DE102011100113A1 - Gas generator fuel composition on the basis of guanyl urea dinitramide, useful e.g. for hydraulic systems, comprises fuel- and/or explosive material and additional fuel- and/or explosive material, polymer binder, and combustion modifier - Google Patents

Abstract

Gas generator fuel composition on the basis of guanyl urea dinitramide comprises: at least one fuel- and/or explosive materials in the form of guanyl urea dinitramide or a mixture of guanyl urea dinitramide and at least one additional fuel- and/or explosives; at least one polymer binder; and at least one combustion modifier comprising oxides of cerium, preferably cerium(IV) oxide, lanthanum oxide, yttrium oxide and/or thorium oxide. An independent claim is also included for producing the gas generator fuel composition comprising mixing at least one fuel and/or explosive material in the form of guanyl urea dinitramide or the mixture of guanyl urea dinitramide, at least one least one additional fuel- and/or explosive- material, at least one combustion modifier, optionally at least one stabilizer and/or combustion catalyst in at least one polymer binder comprising at least one oxygen-containing plasticizer, where the polymer binder is processed by extrusion, extrusion molding or casting.

Description

The invention relates to a gas generator fuel composition based on guanyl urea dinitramide (GUDN, FOX 12), a process for their preparation and their use.

In gas generator fuels, which are used for example for turbine drives, hydraulic units, rescue systems or pyrotechnic actuators, it is desirable that they have very high gas yields in combination with the lowest possible combustion or exhaust gas temperatures. Likewise, they should not contain soot and, moreover, only very small proportions of solid particles in the exhaust gas. Another requirement is a sufficiently high burn rate to generate the required amount of gases to be supplied with a simple propellant geometry. Nevertheless, the burning rates must be lower than z. Example, in the case of gas generator fuel compositions for airbags of motor vehicles, which are there usually about 30 mm / s or more, because the generated gas must be available over a longer period of time. Furthermore, good mechanical and chemical stability as well as low sensitivity, both thermally and mechanically, combined with high application safety and shelf life should be ensured.

Traditional low-energy double base propellants, which are based on cellulose nitrate in conjunction with liquid nitric acid esters as plasticizers and optionally polyurethane binders, are able to meet the requirements mentioned in particular with respect to a low thermal and mechanical sensitivity as well as in terms of high chemical stability. While the relatively high thermal and / or mechanical sensitivity of double base propellants can represent a significant hazard potential with respect to the mass detonability associated therewith, at higher temperatures below about -30 ° C, double base propellants often tend to embrittle, compromising the reliability of the respective Application goes along. Although gas turbine propellants based on ammonium nitrate (AN) with inert polyurethane binders have high gas yields and low combustion temperatures, they have serious disadvantages due to their very low burnup rates and the hygroscopic nature of ammonium nitrate, combined with their ability to undergo crystalline phase transitions with volume changes (cf. z. BK Menke, J. Boehnlein-Mauß, H. Schubert: "Characteristic properties of AN / GAP propellants" - Propellants, Explosives, Pyrotechnics 21, pages 139 to 145, 1996 ; W. Engel, N. Eisenreich, A. Deimling, M. Herrmann, MJ Lorenzo, V. Kolarik: "Ammonium Nitrate, a Less Polluting Oxidizer", 24th Intern. Ann. ICT-Conf., Pages 3.1 to 3.9, 1993 ).

Guanyl urea dinitramide (GUDN, FOX 12) is due to its chemical composition with a very high nitrogen content, an oxygen balance of -19%, its density of about 1.75 g / cm ³ at 20 ° C and its favorable decomposition kinetics in conjunction with a very high thermal stability and low mechanical sensitivity are potentially good for the formulation of gas generator fuel compositions of the type mentioned in the beginning (cf. H. Östmark et al .: "N-guanylurea dinitramide (FOX-12): Properties" - Technical Report FOI-R-2312-SE, 2007 ; H. Östmark, U. Bemm, H. Bergman, A. Langlet: "N-guanylurea-dinitramide: A new Energetic Material with Low Sensitivity for Propellants and Explosive Applications" - Thermochimica Acta 384, pages 263 to 259, 2002 ).

Up to now, this behavior of guanylurea dinitramide has been used almost exclusively in short-term burning airbag formulations with burning rates in the abovementioned ranges. In addition to guanylurea dinitramide, such formulations usually contain as nitrogen-supplying component oxidizing agents in the form of potassium, sodium, ammonium or strontium nitrate, potassium or ammonium perchlorate, sometimes chlorates, and frequently also basic copper hydroxynitrate as an oxygen source.

