DE29821544U1 - Azide-free, gas generating composition - Google Patents
Azide-free, gas generating compositionInfo
- Publication number
- DE29821544U1 DE29821544U1 DE29821544U DE29821544U DE29821544U1 DE 29821544 U1 DE29821544 U1 DE 29821544U1 DE 29821544 U DE29821544 U DE 29821544U DE 29821544 U DE29821544 U DE 29821544U DE 29821544 U1 DE29821544 U1 DE 29821544U1
- Authority
- DE
- Germany
- Prior art keywords
- nitrate
- composition according
- group
- composition
- ammonium perchlorate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 82
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000000446 fuel Substances 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 14
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 claims description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 claims description 4
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- BVEWMNTVZPFPQI-UHFFFAOYSA-N dialuric acid Chemical compound OC1C(=O)NC(=O)NC1=O BVEWMNTVZPFPQI-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- BVGPZRCQJJMXBI-UHFFFAOYSA-N 1,2-diaminoguanidine;nitric acid Chemical compound O[N+]([O-])=O.NN\C(N)=N/N BVGPZRCQJJMXBI-UHFFFAOYSA-N 0.000 claims description 2
- BAKYASSDAXQKKY-UHFFFAOYSA-N 4-Hydroxy-3-methylbenzaldehyde Chemical compound CC1=CC(C=O)=CC=C1O BAKYASSDAXQKKY-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- UFRRRMXNFIGHPC-CPZJCIGYSA-N alloxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C#CC1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC#CC2=C(C)CC(O)CC2(C)C UFRRRMXNFIGHPC-CPZJCIGYSA-N 0.000 claims description 2
- KBJCHZXIAAWHMB-UHFFFAOYSA-N guanidine;perchloric acid Chemical compound NC(N)=N.OCl(=O)(=O)=O KBJCHZXIAAWHMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- UAGLZAPCOXRKPH-UHFFFAOYSA-N nitric acid;1,2,3-triaminoguanidine Chemical compound O[N+]([O-])=O.NNC(NN)=NN UAGLZAPCOXRKPH-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- ZFLIKDUSUDBGCD-UHFFFAOYSA-N parabanic acid Chemical compound O=C1NC(=O)C(=O)N1 ZFLIKDUSUDBGCD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fireproofing Substances (AREA)
Description
Die vorliegende Erfindung betrifft eine azidfreie, gaserzeugende Zusammensetzung, insbesondere zur Verwendung in Sicherheitseinrichtungen für Kraftfahrzeuge.The present invention relates to an azide-free gas-generating composition, in particular for use in safety devices for motor vehicles.
Die US-A-5,780,768 beschreibt eine derartige Zusammensetzung, die ein Brennstoffgemisch aus der Guanidinnitrat, Nitroguanidin und deren Gemischen bestehenden Gruppe sowie einen anorganischen Oxidator umfaßt, der aus der aus Cerammoniumnitrat, Lithiumnitrat, Lithiumperchlorat, Natriumperchlorat, Gemischen von Ammoniumperchlorat und wenigstens einem Alkalimetallsalz, sowie Mischungen davon, ausgewählt ist. Das Oxidator-Brennstoff-Gemisch weist eine Sauerstoffbilanz von zwischen +4% und -4% auf. Der Anteil an festen Verbrennungsrückständen des Gemisches soll nicht größer als 30 Gew.-% sein.US-A-5,780,768 describes such a composition, which comprises a fuel mixture from the group consisting of guanidine nitrate, nitroguanidine and mixtures thereof, as well as an inorganic oxidizer selected from the group consisting of cerium ammonium nitrate, lithium nitrate, lithium perchlorate, sodium perchlorate, mixtures of ammonium perchlorate and at least one alkali metal salt, and mixtures thereof. The oxidizer-fuel mixture has an oxygen balance of between +4% and -4%. The proportion of solid combustion residues in the mixture should not be greater than 30% by weight.
