EP1064242A1 - Propellants for gas generator - Google Patents

Propellants for gas generator

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Publication number
EP1064242A1
EP1064242A1 EP99919100A EP99919100A EP1064242A1 EP 1064242 A1 EP1064242 A1 EP 1064242A1 EP 99919100 A EP99919100 A EP 99919100A EP 99919100 A EP99919100 A EP 99919100A EP 1064242 A1 EP1064242 A1 EP 1064242A1
Authority
EP
European Patent Office
Prior art keywords
gas generator
component
weight
fuel according
generator fuel
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.)
Granted
Application number
EP99919100A
Other languages
German (de)
French (fr)
Other versions
EP1064242B1 (en
Inventor
Eduard Gast
Bernhard Schmid
Peter Semmler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nigu Chemie GmbH
Original Assignee
Nigu Chemie GmbH
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Filing date
Publication date
Application filed by Nigu Chemie GmbH filed Critical Nigu Chemie GmbH
Publication of EP1064242A1 publication Critical patent/EP1064242A1/en
Application granted granted Critical
Publication of EP1064242B1 publication Critical patent/EP1064242B1/en
Anticipated expiration legal-status Critical
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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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt

Definitions

  • the invention relates to solid gas generator fuels (gas-generating mixtures), mainly for gas generator propellants for airbags and belt tensioners based on nitrogen-rich and low-carbon fuels, the solid gas generator fuels additionally containing a high-melting, essentially chemically inert slag trap in highly dispersed form, which acts as an internal filter acts and largely prevents the formation and escape of dust-like particles from the gas generator housing.
  • solid gas generator fuels gas-generating mixtures
  • the solid gas generator fuels additionally containing a high-melting, essentially chemically inert slag trap in highly dispersed form, which acts as an internal filter acts and largely prevents the formation and escape of dust-like particles from the gas generator housing.
  • the invention thus relates to a method for trapping the liquid or solid combustion products or dust-like slag parts within the gas generator propellant immediately as they arise, so that one can manage with a simply structured filter package in the gas generator housing.
  • the invention further relates to the use of catalysts based on platinum metals (Ru, Os, Rh, Ir, Pd, Pt) or metal alloys of platinum metals or copper on the slag catchers as carriers in solid gas generator fuels, in particular the use in solid gas generator propellants for airbags.
  • platinum metals Ru, Os, Rh, Ir, Pd, Pt
  • metal alloys of platinum metals or copper on the slag catchers as carriers in solid gas generator fuels, in particular the use in solid gas generator propellants for airbags.
  • An airbag essentially consists of a gas generator housing, which is filled with the gas generator drive unit, usually in tablet form, and an initial igniter (squib) for igniting the gas generator drive unit, and a gas bag.
  • squib initial igniter
  • Suitable igniters are described, for example, in US Pat. No. 4,931,111.
  • the initially small-folded gas bag is filled after the initial ignition with the gases generated when the gas generator propellant burns up and reaches its full volume in a period of about 10-50 ms.
  • Escaping hot sparks, melts or solids from the gas generator into the gas bag must be largely prevented, since it could lead to the gas bag being destroyed or injuring vehicle occupants. This is achieved by binding and filtering the slag that is produced when the gas generator propellant is burned.
  • DE-A-44 35 790 discloses gas generator fuels based on guanidine compounds on suitable carriers, which essentially have improved combustion behavior and improved slag formation.
  • DE-A-44 35 790 gives no information on the use of high-melting, essentially inert slag catchers in highly dispersed form or of catalysts in gas generator propellants.
  • the gas-generating mixture described in EP-B-0 482 852 contains a) a fuel selected from aminotetrazole, tetrazole, bitetrazole and metal salts of these compounds and triazole compounds and metal salts of triazole compounds; b) an oxygen-containing oxidation compound selected from alkali metal, alkaline earth metal, lanthanide and ammonium nitrates and perchlorates and alkali metal and alkaline earth metal chlorates and peroxides; and either c) a high temperature slag formation material selected from alkaline earth metal oxides, hydroxides, carbonates, oxalates, peroxides, nitrates, chlorates and perchlorates and alkaline earth metal salts of tetrazoles, bitetrazoles and triazoles, and d) a low temperature
  • nitrates, perchlorates and chlorates and alkali metal salts of tetrazoles, bitetrazoles and triazoles or e) a high temperature slag formation material selected from transition metal oxides, hydroxides, carbonates, oxalates, peroxides, nitrates, chlorates and perchlorates; and f) a low temperature slag forming material which is silicon dioxide; wherein the amount of d) or f) is sufficient to result in the formation of a coherent mass or slag, but is not so high that a liquid with low viscosity is formed, it being understood that a single material for more than one of the Categories can serve.
