid decomposition product was also measured. As can be seen from the results shown in Table 15, the pH of the decomposition product was relatively neutral, and the propellant of the present invention is important in that it does not harm passengers of automobiles used in the airbag apparatus in the event of a collision. In addition, the amount of unfiltered poorly soluble and soluble degradation product is relatively low.

As can be seen from the above examples and corresponding tests, the high oxygen balance fuel of the present invention, preferably azodiformamidine dinitrate, shows interesting propellant properties and is useful in many fatigue technique gas generator environments. something to do.

Claims (25)

A pyrotechnic gas generator composition comprising a high oxygen balance fuel, wherein the high oxygen balance fuel is a solid yellow reaction product obtained by reaction of an aminoguanidine salt with nitric acid. The pyrotechnic gas generator composition according to claim 1, wherein the aminoguanidine salt is selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate and mixtures thereof. 3. The fatigue technique gas generator composition according to claim 2, wherein the content of the high oxygen balance fuel is 2-100% by weight based on the total amount of the composition. 4. The fatigue technique gas generator composition according to claim 3, wherein the content of the high oxygen balance fuel is 40-100% by weight based on the total amount of the composition. The yellow reaction product according to claim 2, wherein the yellow reaction product obtained by the reaction of the aminoguanidine salt with nitric acid is (a) providing an aminoguanidine salt; And (b) mixing the aminoguanidine salt with nitric acid to form a dispersion, wherein the dispersion is prepared according to the method comprising the step of forming a dispersion in which the color of the dispersion is changed from transparent colorless to straw or pale yellow similar to potassium dichromate solution. Pyrotechnic Gas Generator Composition. 6. A pyrotechnic gas generator composition according to claim 5, wherein 70% nitric acid of reagent grade is mixed with said aminoguanidine salt. The yellow reaction product according to claim 2, wherein the yellow reaction product obtained by the reaction of the aminoguanidine salt with nitric acid is (a) mixing the aminoguanidine salt with water to form a slurry; (b) stirring 70% nitric acid to the slurry to form a dispersion; (c) heating the dispersion while the dispersion changes color from transparent colorless to pale yellow, similar to straw or potassium bicarbonate solution, dissolving and foaming; And (d) cooling the solution to precipitate the yellow reaction product, wherein the pyrotechnic gas generator composition is prepared by the method. 8. The fatigue technique gas generator composition according to claim 7, wherein a heating temperature of the dispersion is 55-65 ° C and a cooling temperature of the solution is 12 ° C or less. 3. The pyrotechnic gas generator composition of claim 2, further comprising at least one oxidant, wherein the oxidant content is 0-98% by weight based on the total amount of the composition. 10. A pyrotechnic gas generator composition according to claim 9, wherein the at least one oxidant content is 0-60% by weight based on the total amount of the composition. 10. The fatigue technique gas generator composition according to claim 9, wherein at least one said oxidant is substantially non-moisture-proof. The method according to claim 9, wherein the scavenger, the ignition aid, the ignition initiator, the gas conversion catalyst, the ballistic modifier, the slag forming agent, the binder, the strong binder, the plasticizer, the strong plasticizer, the fuel, the stabilizer, the curing agent, the curing catalyst, the crosslinking agent, the inorganic A pyrotechnic gas generator composition further comprising at least one additive selected from the group consisting of a coolant, an organic coolant and a mixing aid and mixtures thereof. 10. The method of claim 9, wherein the at least one oxidant is selected from the group consisting of nitrates, nitrites, hydrochlorides, chlorites, perchlorates, chromates or mixtures of base metals, alkali metals, alkaline earth metals, transition metals and transition metal complexes. A fatigue technique gas generator composition, characterized in that. 14. A pyrotechnic gas generator composition according to claim 13 wherein said oxidant comprises ammonium nitrate. 15. A pyrotechnic gas generator composition according to claim 14, wherein said oxidant further comprises ammonium perchlorate. 10. A pyrotechnic gas generator composition according to claim 9 wherein said oxidant comprises phase stabilized ammonium nitrate. 10. The additive of claim 9 wherein the oxidant comprises ammonium perchlorate and the composition is an additive selected from at least one of the group consisting of ammonium perchlorate, ammonium nitrate, potassium perchlorate, strontium nitrate, potassium nitrate, lithium nitrate, lithium carbonate and mixtures thereof A fatigue technique gas generator composition further comprises. 3. The fatigue technique gas generator composition according to claim 2, wherein the reaction product is crystalline or recrystallized. The pyrotechnic gas generator composition of claim 1, further comprising at least one other high oxygen balance fuel. 20. The method of claim 19, wherein the other high oxygen balance fuel is selected from the group consisting of hydrazodicarbonamidine, diazoguanidine, formamidine, bisporamidine, azobisformamidine derivative fuels and mixtures thereof. A fatigue technique gas generator composition characterized by the above-mentioned. 21. The method of claim 20, wherein the azobisformamidine derivative is selected from the group consisting of guanyl azide nitrate, diazoguanidine nitrate, azobisnitroformamidine, 1,1'-azodiformamidine dipicrate, and mixtures thereof. A fatigue technique gas generator composition, characterized in that selected from the group consisting of. High oxygen balance fuel, which is a reaction product obtained by the reaction of an aminoguanidine salt with nitric acid, and A flame retardant chemical delivery device comprising a container containing a flame retardant chemical. The apparatus of claim 22, wherein the aminoguanidine salt is selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate, and mixtures thereof. Igniting a gas generator composition comprising a high oxygen balance fuel and wherein the high oxygen balance fuel is a yellow reaction product obtained by reaction of an aminoguanidine salt with nitric acid; Producing a gas and a solid material as a reaction product of the high oxygen balance fuel; Passing the gas and solid material through a filter to leave some solid material on the filter and to release all of the gas; And Passing the filtered gas through a gas-storable article to expand the article. The method of claim 24, wherein said aminoguanidine salt is selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate, and mixtures thereof.

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