Die bekannten gaserzeugenden Zusammensetzungen weisen jedoch im allgemeinen Verbrennungstemperaturen von über 2200 K auf. Die hohen Verbrennungstemperaturen begünstigen aber die Bildung von Kohlenmonoxid und Stickoxiden und haben somit höhere Schadgasemissionen zur Folge. Ferner entstehen Probleme mit den neuerdings verwendeten unbeschichteten Airbag-Materialien. Die zum Auffangen der aus demHowever, the known gas-generating compositions generally have combustion temperatures of over 2200 K. The high combustion temperatures, however, promote the formation of carbon monoxide and nitrogen oxides and thus result in higher emissions of harmful gases. Furthermore, problems arise with the uncoated airbag materials that have recently been used. The
Ammoniumperchlorat freigesetzten Salzsäure verwendeten hohen Mengen an Alkalimetallsalzen verursachen darüber hinaus einen hohen Feinstaubgehalt im erzeugten Gasgemisch.The high amounts of alkali metal salts used in the hydrochloric acid released by ammonium perchlorate also cause a high level of particulate matter in the gas mixture produced.
Es besteht daher weiterhin Bedarf an gaserzeugenden Zusammensetzungen, mit denen die vorgenannten Nachteile vermieden werden können.There is therefore still a need for gas-generating compositions that can avoid the aforementioned disadvantages.
Die Erfindung stellt hierzu eine azidfreie, gaserzeugende Zusammensetzung bereit, die einen Brennstoff und einen anorganischen Oxidator umfaßt. Das erfindungsgemäße Gemisch ist dadurch gekennzeichnet, daß der Brennstoff eine Bildungsenthalpie von kleiner als -3,35 kJ/g und eine Sauerstoffbilanz von größer als -90% aufweist, daß der anorganische Oxidator aus der Gruppe der Metallchlorate, Metallperchlorate und Ammoniumperchlorat, der Alkalimetallnitrate und Erdalkalimetallnitrate sowie deren Mischungen ausgewählt ist, und daß die Sauerstoffbilanz der Zusammensetzung zwischen 0 und -4% liegt.For this purpose, the invention provides an azide-free, gas-generating composition which comprises a fuel and an inorganic oxidizer. The mixture according to the invention is characterized in that the fuel has an enthalpy of formation of less than -3.35 kJ/g and an oxygen balance of greater than -90%, that the inorganic oxidizer is selected from the group of metal chlorates, metal perchlorates and ammonium perchlorate, alkali metal nitrates and alkaline earth metal nitrates and mixtures thereof, and that the oxygen balance of the composition is between 0 and -4%.
Unter der Sauerstoffbilanz einer Verbindung oder eines Gemisches wird diejenige Sauerstoffmenge in Gewichtsprozent verstanden, die bei vollständiger Umsetzung der Verbindung oder des Gemisches zu beispielsweise CO2, H2O, AI2O3, B2O3 frei wird (02-Überbilanzierung).The oxygen balance of a compound or mixture is the amount of oxygen in percent by weight that is released when the compound or mixture is completely converted to, for example, CO2, H2O, AI2O3, B2O3 (O2 overbalance).
Reicht der vorhandene Sauerstoff hierzu nicht aus, so wird die zum vollständigen Umsatz notwendige Fehlmenge an Sauerstoff mit negativemIf the available oxygen is not sufficient for this, the missing amount of oxygen required for complete conversion is replaced by negative
25 Vorzeichen angegeben (02-Unterbilanzierung).25 signs specified (02 under-balancing).
Die Sauerstoffbilanz des Brennstoffs ist erfindungsgemäß bevorzugtThe oxygen balance of the fuel is preferably
größer als -80%. Besonders bevorzugt ist der Brennstoff aus der aus Cyanursäure, Harnstoff, Oxamid, Urazol, Dialursäure, Biurea, Urazol, Alloxan, Alloxantin, Parabansäure und deren Mischungen bestehenden Gruppe ausgewählt. Am meisten bevorzugt ist Cyanursäure.greater than -80%. More preferably, the fuel is selected from the group consisting of cyanuric acid, urea, oxamide, urazole, dialuric acid, biurea, urazole, alloxan, alloxantin, parabanic acid and mixtures thereof. Most preferred is cyanuric acid.