  • the main advantage of such a gas generator propellant lies in the favorable formation of a slag which can easily be filtered off from the gaseous combustion products formed. Another advantage is the high gas yield.
  • Airbags described in which a primary gas mixture is initially created by the ignition of a gas generator propellant, which contains at least one tetrazole or triazole compound as fuel, and this primary mixture is diluted by mixing with ambient air in such a way that the content of toxic gaseous combustion products from the primary gas mixture is reduced to a toxicologically acceptable level.
  • DE-C-44 01 213 describes gas-generating mixtures of a fuel, an oxidizer, a "catalyst” and a coolant, characterized in that the oxidizer Cu (NO 3 ) 2 -3Cu (OH) 2 and the catalyst a metal oxide or a metal oxide mixture or a metal mixed oxide is known.
  • DE-C-44 01 214 also discloses gas-generating mixtures of similar compositions in which the catalyst consists of a metal or a metal alloy, preferably a pyrophoric metal or a pyrophoric metal alloy on a support.
  • the carrier is a silicate, preferably a layered or framework silicate. Ag has proven particularly useful as a metal.
  • the known fuels used include triaminoguanidine nitrate (TAGN), nitroguanidine (NIGU or NQ), 3-nitro-l, 2,3-triazol-5-one and especially diguanidinium-5,5'-azotetrazolate (GZT).
  • the main advantage of the gas-generating mixtures described in the two above-mentioned German patents is said to be the lowering of the combustion temperature and the increase in the rate of combustion.
  • the gas-generating mixtures described in DE-C-44 01 213 and DE-C-44 01 214 do not contain any low- or high-melting slag formers or slag scavengers according to the invention; rather, it claims that there is no need for slag formers. Contrary to this claim, the inventors of the present invention have found that the use of low-melting and high-melting slag formers, in particular the slag trap according to the invention, brings about a significant reduction in toxic gaseous combustion products.
  • Part of the high-melting slag catcher according to the invention can act as a carrier for a platinum metal or for a metal alloy made of platinum metals and thus as a catalyst component.
  • catalyst is used in a broader sense and represents an active component of the reaction which can itself be implemented and has a reaction-directing and / or reaction-accelerating effect.
  • the definition of the catalyst also means that it is added to the reaction mixture in only a very low concentration.
  • the proportion of "catalyst" in the gas-generating mixture is up to 30% by mass and is therefore an essential, also proportionate, component of the gas-generating mixture.
  • the present invention is based on the object of providing improved gas generator fuels, in particular for airbags, the combustion behavior of which can be set in a targeted manner and which in particular the formation of 6
  • the gas generator propellants made from the gas generator fuels should be thermally stable, easy to ignite, quick - even at low temperature - to be flammable and storable and ensure a high gas yield.
  • these gas generator propellants should make it possible to downsize, reduce the number of components or simplify the gas generator housing and thus reduce their weight in comparison to known generators.
  • a gas generator fuel comprising
  • GDCA Guanidinium dicyanamide
  • AGB aminoguanidinium bicarbonate
  • a inoguanidinium nitrate AGN
  • triaminoguanidinium nitrate TAGN
  • NIGU nitroguanidine
  • DCD dicyandiamide
  • ADCA azodicarbonamide
  • HTZ tetrazole
  • ATZ 5-aminotetrazole
  • NTO NTO
  • At least one slag former selected from alkali and alkaline earth metal carbonates and oxides, silicates, aluminates and aluminum silicates, iron (III) oxide and silicon nitride (Si 3 N 4 ), which burns nitrogen (N 2 ) and silicon dioxide (SiO 2 ) for further reaction and 7
  • Preferred fuels are nitroguanidine (NIGU), 5-aminotetrazole (ATZ), dicyandiamide (DCD), dicyanamide, their salts, in particular sodium and calcium dicyanamide and guanidinium nitrate, and mixtures thereof.