The US 6 291 711 B2 . US 6 117 255 B2 and US Pat. No. 6,824,626 82 describe formulations as well as the processing and the burn-off behavior of such guanylurea-dinitramide-based gas generator fuels designed primarily for airbag applications and other nitrogen-containing compounds, such as guanidine nitrate, nitroguanidine, dicyanamides or tretrazole derivatives. By means of the excess oxidant added there, balanced oxygen balances and high burnup rates are achieved, but this occurs at the expense of high burnup temperatures and high levels of solid burnup products. Due to the high exhaust gas temperatures and slag content in the exhaust gas, these known formulations are not suitable for gas generators for longer-lasting compressed gas production of the type mentioned, such as for turbine drives, hydraulic systems or pyrotechnic actuators.

Furthermore, gas generator fuel compositions are known which contain burn-off modifiers in the form of rare earth metal compounds for guanyl urea dinitramide-free propellants and / or explosives and which in turn should be used especially in fast-burning airbag formulations. That's how it describes US Pat. No. 6,277,221 B1 the use of ammonium or aminoguanidine, cerium or scandium nitrate as oxygen-supplying components in concentrations of greater than 20% by mass, based on the respective propellant or explosive. Of the US 2007/0200090 A1 Scandium, yttrium, lanthanum, cerium, praseodymium and Neodymoxide are as Abbrandbeschleuniger as well as gas-cleaning component in traditional airbag fuel compositions refer to which have a largely balanced oxygen balance. However, the latter are again designed for burn times in the millisecond range and do not fulfill the properties of a fuel for a relatively long-lasting compressed gas production.

It is an object of the present invention to propose a detonation-insensitive gas generator propellant composition based on guanyl urea dinitramide having high gas yield at low burnout temperatures, a very low particulate content in the exhaust, and one compared to airbag inflator fuel compositions has relatively low burning rate, which ensures a relatively long-term burning and a related, relatively long-term pressure gas development. It is further directed to a method of making such a gas generator fuel composition and to the use thereof.

• – wenigstens einen Treib- und/oder Explosivstoff in Form von Guanylharnstoffdinitramid oder einer Mischung aus Guanylharnstoffdinitramid und wenigstens einem weiteren Treib- und/oder Explosivstoff;
• – wenigstens einen Polymerbinder; und
• – wenigstens einen Abbrandmodifikator aus der Gruppe der Oxide der Metalle Cer, insbesondere Cer(IV)oxid (CeO₂), Lanthan (La₂O₃), Yttrium (Y₂O₃) und/oder Thorium (ThO₂)

enthält.According to the invention, this object is achieved with a gas generator fuel composition based on guanyl urea dinitramide, which

• - At least one propellant and / or explosive in the form of guanyl urea dinitramide or a mixture of guanyl urea dinitramide and at least one other propellant and / or explosive;
• - at least one polymer binder; and
• At least one burn-up modifier from the group of the oxides of the metals cerium, in particular cerium (IV) oxide (CeO ₂ ), lanthanum (La ₂ O ₃ ), yttrium (Y ₂ O ₃ ) and / or thorium (ThO ₂ )

contains.

The advantages of the gas generator fuel composition according to the invention are in particular in very low exhaust gas temperatures (see below), which is due to the Abbrandmodifikatoren invention despite a relatively high selectable portion of the polymer binder not only flawless flammability, but in particular a virtually complete burn is ensured which provides a vent gas that is substantially free of particulate residue including soot. In this case, it is also possible to prevent the fuel composition from producing, as a result of incomplete combustion, vaporous and later condensed hydrocarbon compounds which otherwise could impair the required gas purity and at the same time substantially limit the gas yield. The relative to conventional airbag fuel compositions relatively low burning rate can provide for burning times in the second to minutes range and for a consequent relatively long, continuous gas evolution (see also below), the burnup rate is nevertheless higher than in conventional Gas generator fuels based on ammonium nitrate (AN). The burn-off modifiers according to the invention from the group of the oxides of the metals cerium, in particular cerium (IV) oxide (CeO ₂ ), lanthanum (La ₂ O ₃ ), yttrium (Y ₂ O ₃ ) and / or thorium (ThO ₂ ) can hereby be separate or come in the form of mixtures used. They also cause virtually complete residue-free conversion of the fuel composition upon combustion of the fuel composition, even if the guanylurea dinitramide based gas-generator fuel composition is under-balanced with an oxygen balance of about -55% to about -30%. In this connection, it is assumed that the burn-up modifiers added according to the invention catalyze the formation of the thermodynamically calculated gaseous end products at a low burnup temperature.