Der anorganische Oxidator ist bevorzugt Natriumnitrat, Lithiumnitrat, Kaliumnitrat oder eine Mischung davon. Weiterhin ist bevorzugt, als anorganischen Oxidator eine Mischung aus Ammoniumperchlorat und einem Alkalimetallnitrat einzusetzen, wobei das Alkalimetallnitrat aus der aus Natriumnitrat, Lithiumnitrat, Kaliumnitrat oder deren Mischungen bestehenden Gruppe ausgewählt ist. In vorteilhafter WeiseThe inorganic oxidizer is preferably sodium nitrate, lithium nitrate, potassium nitrate or a mixture thereof. It is also preferred to use a mixture of ammonium perchlorate and an alkali metal nitrate as the inorganic oxidizer, the alkali metal nitrate being selected from the group consisting of sodium nitrate, lithium nitrate, potassium nitrate or mixtures thereof. Advantageously
kann auch eine Mischung aus Ammoniumperchlorat und Strontiumnitrat als Oxidator eingesetzt werden.A mixture of ammonium perchlorate and strontium nitrate can also be used as an oxidizer.
Die erfindungsgemäße gaserzeugende Zusammensetzung kann ferner bis zu 10 Gew.-%, bezogen auf die Gesamtzusammensetzung, eines Abbrandbeschleunigers enthalten, der aus der Gruppe Guanidincarbonat, Guanidinnitrat, Guanidinperchlorat, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Nitroguanidin und deren Mischungen ausgewählt ist.The gas-generating composition according to the invention can further contain up to 10% by weight, based on the total composition, of a combustion accelerator selected from the group consisting of guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine and mixtures thereof.
Der Zusammensetzung können darüber hinaus in vorteilhafter Weise Abbrandmoderatoren in einem Anteil von bis zu 5 Gew.-%, bezogen auf die Gesamtzusammensetzung, zugesetzt werden, die aus der Gruppe Cr2Ü3, MnO2, Fe2C>3, Fe3Ü4, CuO, Q12O und deren Mischungen ausgewählt sind.Furthermore, combustion moderators selected from the group Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Q12O and mixtures thereof can advantageously be added to the composition in a proportion of up to 5 wt.%, based on the total composition.
Schließlich kann das Gemisch noch übliche Verarbeitungshilfen in einem Anteil von bis zu 3 Gew.-% enthalten. Die Verarbeitungshilfen sind bevorzugt aus der Gruppe der Rieselhilfen, Preßhilfsmittel und/oder Gleitmittel ausgewählt.Finally, the mixture can also contain conventional processing aids in a proportion of up to 3% by weight. The processing aids are preferably selected from the group of flow aids, pressing aids and/or lubricants.