  • NIGU nitroguanidine
  • ATZ 5-aminotetrazole
  • DCD dicyandiamide
  • dicyanamide their salts, in particular sodium and calcium dicyanamide and guanidinium nitrate, and mixtures thereof.
  • These are practically non-toxic, not hygroscopic, not very soluble in water, thermally stable, they burn at low temperatures and are not sensitive to impact and friction.
  • the gas yield during combustion is high, with a large proportion of nitrogen gas being generated.
  • Alkali Li, Na, K
  • alkaline earth salts Mg, Ca, Sr, Ba
  • alkali metal or alkaline earth metal nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate or barium nitrate
  • ammonium nitrate alkali metal or alkaline earth metal chlorates or perchlorates (such as lithium, sodium or potassium , Magnesium, calcium, strontium or barium chlorate and lithium, sodium, potassium, magnesium, calcium, strontium or barium perchlorate) and ammonium perchlorate and mixtures thereof.
  • Potassium nitrate and strontium nitrate are preferably used.
  • Strontium nitrate is non-hygroscopic, non-toxic and enables a high gas yield when burned. Potassium nitrate also has a low burning temperature.
  • Al, O 3 , TiO 2 and ZrO, in highly dispersed form or mixtures thereof, can be used as high-melting, essentially chemically inert slag catchers, component (C).
  • TiO 2 with a BET surface area of 50+ are particularly preferred / - 15 m 2 / g (melting point approx. 1850 ° C)
  • These highly disperse oxides are commercially available, for example, under the trade names aluminum oxide C, titanium oxide P25 and VP zirconium oxide (Degussa AG).
  • pyrogenic oxides are produced by reacting the metal chlorides with H 2 and O 2 in the appropriate molar ratio by means of a gas phase reaction (flame hydrolysis).
  • Slag scavenger (component (C)) for the purposes of the present invention is understood to mean high-melting, essentially chemically inert metal oxides in highly disperse form, i.e. these oxides have a much larger surface area than the oxides in their conventional form.
  • conventional Al 2 O 3 as the ⁇ -oxide has a BET surface area of only 5-10 m 2 / g
  • conventional pigment TiO 2 has a BET surface area of only 5-10 m 2 / g and conventional ZrO
  • a BET Surface area of only 3-8 m 2 / g for refractory products
  • the metal oxides BET surfaces used in the gas generator propellant sets of the present invention range from about 40 to about 100 m 2 / g, particularly preferably about 50 to about 100 have m 2 / g and in particular about 100 m 2 / g.
  • the slag catchers of the present invention are distinguished by their high melting point of approximately 1850 to approximately 2700 ° C. These high melting points mean that the slag catchers do not melt during the reaction and thus act as solids.
  • the slag scavengers of the present invention are essentially chemically inert compounds, ie the slag scavengers of the present invention do not participate in the combustion reaction of the gas generator propellants in chemical reactions or only to a small extent on the surface of the metal oxides serving as slag scavengers.
  • the high-resolution room grids ie the large inner surface of Al 2 O 3 , TiO 2 or ZrO 2 , on the one hand, cause the combustion products to cool down due to their inactivity and, on the other hand, specifically store liquid and / or solid slag parts or particles that arise during combustion .
  • the tablet form in which the gas generator propellants are used is preserved during and after the burn-up, or fragments that may have formed can be easily filtered. This means that there is hardly any dust that could escape from the gas generator propulsion unit and thus from the gas generator housing during combustion.
  • the slag catchers work 9
  • Respirable dust-like particles have a diameter of about 6 ⁇ m or smaller.
  • component (D) alkali metal and alkaline earth metal carbonates (such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate or barium carbonate), alkali metal or alkaline earth metal oxides (such as sodium, potassium, magnesium, calcium, strontium or barium oxide), silicates (such as hectorite), aluminates (such as sodium beta-aluminate (NajOnALjOj) or tricalcium aluminate (Ca 3 Al 2 O 6 )) or aluminum silicates (such as bentonites or zeolites) or iron (III) oxide or mixtures thereof become.
  • alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate or barium carbonate
  • alkali metal or alkaline earth metal oxides such as sodium, potassium, magnesium, calcium, strontium or barium oxide
  • silicates such as hectorite
  • aluminates such
  • Component (D) is used to form an easily filterable slag when the gas generator fuel burns.
  • the slag formers, component (D) can also act as a coolant.
  • the silicates, aluminates and aluminum silicates react with the alkali metal and alkaline earth metal oxides that are formed during the combustion.
  • the invention further relates to the use of catalysts based on platinum metals (Ru, Os, Rh, Ir, Pd, Pt) or metal alloys made of platinum metals or copper on the highly disperse slag traps as carriers, in the solid gas generator fuels of the present invention, in particular the use in fixed gas generator propellants for airbags. 10
  • platinum metals Ru, Os, Rh, Ir, Pd, Pt
  • metal alloys made of platinum metals or copper on the highly disperse slag traps as carriers
  • a part of the slag catcher (component (C)) can serve as a support on which a platinum metal or a metal alloy made of platinum metals or copper is applied in a catalytically effective layer thickness.
  • Platinum metals are ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt).
  • the catalysts used in the present invention are preferably based on Rh, Pd or Pt and in particular Pt.
  • metal alloys made of platinum metals are all catalytically active metal alloys of the platinum metals mentioned above, preferably Pt / Pd and Pt / Rh alloys.
  • the metals or metal alloys made of platinum metals are applied to the support in a catalytically effective layer thickness, preferably in a one-atom layer (“monolayer”).
  • the catalytic converters are only contained in catalytic quantities in the gas generator propulsion unit.
  • Their weight fraction in component (C) is 0.1-5% by weight, preferably 0.2-1.2% by weight of component (C).
  • Preferred catalysts are those in which the highly disperse support A1 2 0 3 and the metal is Pt, Pd or Cu, in particular Pt.
  • Suitable catalysts are available from Degussa AG, for example 1% Pt on gamma-Al 2 0 3 or 1% Pd + Pt on gamma-Al 2 O 3 .
  • the catalysts serve to control the reaction so that hardly toxic gaseous combustion products such as carbon monoxide (CO), nitrogen oxides (NO x ) and ammonia (NH 3 ) are formed.
  • CO carbon monoxide
  • NO x nitrogen oxides
  • NH 3 ammonia
  • the catalysts mentioned above are particularly well suited for use in gas generator propellants in airbags. 11
  • the catalysts can be triggered, i.e. used airbags, as well as from non-deployed, i.e. can be recycled from airbags from old motor vehicles according to already known methods. This leads to less pollution of the environment and enables the catalyst metals to be reused.
  • the catalyst metal or the metal alloy is not oxidized during the combustion.
  • the catalyst does not have to be added to the gas generator propulsion unit as an additional component, but the catalyst is part of a component (component C) which is already present in the gas generator propulsion unit.
  • Component (A) is present in an amount of approximately 20 to 60% by weight, preferably approximately 28 to 52% by weight and in particular approximately 45 to 51% by weight, component (B) in an amount of approximately 38 to about 63% by weight, preferably from about 38 to about 55% by weight and in particular from about 39 to 45% by weight, component (C) in an amount of from about 5 to 22% by weight, preferably from about 8 to 20% by weight and in particular from about 9 to 11% by weight and component (D), if present, in an amount of from about 2 to 12% by weight, preferably from about 4 to 10% by weight .-% before, each based on the total composition of the gas generator propellant.
  • the gas generator fuel may also contain, as component (E), a binder which is soluble in water at room temperature.
  • binders are cellulose compounds or polymers made from one or more polymerizable olefinically unsaturated monomers.
  • cellulose compounds are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose ethers, in particular methyl hydroxyethyl cellulose.
  • a usable methylhydroxyethyl cellulose is CULMINAL® MHEC 30000 PR from Aqualon.
  • Suitable polymers with binding action are polyvinylpyrrolidone, polyvinyllace- 12
  • a metal salt of stearic acid such as aluminum stearate, magnesium stearate, calcium stearate or zinc stearate, which is insoluble in water at room temperature, can also be used as the binder, component (E).
  • Graphite is also suitable as a binder.
  • Component (E) is present in an amount of 0 to 2% by weight and preferably 0.3-0.8% by weight.