In an advantageous embodiment it can be provided that the gas generator fuel composition, the at least one oxide of the metals cerium, lanthanum, yttrium and / or thorium singly or in the form of a mixture in an amount between about 0.1 Mass .-% and about 5 mass. %, in particular in a proportion between about 0.2% by mass and about 4% by mass, based on the total composition. Such a proportion has proven to be sufficient to fulfill its intended functions completely.

In a further advantageous embodiment, it may be provided that the gas generator fuel composition, the at least one oxide of the metals cerium, lanthanum, yttrium and / or thorium singly or in the form of a mixture having a particle size between about 10 nm and about 10 .mu.m, in particular between about 20 nm and about 1 μm, preferably between about 20 nm and about 500 nm. That way is a very fine distribution of Abbrandmodifikatoren invention ensures a large, catalytically active surface thereof. The particle sizes mentioned here relate to the mean particle size (mps, median particle size) of the cerium, lanthanum, yttrium and / or thorium oxide particles.

With regard to the guanylurea dinitramide-based propellant and / or explosive, it has proven particularly advantageous if the at least one propellant and / or explosive substance is essentially pure guanylurea dinitramide or a mixture of guanylurea dinitramide and 1,1-diamino-2-one , 2-dinitroethylene (FOX 7), in particular in a mass ratio of guanyl urea dinitramide to 1,1-diamino-2,2-dinitroethylene between about 1: 9 and about 9: 1, preferably between about 2: 8 and about 8: 2, is. A particularly preferred mass ratio here is between about 20 mass% 1,1-diamino-2,2-dinitroethylene / 80 mass% guanyl urea dinitramide and about 70 mass% 1,1-diamino-2,2-dinitroethylene / 30 mass% guanyl urea dinitramide.

The gas generator fuel composition according to the invention preferably contains substantial proportions of the at least one polymer binder, wherein it preferably contains the at least one propellant and / or explosive in a proportion of between about 50% by mass and 95% by mass, in particular between about 60% by mass. % and about 90% by mass, based on the total composition.

The at least one blowing and / or explosive based on guanyl urea dinitramide may preferably have a particle size of between about 1 μm and about 1000 μm, in particular between about 2 μm and about 500 μm, preferably between about 5 μm and about 400 μm.

• – der Polyester- und/oder Polyetherurethane, insbesondere der Isocyanat-gehärteten Polyester- und/oder Polyetherurethane,
• – der Azid-substituierten Polyether, insbesondere der Isocyanat- oder Acetylen-gehärteten Azid-substituierten Polymeren, vorzugsweise der Glycidylazidopolymere (GAP),
• – der Nitratester-substituierten Polyether, insbesondere der Isocyanat-gehärteten Nitratester-substituierten Polyether, vorzugsweise Polyglycidylnitrat (PolyGLYN) und/oder Polynitratomethylmethyloxetan (PolyNIMMO),
• – der Epoxypolymere, und
• – der Acrylatpolymere

erwiesen.According to a preferred embodiment, it is provided that the at least one polymer binder is an inert or energetic polymer binder from the group of the polyurethanes, the epoxy and the acrylate polymers. Polymer binders from the group are particularly preferred

• The polyester and / or polyether urethanes, in particular the isocyanate-cured polyester and / or polyether urethanes,
• The azide-substituted polyether, in particular the isocyanate- or acetylene-cured azide-substituted polymers, preferably the glycidyl azido copolymers (GAP),
• The nitrate ester-substituted polyether, in particular the isocyanate-cured nitrate ester-substituted polyether, preferably polyglycidyl nitrate (PolyGLYN) and / or polynitratomethylmethyloxetane (PolyNIMMO),
• - the epoxy polymers, and
• - The acrylate polymers

proved.

According to a particularly preferred embodiment, it is provided that the at least one polymer binder further contains at least one oxygen-containing, especially oxygen-rich, plasticizer. With regard to advantageous proportions by weight of such an oxygen-containing plasticizer, it is preferably provided that the polymer binder contains the plasticizer containing at least one oxygen in a proportion of between 5 mass% and 75 mass%, in particular between 10 mass% and 70 mass .-%, preferably between 20 Mass .-% and 60 Mass .-%, based on the mass of the polymer binder contains.

In connection with an oxygen-rich plasticizer of the aforementioned type, it can be provided in an advantageous embodiment that the plasticizer comprising at least one oxygen from the group bis-dinitropropyl formal / acetal (BDNPF / A), metrioltrinitrate (TMETN), 1,2,4-butanetriol trinitrate (BTTN ), 2-nitrate ester ethylnitroamine (NENA), n-alkyl-2-nitrate ester ethylnitroamine, especially methyl 2-nitrate ester ethylnitroamine (MeNENA), ethyl 2-nitrate ester ethylnitroamine (EtNENA), n-butyl 2-nitrate ester ethylnitroamine (BuNENA) or mixtures thereof, as Me / EtNENA, triacetin (TA), alkyl citrate, in particular ethyl citrate or butyl citrate, and Dinitrodiazaalkane, in particular five- to seven-membered Dinitrodiazaalkane or mixtures thereof is selected.