Besonders bevorzugte erfindungsgemäße Zusammensetzungen bestehen aus 30 bis 45 Gew.-% Cyanursäure, 0 bis 5 Gew.-% Guanidinnitrat, 10 bis 35 Gew.-% Natriumnitrat, 20 bis 50 Gew.-% Ammoniumperchlorat sowie jeweils 0 bis 2 Gew.-% CuO und Fe2O3. Eine weitere, besonders bevorzugte Zusammensetzung besteht aus 30 bis 45 Gew.-% Cyanursäure, 0 bis 5 Gew.-% Guanidinnitrat, 10 bis 35 Gew.-% Strontiumnitrat, 20 bis 50 Gew.-% Ammoniumperchlorat sowie jeweils 0 bis 2 Gew.-% CuO undParticularly preferred compositions according to the invention consist of 30 to 45% by weight of cyanuric acid, 0 to 5% by weight of guanidine nitrate, 10 to 35% by weight of sodium nitrate, 20 to 50% by weight of ammonium perchlorate and 0 to 2% by weight of each of CuO and Fe2O3. Another, particularly preferred composition consists of 30 to 45% by weight of cyanuric acid, 0 to 5% by weight of guanidine nitrate, 10 to 35% by weight of strontium nitrate, 20 to 50% by weight of ammonium perchlorate and 0 to 2% by weight of each of CuO and
Die erfindungsgemäßen Zusammensetzungen zeichnen sich im Vergleich zu den in der US 5,780,768 beschriebenen Zusammensetzungen durch äußerst niedrige Verbrennungstemperaturen von unterhalb 2200 K sowie eine gute Anzündwilligkeit in Verbindung mit einer ausreichend hohen Abbrandgeschwindigkeit aus. Die Kohlenmonoxid- und Stickoxidanteile im freigesetzten Gasgemisch sind ebenfalls erheblich niedriger. Die erfindungsgemäßen Zusammensetzungen ergeben zudem eine hoheThe compositions according to the invention are characterized by extremely low combustion temperatures of below 2200 K as well as a good ignition readiness in conjunction with a sufficiently high burning rate in comparison to the compositions described in US 5,780,768. The carbon monoxide and nitrogen oxide contents in the released gas mixture are also considerably lower. The compositions according to the invention also result in a high
Gasausbeute bei deutlich verringertem Partikelausstoß.Gas yield with significantly reduced particle emissions.
AIs günstig für die Erzeugung möglichst niedriger Verbrennungstemperaturen und damit niedrigerer Schadgasemissionen hat sich die Verwendung eines C, H, N und O enthaltenden Brennstoffs mit einer Bildungsenthalpie AHf von kleiner als -3,35 kJ/g erwiesen, dessen Sauerstoffbilanz gleichzeitig größer als -90% ist. Damit ist gewährleistet, daß der Anteil an Oxidator in der Zusammensetzung gering gehalten werden kann. Geeignete Brennstoffe, mit denen die Sauerstoffbilanz verbessert oder nur geringfügig beeinflußt werden kann, ohne die Bildungswärmen AHf zu stark anzuheben, sind organische Verbindungen, die beispielsweise C = O, -OH, -CO2H, -NH2, nicht jedoch NO2, als Substitutenten enthalten. Die im Stand der Technik beschriebenen Substanzen Guanidinnitrat (AHf = -3,18 kJ/g, Sauerstoffbilanz = -26,2%) und Nitroguanidin (AHf = -0,88 kJ/g, Sauerstoffbilanz = -30,7%) ergeben bei gleicher Sauerstoffbilanz der Mischung mit einem vorgegebenen Oxidator höhere Verbrennungstemperaturen als die erfindungsgemäß bevorzugten Verbindungen, wie z.B. Cyanursäure, Harnstoff, Oxamid, Urazol, Dialursäure und Biurea.The use of a fuel containing C, H, N and O with an enthalpy of formation AHf of less than -3.35 kJ/g and whose oxygen balance is at the same time greater than -90% has proven to be beneficial for generating the lowest possible combustion temperatures and thus lower harmful gas emissions. This ensures that the proportion of oxidizer in the composition can be kept low. Suitable fuels with which the oxygen balance can be improved or only slightly influenced without increasing the heats of formation AHf too much are organic compounds that contain, for example, C = O, -OH, -CO2H, -NH2, but not NO2, as substitutes. The substances described in the prior art, guanidine nitrate (AHf = -3.18 kJ/g, oxygen balance = -26.2%) and nitroguanidine (AHf = -0.88 kJ/g, oxygen balance = -30.7%), result in higher combustion temperatures than the compounds preferred according to the invention, such as cyanuric acid, urea, oxamide, urazole, dialuric acid and biurea, with the same oxygen balance of the mixture with a given oxidizer.