  • the binder, component (E) serves as a desensitizing agent and as a processing aid in the production of granules or tablets (pellets) from the gas generator fuel. It also serves to reduce the hydrophilicity and to stabilize the gas generator propellants.
  • gas generator fuels Examples 1 to 57 of Table I below
  • gas generator propellants were produced according to the following procedure:
  • the roughly premixed raw materials (components (A), (B), (C) and optionally (D) and
  • the tablets or pellets from the gas generator fuel used in the gas generators can be produced by known processes, for example by extrusion, extrusion, in rotary presses or tableting machines.
  • the size of the pellets or tablets depends on the desired burning time in the respective application.
  • the gas generator fuel according to the invention consists of non-toxic, easily manufactured and inexpensive components, the processing of which is unproblematic.
  • the component that is less cost-effective, namely the catalyst metal, can be recycled using known methods.
  • the thermal stability of the components results in a good shelf life.
  • the mixtures are easy to ignite. They burn quickly and deliver large gas yields with very low CO, NO x and NH 3 contents, which are below the permissible maximum limit.
  • the mixtures according to the invention are therefore particularly suitable for use as gas generants in the various airbag systems, as extinguishing agents or propellants.
  • Examples 1 to 57 below illustrate the invention but do not limit it.
  • Examples 15, 18 and 21 are comparative examples in which conventional ZrO 2 , TiO 2 and Al 2 O 3 were used.
  • A ATZ [%] 30.2 32.8 29.75 29J 29.75 29.7
  • Nitrogen oxides [ppm] 150 300 200 350 200 250
  • Coarse dust in the can [g] 1, 2 0.6 1, 2 1, 0 1, 1 1, 2
  • Fine dust in the jug [g] 0.2 0.1 0.3 0.3 0.3 0.3 15
  • Nitrogen oxides [ppm] 200 250 200 250 400 250
  • A ATZ [%] - - - - - - - -
  • A ATZ [%] - - - - - - - -
  • A ATZ [%] - - - - - - - -
  • Nitrogen oxides [ppm] 250 250 400 450 150 900
  • A ATZ [%] - - - - - - - -
  • Nitrogen oxides [ppm] 700 1000 800 500 800 100
  • A ATZ [%] - - - - - - - -
  • Nitrogen oxides [ppm] 300 800 500 1000 150 350
  • A ATZ [%] 17.7 - - - - - -
  • Nitrogen oxides [ppm] 150 400 150 800 100 500
  • Coarse dust in the can [g] 1, 0 2.0 1, 8 1, 5 1, 0 0.5
  • A ATZ [%] 29.75 30.2 30.2 26.5 26.8 33.7
  • Nitrogen oxides [ppm] 300 200 300 800 500 250
  • Coarse dust in the can [g] 1.0 1, 1 1, 2 0.8 1, 0 0.8
  • A ATZ [%] 30.35 31, 66 29.75
  • the burns were carried out in a practical gas generator housing for the 60 liter driver airbag, with original dimensions, lighter and filter package made of stainless steel.
  • the gas generator propellant weight used was 50 to 55 g, depending on the gas yield of the respective gas generator propellant formulation.
  • the pellets had a diameter of 4 to 6 mm, with a pellet height of 1.5 or 2.1 mm.
  • the gas yield and the temperature are in the range favorable for gas generator fuels for airbags.
  • the "coarse dust” and "fine dust” information in the table relates to the dirt in the jug after combustion.
  • the measured values for CO, NO x and NH 3 given in the table above refer to a 60 liter jug. These are good values for a non-optimized test gas generator.
  • compositions are those of Examples 14, 17 and 20.
  • thermodynamic data of the individual gas formulations were calculated based on the excess oxygen balance, which promised as little toxic gas development as possible on combustion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)
  • Catalysts (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Glass Compositions (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The present invention relates to solid propellants for gas generators (gas-generating mixtures), wherein said propellants are mainly intended for use in propelling charges for gas generators used in airbags or seat-belt pre-tensioning devices. The solid propellants for gas generators further include an essentially chemically-inert slag trap which has a high fusion point and a good dispersion, wherein said slag trap acts as an inner filter and globally prevents the formation of powder particles as well as their exit from the housing of the gas generator. A portion of the slag trap having a good dispersion may be used as a carrier substance for catalyst metals.