In addition, the gas generator composition according to the invention may contain at least one stabilizer, as it is known as such, in particular for the chemical stabilization of nitrate ester or polyether urethanes. A preferred embodiment in this context may provide that the at least one polymer binder comprises at least one such stabilizer in a proportion of between about 0.1 mass% and about 5 mass%, preferably between about 0.2 mass% and about 2 Mass .-%, based on the mass of the polymer binder contains.

Advantageous representatives of such stabilizers include phenol-substituted ureas, especially centralites and acardites, phenylamines, especially diphenylamine (DPA), triphenylamine (TPA), 2-nitrodiphenylamine (2NDPA) and N-methyl-4-nitroaniline (MNA), organic thioethers, magnesium oxide (MgO), 3-aminotriazole and sulfur (S), especially in fine crystalline form.

Moreover, it is conceivable that the gas generator composition according to the invention further contains at least one burn-off catalyst, in particular from the group of the copper compounds and / or the transition metal oxides. A preferred embodiment may provide in this regard that the gas generator composition comprises the at least one burnup catalyst in an amount between about 0.1 mass% and about 5 mass%, in particular between about 0.2 mass% and about 3 Mass .-%, based on the total composition contains. The at least one burnup catalyst may preferably have a particle size of at most about 100 .mu.m, in particular of at most about 50 .mu.m, preferably of at most about 10 .mu.m, wherein the particle size again refers to the average particle size (mps, median particle size) of the burnup catalysts ,

Advantageous representatives of such Abbrandkatalysataren include copper oxide (CuO), copper phthalocyanate, copper salicylate, copper chromite, copper nitrate, in particular basic copper nitrate, iron oxide, in particular iron (III) oxide (Fe ₂ O ₃ ) and / or Fe ₃ O ₄ , cobalt oxide, in particular cobalt (III ) oxide (Co ₂ O ₃ ), manganese oxide, in particular manganese (IV) oxide (manganese dioxide, MnO ₂ ), chromium oxide, in particular chromium (VI) oxide (CrO ₃ ), vanadium oxide, in particular vanadium (V) oxide (V ₂ O ₅ ), Molybdenum oxide, especially molybdenum (VI) oxide (MoO ₃ ), and mixed oxides thereof, such as V ₆ moles of ₁₅ O ₆₀ .

By means of such burnup catalysts z. B. the burning behavior of the gas generator fuel composition varies and in particular the burning rate can be increased and adapted exactly to the respective needs. Furthermore, for example, the pressure exponent can be reduced according to the respective requirements.

• – die Abgastemperatur (gemessen nach 70:1-Entspannung) der Gasgenerator-Treibstoffzusammensetzung höchstens etwa 400°C, insbesondere höchstens etwa 350°C, vorzugsweise höchstens etwa 300°C, oder weniger beträgt; und/oder
• – die Abbrandgeschwindigkeit (gemessen bei 10 MPa) der Gasgenerator-Treibstoffzusammensetzung zwischen etwa 1 mm/s und etwa 12 mm/s, insbesondere zwischen etwa 2 mm/s und etwa 10 mm/s, vorzugsweise zwischen etwa 4 mm/s und etwa 8 mm/s,

beträgt.As already mentioned, the gas generator composition according to the invention offers, in particular, the possibility of ensuring low combustion or exhaust gas temperatures as well as practicable combustion rates at low pressures. In a preferred embodiment can therefore be provided that

• The exhaust gas temperature (measured after 70: 1 relaxation) of the gas generator fuel composition is at most about 400 ° C, more preferably at most about 350 ° C, preferably at most about 300 ° C, or less; and or
• The burnup rate (measured at 10 MPa) of the inflator fuel composition is between about 1 mm / s and about 12 mm / s, in particular between about 2 mm / s and about 10 mm / s, preferably between about 4 mm / s and about 8 mm / s,

is.