In manchen Fällen kann es jedoch vorteilhaft sein, Guanidinnitrat oder eine andere Guanidinverbindung in geringen Mengen von bis zuHowever, in some cases it may be beneficial to use guanidine nitrate or another guanidine compound in small amounts of up to
10 Gew.-% als Beschleuniger zuzusetzen.10 wt.% as an accelerator.
Überraschenderweise wurde gefunden, daß bei Verwendung eines Gemisches aus Ammoniumperchlorat und Alkalimetallnitraten oder Erdalkalimetallnitrat als Oxidator der Anteil der Alkali- oder Erdalkalimetallsalze im Oxidatorgemisch auch unter die zum Auffangen der aus dem Ammoniumperchlorat freigesetzten Salzsäure notwendige stöchiometrische Menge verringert werden kann, ohne daß im freigesetzten Gasgemisch nennenswerte Mengen an Salzsäure nachzuweisen wären. Auch diese Maßnahme trägt zur Verringerung des Feststoffanteils im GasSurprisingly, it was found that when using a mixture of ammonium perchlorate and alkali metal nitrates or alkaline earth metal nitrate as an oxidizer, the proportion of alkali or alkaline earth metal salts in the oxidizer mixture can be reduced to below the stoichiometric amount required to capture the hydrochloric acid released from the ammonium perchlorate, without detecting significant amounts of hydrochloric acid in the released gas mixture. This measure also contributes to reducing the proportion of solids in the gas.
gemisch bei.mixture.
Das molare Verhältnis von Ammoniumperchlorat zu Alkalinitrat kann dabei zwischen 1,05:1 und 6:1, bevorzugt zwischen 1,5:1 und 3,5:1, variieren. Das molare Verhältnis von Ammoniumperchlorat und Erdalkalinitrat liegt entsprechend zwischen 1,05:0,5 und 6:0,5, bevorzugt zwischen 1,5:0,5 und 3,5:0,5.The molar ratio of ammonium perchlorate to alkali nitrate can vary between 1.05:1 and 6:1, preferably between 1.5:1 and 3.5:1. The molar ratio of ammonium perchlorate and alkaline earth nitrate is accordingly between 1.05:0.5 and 6:0.5, preferably between 1.5:0.5 and 3.5:0.5.
Schließlich wurde gefunden, daß im Gegensatz zu der in den Ausführungsbeispielen der US-A 5,780,768 angegebenen Überbilanzierung an Sauerstoff die Einstellung einer Sauerstoffbilanz von zwischen 0 und -4% weitaus günstiger ist, da der Grenzwert für das bevorzugt bei Sauerstoffüberbilanzierung entstehende NOx wesentlich niedriger ist als der Grenzwert für das bei bevorzugt bei Unterbilanzierung entstehende Kohlenmonoxid.Finally, it was found that, in contrast to the oxygen overbalance specified in the embodiments of US-A 5,780,768, the setting of an oxygen balance of between 0 and -4% is far more favorable, since the limit value for the NO x which is preferentially produced in the case of oxygen overbalance is considerably lower than the limit value for the carbon monoxide which is preferentially produced in the case of underbalance.
Die Erfindung wird nachfolgend anhand einiger Ausführungsbeispiele beschrieben, die jedoch nicht in einem einschränkenden Sinn zu verThe invention is described below using some embodiments, which, however, are not to be interpreted in a restrictive sense.
stehen sind.are standing.
wurden gemeinsam in eine Kugelmühle eingewogen, 3 Stunden lang gemahlen und miteinander vermischt. Das erhaltene Gemisch wurde ohne weitere Verarbeitungsschritte direkt zu Tabletten verpreßt.were weighed together in a ball mill, ground for 3 hours and mixed together. The resulting mixture was pressed directly into tablets without any further processing steps.