Description

GASGENERATORTREIBSTOFFE GAS GENERATOR FUELS
Die Erfindung betrifft feste Gasgeneratortreibstoffe (gaserzeugende Mischungen), hauptsächlich für Gasgeneratortreibsätze für Airbags und Gurtstraffer auf Basis von stickstoffreichen und möglichst kohlenstoffarmen Brennstoffen, wobei die festen Gasgenera- tortreibstoffe zusätzlich einen hochschmelzenden, im wesentlichen chemisch inerten Schlackenfänger in hochdisperser Form enthalten, der als internes Filter wirkt und die Entstehung und den Austritt von staubförmigen Teilchen aus dem Gasgeneratorgehäuse weitgehend verhindert.The invention relates to solid gas generator fuels (gas-generating mixtures), mainly for gas generator propellants for airbags and belt tensioners based on nitrogen-rich and low-carbon fuels, the solid gas generator fuels additionally containing a high-melting, essentially chemically inert slag trap in highly dispersed form, which acts as an internal filter acts and largely prevents the formation and escape of dust-like particles from the gas generator housing.
Die Erfindung betrifft somit ein Verfahren zum Abfangen der flüssigen bzw. festen Verbrennungsprodukte bzw. staubförmigen Schlackenteile innerhalb des Gasgeneratortreibsatzes unmitttelbar bei der Entstehung, so daß man mit einem einfach strukturierten Filterpaket im Gasgeneratorgehäuse auskommt.The invention thus relates to a method for trapping the liquid or solid combustion products or dust-like slag parts within the gas generator propellant immediately as they arise, so that one can manage with a simply structured filter package in the gas generator housing.
Die Erfindung betrifft ferner die Verwendung von Katalysatoren auf der Basis von Platinmetallen (Ru, Os, Rh, Ir, Pd, Pt) oder Metallegierungen aus Platinmetallen oder Kupfer auf den Schlackenfängern als Träger in festen Gasgeneratortreibstoffen, insbesondere die Verwendung in festen Gasgeneratortreibsätzen für Airbags.The invention further relates to the use of catalysts based on platinum metals (Ru, Os, Rh, Ir, Pd, Pt) or metal alloys of platinum metals or copper on the slag catchers as carriers in solid gas generator fuels, in particular the use in solid gas generator propellants for airbags.
Ein Airbag besteht im wesentlichen aus einem Gasgeneratorgehäuse, das mit dem Gasgeneratortreibsatz, in der Regel in Tablettenform, gefüllt ist, und einem Initialzünder (squib) zur Zündung des Gasgeneratortreibsatzes, sowie einem Gassack. Geeignete Zünder sind beispielsweise in der US-PS 4,931,111 beschrieben. Der zunächst kleingefaltete Gassack wird nach der Initialzündung von den beim Abbrand des Gasgeneratortreibsatzes entstehenden Gasen gefüllt und erreicht in einem Zeitraum von etwa 10-50 ms sein volles Volumen. Der 2An airbag essentially consists of a gas generator housing, which is filled with the gas generator drive unit, usually in tablet form, and an initial igniter (squib) for igniting the gas generator drive unit, and a gas bag. Suitable igniters are described, for example, in US Pat. No. 4,931,111. The initially small-folded gas bag is filled after the initial ignition with the gases generated when the gas generator propellant burns up and reaches its full volume in a period of about 10-50 ms. The 2
Austritt von heißen Funken, Schmelzen oder Festkörpern aus dem Gasgenerator in den Gassack muß weitgehend verhindert werden, da er zu einer Zerstörung des Gassacks oder zur Verletzung von Fahrzeuginsassen führen könnte. Dies wird durch Binden und Filtrieren der Schlacke erreicht, die bei der Verbrennung des Gasgeneratortreibsatzes entsteht.Escaping hot sparks, melts or solids from the gas generator into the gas bag must be largely prevented, since it could lead to the gas bag being destroyed or injuring vehicle occupants. This is achieved by binding and filtering the slag that is produced when the gas generator propellant is burned.