In Table 1 below, the property profiles of various cured gas generator fuel compositions according to the present invention are exemplified. The fuel compositions each contain a proportion of between 70% by mass and 78% by mass of guanylurea dinitramide and four different isocyanate-cured and energy-softening polymer binder systems based on glycidyl azide polymer (GAP) / triacetin (TA) (third column) , Polyesterurethane (PU) / bisdinitropropylformal / acetal mixture (BDNPF / A) (fourth column), glycidyl azide polymer GAP / polyesterurethane (PU) / bisdinitropropylformal / acetal mixture (BDNPF / A) (fifth column) and polyether urethane (PEtherU) / Bisdinitropropylformal / acetal mixture (BDNPF / A) / triacetin (TA) (sixth and last column). Table 1: Exemplified properties of guanylurea dinitramide (GUDN) gas generator fuel compositions with varied polymer binder systems. unit CAP / TA PU / BDNPF / A GAP / PU / BDNPF / A PEtherU / BDNPF / A Abbrandtemp. tc K 1248-1325 1305-1490 1495-1727 1490-1548 Exhaust gas temperature Te 70: 1 ° C 170-185 183-250 248-360 246-275 Weight spec. gas yield Nl / kg 1073-1102 1112-1180 1064-1110 1065-1102 Vol. Spec. gas yield Nl / dm ³ 1650-1735 1680-1718 1716-1758 1695-1769 O2 balance sheet % -48 ♢ -54 -44 ♢ -50 -38 ♢ -45 -46 ♢ -52 Working viscosity Pas 12-80 52-296 92-800 56-256 Flam. Point 20 ° / min ° C 197-198 201-206 204-208 197 Holland T. 8-72 h / 105 ° C ma% 0.25 to 0.26 from 0.31 to 0.43 0.14 to 0.18 1.3-2.3 Vak. Rod. 40 h / 100 ° C ml / g 0.19 0.14 to 0.19 0.15 to 0.22 1.8-2.4 Glass transition temp. ° C -55 ♢ -59 -46 ♢ -54 -44 ♢ -50 -53 _Burn rate, _10MPa mm / s 3.1 to 4.9 3.9 to 5.4 6.1 to 8.1 5.3-5.8 Pressure exponent n 5-13 MPa 0.5 ♢ 0.6 0.5 ♢ 0.7 0.6 ♢ 0.7 0.3-0.5 Blow Rec. BAM nm 15-30 15-20 10-20 15 Reibempf. BAM N ≥360 > 360 > 360 > 360 Gap test 21 mm mm PMMA 0- 0- 0- 0-

As can be seen from Table 1, after the composition of the polymer binder system, burnup temperatures of 1240 K <Tc <1730 K and exhaust gas temperatures of 170 ° C. <Te <360 ° C. are observed at a relaxation of 70: 1. Specific gas yields based on fuel weight (normal volume, NV = gas volume under standard conditions) range between 1060 Nl / kg (standard liters per kilogram) and 1115 Nl / kg; The fuel volume values range from 1650 Nl / dm ^{3 to} 1770 Nl / dm ³ . The burnup rates at 10 MPa range between 3 mm / s <r ₁₀ <8.5 mm / s and are thus more than twice as high as comparable fuels with ammonium nitrate (AN) as an oxidizer, but lower than the burning rates of conventional airbag gas generator compositions. The pressure exponents are best adjusted for polyetherurethane (PEtherU) bound fuels with n = 0.3 to 0.5 in the pressure range of 5 to 13 MPa.

All gas generator fuel compositions formulated according to the present invention provide chlorine-free and low-particle exhaust gases having a much higher elemental nitrogen content (N ₂ ) than conventional double base or ammonium nitrate-containing formulations. They are hardly susceptible to friction and impact and are not or only to a limited extent sensitive to detonation. Thermal sensitivity and chemical stability vary with the composition of the binder and may be improved beyond the values shown in Table 1 by the addition of known stabilizers, in particular those of the type mentioned above.

The property profiles presented in Table 1 thus provide excellent conditions for guanyl urea dinitramide based gas generator fuel compositions in the described compositions to be suitable for sustained, more or less continuous, pressurized gas production lasting for several seconds to minutes.

The invention also relates to a process for the preparation of a gas generator composition based on guanyl urea dinitramide (GUDN, FOX 12) of the aforementioned type, by the at least one propellant and / or explosive in the form of guanyl urea dinitramide or a mixture of guanyl urea dinitramide and at least one other Propellant and / or explosive, in particular 1,1-diamino-2,2-dinitroethylene (FOX 7), and the at least one Abbrandmodifikator from the group of oxides of the metals cerium, in particular cerium (IV) oxide (CeO ₂ ), lanthanum (La ₂ O ₃ ), yttrium (Y ₂ O ₃ ) and / or thorium (ThO ₂ ) and optionally at least one stabilizer and / or combustion catalyst in at least one polymer binder, which contains in particular at least one oxygen-containing plasticizer is mixed, wherein the Polymer binder is processed in particular by extrusion, extrusion or casting. The polymer binders, plasticizers, burn-off catalysts and / or stabilizers preferably used are the abovementioned representatives thereof. The same applies to their percentages and their particle size.