Das so erhaltene Gemisch wurde in einer geschlossenen 60 1-Kanne gezündet. Der auf diese Weise ermittelte maximale Kannendruck betrugThe mixture thus obtained was ignited in a closed 60 liter can. The maximum can pressure determined in this way was
216 kPa. Die Kohlenmonoxidkonzentration im freigesetzten Gasgemisch,
gemessen in einer 2,5 m^ Kammer, betrug 289 ppm, die &Ngr;&Ogr;&khgr;-Konzentration
betrug 56 ppm. Der ausgestoßene Feinstaub lag bei 1,05 g. Die berechnete Verbrennungstemperatur betrug 2165 K.
30216 kPa. The carbon monoxide concentration in the released gas mixture, measured in a 2.5 m^ chamber, was 289 ppm, the �Ngr;�Ogr;θ concentration was 56 ppm. The fine dust emitted was 1.05 g. The calculated combustion temperature was 2165 K.
30
372 g mikronisiertes Guanidinnitrat,372 g micronized guanidine nitrate,
144,2 g Ammoniumperchlorat und 35 83,8 g Natriumnitrat144.2 g ammonium perchlorate and 35 83.8 g sodium nitrate
wurden gemeinsam in eine Kugelmühle eingewogen, 3 Stunden lang gemahlen und miteinander vermischt. Das so erhaltene Gemisch wurdewere weighed together in a ball mill, ground for 3 hours and mixed together. The resulting mixture was
-6-ohne
weitere Verarbeitungsschritte direkt zu Tabletten verpreßt.-6-without
further processing steps directly pressed into tablets.
Der Kannenversuch (60 1) ergab einen maximalen Kannendruck vonThe can test (60 1) resulted in a maximum can pressure of
207 kPa. Die CO-Konzentration im Gasgemisch (2,5 m3) betrug 570 ppm, die NOx-Konzentration betrug 117 ppm. Der Feinstaubanteil wurde zu 1,42 g bestimmt. Die berechnete Verbrennungstemperatur lag bei207 kPa. The CO concentration in the gas mixture (2.5 m3) was 570 ppm, the NO x concentration was 117 ppm. The fine dust content was determined to be 1.42 g. The calculated combustion temperature was
2355 K.2355 K.
In der nachfolgenden Tabelle sind erfindungsgemäße Zusammensetzungen, einschließlich der Sauerstoffbilanz des verwendeten Brennstoffs, dessen Bildungsenthalpie AHf sowie die berechnete Verbrennungstemperatur der Zusammensetzung angegeben und entsprechenden Gemischen mit Guanidinnitrat und Nitroguanidin gegenübergestellt. In den jeweiligen Zusammensetzungen liegen Brennstoff und Oxidator im stöchiometrischen Verhältnis vor.The following table shows compositions according to the invention, including the oxygen balance of the fuel used, its enthalpy of formation AHf and the calculated combustion temperature of the composition, and compares them with corresponding mixtures with guanidine nitrate and nitroguanidine. In the respective compositions, fuel and oxidizer are present in a stoichiometric ratio.
BrennstoffO 2 balance
fuel
Brennstoff
[Gew.-%]Portion
fuel
[Wt.%]
[Gew.-%]KNO3
[Wt.%]
Verbrennungs
temperatur [K]calculated
Combustion
temperature [K]
beipiel Nr.Comparison
example no.
Claims (17)
35Total composition contains up to 10 wt.% of combustion accelerators selected from the group consisting of guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine and mixtures thereof.