Herkömmliche Gasgeneratortreibsätze für die Verwendung in Airbags auf der Basis von Natriumazid sind seit längerem bekannt. Die Verwendung des hochtoxischen Natriumazids erfordert jedoch ein aufwendiges und kostspieliges Herstellungsverfahren der Gasgeneratortreibsätze. Zudem führt die weltweit ständig zunehmende Zahl von nicht abgebrannten Gas- generatortreibsätzen in Alt-Kraftfahrzeugen zu einem Entsorgungs- und Sicherheitsproblem.Conventional gas generator propellants for use in airbags based on sodium azide have long been known. However, the use of the highly toxic sodium azide requires a complex and costly production process for the gas generator propellants. In addition, the ever-increasing number of unburned gas generator propellants in old motor vehicles is causing a disposal and safety problem.
In den vergangenen Jahren wurden daher Anstrengungen unternommen, geeignete Ersatzstoffe für Natriumazid zu finden.In recent years, efforts have therefore been made to find suitable substitutes for sodium azide.
Aus der DE-A-44 35 790 sind Gasgeneratortreibstoffe auf der Basis von Guanidinverbindun- gen auf geeigneten Trägern bekannt, die im wesentlichen ein verbessertes Abbrandverhalten und eine verbesserte Schlackenbildung aufweisen. Die DE-A-44 35 790 gibt keine Hinweise auf die Verwendung von hochschmelzenden, im wesentlichen inerten Schlackenfängern in hochdisperser Form oder von Katalysatoren in Gasgeneratortreibsätzen.DE-A-44 35 790 discloses gas generator fuels based on guanidine compounds on suitable carriers, which essentially have improved combustion behavior and improved slag formation. DE-A-44 35 790 gives no information on the use of high-melting, essentially inert slag catchers in highly dispersed form or of catalysts in gas generator propellants.
Aus der EP-B-0 482 852 und dem dort zitierten Stand der Technik sind azidfreie Gasgeneratortreibsätze, insbesondere für Airbags, bekannt. Die in der EP-B-0 482 852 beschriebene, gaserzeugende Mischung enthält a) einen Treibstoff, ausgewählt aus Aminotetrazol, Tetrazol, Bitetrazol und Metallsalzen dieser Verbindungen und Triazolverbindungen und Metallsalzen von Triazolverbindungen; b) eine sauerstoffhaltige Oxidationsverbindung, ausgewählt aus Alkalimetall-, Erdalkalimetall-, Lanthanid- und Ammoniumnitraten und -perchloraten und Alkalimetall- und Erdalkalimetallchloraten und -peroxiden; und entweder c) ein Hochtemperatur-Schlackenbildungsmaterial, ausgewählt aus Erdalkalimetalloxiden, -hydroxiden, -carbonaten, -oxalaten, -peroxiden, -nitraten, -chloraten und -perchloraten und Erdalkalime- tallsalzen von Tetrazolen, Bitetrazolen und Triazolen, und d) ein Niedertemperatur- Schlackenbildungsmaterial, ausgewählt aus Siliciumdioxid, Boroxid, Vanadiumpentoxid, natürlich vorkommenden Tonen und Talken, Alkalimetallsilikaten, -boraten, -carbonaten, 3From EP-B-0 482 852 and the prior art cited therein, azide-free gas generator propellants, in particular for airbags, are known. The gas-generating mixture described in EP-B-0 482 852 contains a) a fuel selected from aminotetrazole, tetrazole, bitetrazole and metal salts of these compounds and triazole compounds and metal salts of triazole compounds; b) an oxygen-containing oxidation compound selected from alkali metal, alkaline earth metal, lanthanide and ammonium nitrates and perchlorates and alkali metal and alkaline earth metal chlorates and peroxides; and either c) a high temperature slag formation material selected from alkaline earth metal oxides, hydroxides, carbonates, oxalates, peroxides, nitrates, chlorates and perchlorates and alkaline earth metal salts of tetrazoles, bitetrazoles and triazoles, and d) a low temperature Slag formation material selected from silicon dioxide, boron oxide, vanadium pentoxide, naturally occurring clays and talc, alkali metal silicates, borates, carbonates, 3
-nitraten, -perchloraten und -chloraten und Alkalimetallsalzen von Tetrazolen, Bitetrazolen und Triazolen; oder e) ein Hochtemperatur-Schlackenbildungsmaterial, ausgewählt aus Übergangsmetalloxiden, -hydroxiden, -carbonaten, -oxalaten, -peroxiden, -nitraten, -chloraten- und perchloraten; und f) ein Niedertemperatur-Schlackenbildungsmaterial, welches Silici- umdioxid ist; wobei die Menge von d) oder f) ausreicht, um zur Bildung einer kohärenten Masse oder Schlacke zu führen, aber nicht so hoch ist, daß eine Flüssigkeit mit niederer Viskosität entsteht, wobei es sich versteht, daß ein einzelnes Material für mehr als eine der Kategorien dienen kann.nitrates, perchlorates and chlorates and alkali metal salts of tetrazoles, bitetrazoles and triazoles; or e) a high temperature slag formation material selected from transition metal oxides, hydroxides, carbonates, oxalates, peroxides, nitrates, chlorates and perchlorates; and f) a low temperature slag forming material which is silicon dioxide; wherein the amount of d) or f) is sufficient to result in the formation of a coherent mass or slag, but is not so high that a liquid with low viscosity is formed, it being understood that a single material for more than one of the Categories can serve.