The gas generator fuel compositions formulated in accordance with the invention can be advantageously up to a solids content of about 80% by weight with (pre) polymeric plastic binders in a slurry casting process and up to a solids content of about 90% by weight, if appropriate even with small amounts of solvents, by extrusion or extrusion process.

Finally, the invention also relates to the use of a gas generator propellant composition based on guanyl urea dinitramide (GUDN, FOX 12) of the aforementioned type for hydraulic systems, eg. As for driving internal power plants and / or feed pumps in rockets, for conveying pressurized gas for (gel) propellants and the like, for pyrotechnic actuators, z. As for inflating lifting cushion of salvaging equipment and the like, for turbine drives, for conveying and control systems, especially in rocket engines, rescue systems etc. It should be noted that the gas generator fuel compositions according to the invention are in principle particularly suitable for such applications, in which is a high gas yield at low Abbrand- or exhaust gas temperatures, low levels of noxious gases and particulate products in the exhaust gas and especially low compared to airbag gas generator fuel compositions Abbrandgeschwindigkeiten and associated, relatively long combustion times or long-lasting pressure gas developments is desired.

The invention is explained in more detail by means of exemplary embodiments with reference to the drawing. The only figure shows
a burn-off diagram for three embodiments of gas generator fuel compositions according to the invention according to the following examples 1 to 3, wherein the lgr = f (lgp) diagrams of burning rates measured in the Crawford bomb under nitrogen pressure (N ₂ ) were obtained by Crawford measurements;
r = linear burning rate (burning rate) in
[mm / s] and
p = pressure in [MPa]

Five exemplary formulations of embodiments of the inventive gas generator fuel composition are summarized in Table 2 below.

All of these gas generator fuel compositions burn smoke-free with low flame at ambient pressure and produce small, loose, white residues of cerium / yttrium oxides (CeO ₂ / Y ₂ O ₃ ). When burned under nitrogen pressure (N ₂ ) in the Crawford bomb they burn without any organic residues and only under residue of oxidic powders in very small quantities. Likewise constructed fuel compositions without CeO ₂ and Y ₂ O ₃ produce greasy oily residues when burned under nitrogen pressure (N ₂ ) in the bomb. At ambient pressure, the latter either burn largely smoke-free with flame and carbon skeleton as residue, or they pyrolyze without flame, but with the formation of gray smoke.

Of particular advantage for the combustion behavior with regard to a reduction of the pressure exponent at pressures above 100 bar proves to be a mixture of guanylurea dinitramide (GUDN, FOX 12) and 1,1-diamino-2,2-dinitroethylene (FOX 7) with proportions of 20 mass % FOX 7 up to 70% by mass FOX 7 based on the total proportion of the mixture of both energetic solid components (Example 5 of Table 2, right-hand column). Table 2: Exemplary formulations of gas generator fuel compositions according to the invention (all percentages in [% by mass]. Gas generator fuels with the addition of nanoscale CeO ₂ / Y ₂ O ₃ example 1 Example 2 Example 3 Example 4 Example 5 Burning rate at 10 MPa in mm / s 6.7 6.5 5.8 3.8 4.9 Composition: GUDN 270 μm / 25 μm 70.0% 70.0% 70.0% 75.0% 35.6% FOX 7 160 μm - - - 34.4% CeO ₂ nanoscale 1.0% 1.0% 1.0% 1.0% 1.0% Y ₂ O ₃ nanoscale 1.0% 1.0% 1.0% 1.0% 1.0% GAP / N100-polymer 11.2% - - 10.0% - Palyester / N3400 polymer - 8.4% - - - Polyether / HDI polymer - - 8.4% - 14% BDNPA / F 13.4% 19.6% 19.6% - 14% triacetin 3.4% - - 13.0% - Properties: theoretical density in g / cm ³ 1.625 1,619 1,604 1,607 1,605 Gas yield in mol / kg 47.39 47.06 48,80 47.86 50.06 specific gas yield in Nl / kg 1061 1054 1093 1072 1121 volumetric gas yield in Nl / dm ³ 1722 1716 1739 1723 1800 Oxygen balance in% -39.3 -38.4 -42.7 -45.31 -52.4 Adiabatic burning temperature in ° C 1387 1371 1253 1048 1162 Flue gas temperature after expansion (70: 1) in ° C 327 327 267 188 224