35
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29821544U DE29821544U1 (en) | 1998-12-02 | 1998-12-02 | Azide-free, gas generating composition |
| DE59909590T DE59909590D1 (en) | 1998-12-02 | 1999-12-01 | AZIDFREE, GAS-CREATING COMPOSITION |
| PCT/EP1999/009382 WO2000032541A1 (en) | 1998-12-02 | 1999-12-01 | Acid-free, gas-generating composition |
| EP99961043A EP1051373B1 (en) | 1998-12-02 | 1999-12-01 | Acid-free, gas-generating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29821544U DE29821544U1 (en) | 1998-12-02 | 1998-12-02 | Azide-free, gas generating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE29821544U1 true DE29821544U1 (en) | 1999-02-18 |
Family
ID=8066130
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE29821544U Expired - Lifetime DE29821544U1 (en) | 1998-12-02 | 1998-12-02 | Azide-free, gas generating composition |
| DE59909590T Expired - Lifetime DE59909590D1 (en) | 1998-12-02 | 1999-12-01 | AZIDFREE, GAS-CREATING COMPOSITION |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE59909590T Expired - Lifetime DE59909590D1 (en) | 1998-12-02 | 1999-12-01 | AZIDFREE, GAS-CREATING COMPOSITION |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1051373B1 (en) |
| DE (2) | DE29821544U1 (en) |
| WO (1) | WO2000032541A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001019760A2 (en) * | 1999-09-13 | 2001-03-22 | Dynamit Nobel Gmbh | Gas-generating mixtures |
| EP1114010A1 (en) * | 1998-07-25 | 2001-07-11 | Breed Automotive Technology, Inc. | Gas generant compositions containing guanadines |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2959508B1 (en) * | 2010-04-29 | 2015-01-02 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING |
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| DE4401214C1 (en) | 1994-01-18 | 1995-03-02 | Fraunhofer Ges Forschung | Gas-generating mixture |
| DE4401213C1 (en) | 1994-01-18 | 1995-03-02 | Fraunhofer Ges Forschung | Gas-generating mixture |
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| US5842325A (en) * | 1997-12-11 | 1998-12-01 | Bausch & Lomb Incorporated | Method for labeling packages |
| FR2772370B1 (en) * | 1997-12-12 | 2000-01-07 | Poudres & Explosifs Ste Nale | PYROTECHNIC COMPOSITIONS GENERATING NON-TOXIC GASES BASED ON AMMONIUM PERCHLORATE |
| KR100381107B1 (en) * | 1998-02-25 | 2003-04-18 | 니뽄 가야쿠 가부시키가이샤 | Gas generator composition |
| CA2333942A1 (en) * | 1998-06-10 | 2000-01-06 | Robert S. Scheffee | Pyrotechnic gas generant composition including high oxygen balance fuel |
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| DE29821541U1 (en) * | 1998-12-02 | 1999-02-18 | TRW Airbag Systems GmbH & Co. KG, 84544 Aschau | Azide-free, gas generating composition |
-
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- 1998-12-02 DE DE29821544U patent/DE29821544U1/en not_active Expired - Lifetime
-
1999
- 1999-12-01 EP EP99961043A patent/EP1051373B1/en not_active Expired - Lifetime
- 1999-12-01 WO PCT/EP1999/009382 patent/WO2000032541A1/en active IP Right Grant
- 1999-12-01 DE DE59909590T patent/DE59909590D1/en not_active Expired - Lifetime
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| DE4233088A1 (en) | 1991-10-07 | 1993-04-08 | Kvaerner Eureka As | Safety device partic. for protecting operators when belt fitting - has emergency stop switch connected to cord carried on arms which move with tensioning roller to be always within reach |
| DE4411654A1 (en) | 1993-10-20 | 1995-04-27 | Temic Bayern Chem Airbag Gmbh | Gas-generating mixture |
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| EP1114010A1 (en) * | 1998-07-25 | 2001-07-11 | Breed Automotive Technology, Inc. | Gas generant compositions containing guanadines |
| EP1114010A4 (en) * | 1998-07-25 | 2002-07-17 | Breed Automotive Tech | Gas generant compositions containing guanadines |
| WO2001019760A2 (en) * | 1999-09-13 | 2001-03-22 | Dynamit Nobel Gmbh | Gas-generating mixtures |
| WO2001019760A3 (en) * | 1999-09-13 | 2001-10-18 | Dynamit Nobel Gmbh | Gas-generating mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1051373A1 (en) | 2000-11-15 |
| EP1051373B1 (en) | 2004-05-26 |
| WO2000032541A1 (en) | 2000-06-08 |
| DE59909590D1 (en) | 2004-07-01 |
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