Table 2 shows the thermodynamic data and burnup rate of the exemplary formulation. According to Vieille's law, the pressure exponent for the dependency of the combustion rate on the pressure of these gas generator fuel compositions manifests itself at n = 0.45 for the pressure range of 100 bar ≤ p ≤ 250 bar. At the same time, the low combustion and exhaust gas temperatures shown in conjunction with a good combustion rate of 10 mm / s ≥ r ≥ 4 mm / s at 100 bar result.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 6291711 B2 [0006]
• US 6117255 B2 [0006]
• US 682462682 [0006]
• US 6277221 B1 [0007]
• US 2007/0200090 A1 [0007]

Cited non-patent literature

• BK Menke, J. Boehnlein-Mauß, H. Schubert: "Characteristic properties of AN / GAP propellants" - Propellants, Explosives, Pyrotechnics 21, pp. 139-145, 1996 [0003]
• W. Engel, N. Eisenreich, A. Deimling, M. Herrmann, MJ Lorenzo, V. Kolarik: "Ammonium Nitrate, a Less Polluting Oxidizer", 24th Intern. Ann. ICT-Conf., Pages 3.1 to 3.9, 1993 [0003]
• H. Östmark et al .: "N-guanylurea dinitramide (FOX-12): Properties" - Technical Report FOI-R-2312-SE, 2007 [0004]
• H. Östmark, U. Bemm, H. Bergman, A. Langlet: "N-Guanylurea-dinitramide: A New Energetic Material with Low Sensitivity for Propellants and Explosive Applications" - Thermochimica Acta 384, pages 263 to 259, 2002 [0004]

Claims (20)

Guanylurea dinitramide (GUDN, FOX 12) gas generator propellant composition comprising: - at least one propellant and / or explosive in the form of guanyl urea dinitramide or a mixture of guanyl urea dinitramide and at least one other propellant and / or explosive; - at least one polymer binder; and - at least one Abbrandmodifikator from the group of oxides of the metals cerium, in particular cerium (IV) oxide (CeO ₂ ), lanthanum (La ₂ O ₃ ), yttrium (Y ₂ O ₃ ) and / or thorium (ThO ₂ ). Gas generator fuel composition according to claim 1, characterized in that it contains the at least one oxide of the metals cerium, lanthanum, yttrium and / or thorium singly or in the form of a mixture in an amount between 0.1 mass% and 5 mass% , in particular in a proportion between 0.2 mass% and 4 mass%, based on the total composition. Gas generator fuel composition according to claim 1 or 2, characterized in that it comprises the at least one oxide of the metals cerium, lanthanum, yttrium and / or thorium singly or in the form of a mixture having a particle size between 10 nm and 10 .mu.m, in particular between 20 nm and 1 μm, preferably between 20 nm and 500 nm. Gas generator fuel composition according to any one of claims 1 to 3, characterized in that the at least one propellant and / or explosive substance is substantially pure guanyl urea dinitramide or a mixture of guanyl urea dinitramide and 1,1-diamino-2,2-dinitroethylene (FOX 7), especially in a mass ratio of guanylurea dinitramide to 1,1-diamino-2,2-dinitroethylene between 1: 9 and 9: 1, preferably between 2: 8 and 8: 2. A gas generator fuel composition according to any one of claims 1 to 4, characterized in that it contains the at least one propellant and / or explosive in an amount between 50 mass% and 95 mass%, in particular between 60 mass% and 90 Mass .-%, based on the total composition contains. Gas generator fuel composition according to one of claims 1 to 5, characterized in that the at least one propellant and / or explosive has a particle size between 1 .mu.m and 1000 .mu.m, in particular between 2 .mu.m and 500 .mu.m, preferably between 5 .mu.m and 400 .mu.m , Gas generator composition according to one of claims 1 to 6, characterized in that the at least one polymer binder is an inert or energetic polymer binder from the group of polyurethanes, the epoxy and the acrylate polymers. Gas generator composition according to one of claims 1 to 7, characterized in that the at least one polymer binder from the group The polyester and / or polyether urethanes, in particular the isocyanate-cured polyester and / or polyether urethanes, The azide-substituted polyether, in particular the isocyanate- or acetylene-cured azide-substituted polymers, preferably the glycidyl azido copolymers (GAP), The nitrate ester-substituted polyether, in particular the isocyanate-cured nitrate ester-substituted polyether, preferably polyglycidyl nitrate (poly-GLYN) and / or polynitratomethylmethyloxetane (poly NIMMO), - the epoxy polymers, and - The acrylate polymers is selected. Gas generator composition according to one of claims 1 to 8, characterized in that the at least one polymer binder contains at least one oxygen-containing, especially oxygen-rich, plasticizer. Gas generator composition according to claim 9, characterized in that the polymer binder contains the at least one oxygen-containing plasticizer in a proportion between 5 mass% and 75 mass%, in particular between 10 mass% and 70 mass%, preferably between 20 mass% and 60 mass%, based on the mass of the polymer binder. Gas generator composition according to claim 9 or 10, characterized in that the at least one oxygen-containing plasticizer from the group bis-dinitropropyl formal / acetal (BDNPF / A), metrioltrinitrate (TMETN), 1,2,4-butanetriol trinitrate (BTTN), 2- Nitrate ester ethylnitroamine (NENA), n-alkyl-2-nitrate ester ethylnitroamine, especially methyl 2-nitrate ester ethylnitroamine (MeNENA), ethyl 2-nitrate ester ethylnitroamine (EtNENA), n-butyl 2-nitrate ester ethylnitroamine (BuNENA) or mixtures thereof, such as Me / EtNENA , Triacetin (TA), alkyl citrate, in particular ethyl citrate or butyl citrate, and dinitrodiazaalkanes, in particular five- to seven-membered dinitrodiazaalkanes or mixtures thereof. Gas generator composition according to one of claims 1 to 11, characterized in that the at least one polymer binder at least one stabilizer, in particular in a proportion of between 0.1 mass% and 5 mass%, preferably between 0.2 mass. % and 2 mass .-%, based on the mass of the polymer binder contains. Gas generator composition according to claim 12, characterized in that the stabilizer from the group of phenyl-substituted ureas, in particular the Centralite and Akardite, the phenylamines, in particular diphenylamine (DPA), triphenylamine (TPA), 2-nitrodiphenylamine (2NDPA) and N-methyl-4-nitroaniline (MNA), the organic thioether, magnesium oxide (MgO), 3-aminotriazole and sulfur (S), especially in fine crystalline form, is selected. Gas generator composition according to one of claims 1 to 12, characterized in that it further contains at least one burn-off catalyst, in particular from the group of copper compounds and / or the transition metal oxides. Gas generator composition according to claim 14, characterized in that it contains the at least one burnup catalyst in an amount between 0.1% by mass and 5% by mass, in particular between 0.2% by mass and 3% by mass, based on the total composition. Gas generator composition according to claim 14 or 15, characterized in that the at least one burnup catalyst has a particle size of at most 100 .mu.m, in particular of at most 50 .mu.m, preferably of at most 10 .mu.m. Gas generator composition according to one of claims 14 to 16, characterized in that the at least one burnup catalyst from the group copper oxide (CuO), copper phthalocyanate, copper salicylate, copper chromite, copper nitrate, in particular basic copper nitrate, iron oxide, in particular iron (III) oxide (Fe ₂ O ₃ ) and / or Fe ₃ O ₄ , cobalt oxide, in particular cobalt (III) oxide (Co ₂ O ₃ ), manganese oxide, in particular manganese (IV) oxide (manganese dioxide, MnO ₂ ), chromium oxide, in particular chromium (VI) oxide ( CrO ₃ ), vanadium oxide, in particular vanadium (V) oxide (V ₂ O ₅ ), molybdenum oxide, in particular molybdenum (VI) oxide (MoO ₃ ), and mixed oxides thereof, such as V ₆ Mo ₁₅ O ₆₀ , is selected. Gas generator composition according to one of claims 1 to 17, characterized in that - Its exhaust gas temperature (measured after 70: 1 relaxation) at most 400 ° C, in particular at most 350 ° C, preferably at most 300 ° C, is; and or - Its burning rate (measured at 10 MPa) between 1 mm / s and 12 mm / s, in particular between 2 mm / s and 10 mm / s, preferably between 4 mm / s and 8 mm / s, is. A process for producing a guanylurea dinitramide (GUDN, FOX 12) gas generator composition according to any one of claims 1 to 18, wherein the at least one guanyl urea dinitramide blowing or explosive or guanyl urea dinitramide mixture and at least one other propellant and / or explosive and the at least one burn-up modifier from the group of the oxides of the metals cerium, in particular cerium (IV) oxide (CeO ₂ ), lanthanum (La ₂ O ₃ ), yttrium (Y ₂ O ₃ ) and / or thorium ( ThO ₂ ) and optionally at least one stabilizer and / or Abbrandkatalysator in at least one polymer binder, which contains in particular at least one oxygen-containing plasticizer, is mixed, wherein the polymer binder is processed in particular by extrusion, extrusion or casting. Use of a guanylurea dinitramide (GUDN, FOX 12) gas generator composition according to any one of claims 1 to 18 for hydraulic systems, pyrotechnic actuators, turbine drives, conveyor and control systems, in particular for rocket engines, and rescue systems.

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