Der wesentliche Vorteil eines derartigen Gasgeneratortreibsatzes liegt in der günstigen Bildung einer Schlacke, die leicht von den gebildeten gasförmigen Abbrandprodukten abfiltriert werden kann. Ein weiterer Vorteil besteht in der hohen Gasausbeute.The main advantage of such a gas generator propellant lies in the favorable formation of a slag which can easily be filtered off from the gaseous combustion products formed. Another advantage is the high gas yield.
Nachteile derartiger Gasgeneratortreibsätze sind jedoch, daß hinsichtlich der Bereitstellung eines Gasgeneratortreibsatzes mit einer möglichst günstigen Schlackenbildung Kompromisse beim Abbrandverhalten (Abbrandgeschwindigkeit), bei der Gasbildung, den Eigenschaften hinsichtlich der Herstellung der Pellets und anderen Verfahrensfaktoren und insbesondere bei der Gasqualität, d.h. dem Anteil von toxischen gasförmigen Abbrandprodukten eingegangen werden mußten. Weiterhin ist die Anzahl der geeigneten Treibstoffe relativ begrenzt.Disadvantages of such gas generator propellants are, however, that with regard to the provision of a gas generator propellant with the cheapest possible formation of slag, compromises are made in the combustion behavior (combustion rate), in the gas formation, the properties with regard to the production of the pellets and other process factors and in particular in the gas quality, i.e. the proportion of toxic gaseous combustion products had to be considered. Furthermore, the number of suitable fuels is relatively limited.
In der EP-B-0 482 852 gibt es keine Hinweise darauf, wie diese Probleme durch eine Modifizierung der Zusammensetzung des Gasgeneratortreibsatzes gelöst werden können.In EP-B-0 482 852 there is no indication of how these problems can be solved by modifying the composition of the gas generator propellant.
In der US-PS 4,948,439 wird von dem gleichen Erfinder auf die Problematik hinsichtlich der Bildung von toxischen gasförmigen Abbrandprodukten bei der Verwendung von Azid- Ersatzstoffen, wie Tetrazolverbindungen (z.B. Aminotetrazol und dessen Metallsalze) und deren Gemische in Gasgeneratortreibsätzen hingewiesen.In US Pat. No. 4,948,439, the same inventor pointed out the problems with regard to the formation of toxic gaseous combustion products when using azide substitutes, such as tetrazole compounds (e.g. aminotetrazole and its metal salts) and their mixtures in gas generator propellants.
In der US-PS 4,948,439 wird jedoch kein Lösungsvorschlag beschrieben, wie der Anteil an toxischen gasförmigen Abbrandprodukten bei der Verbrennung von Gasgeneratortreibsätzen, die als Treibstoff Tetrazol- oder Triazolverbindungen, deren Metallsalze oder Gemische davon enthalten, reduziert werden könnte. Vielmehr wird ein Verfahren zum Aufblasen eines 4In US Pat. No. 4,948,439, however, no proposed solution is described as to how the proportion of toxic gaseous combustion products in the combustion of gas generator propellants that contain tetrazole or triazole compounds, the metal salts or mixtures thereof, as the fuel could be reduced. Rather, a method of inflating a 4
Airbags beschrieben, bei dem zunächst ein Primärgasgemisch durch die Zündung eines Gasgeneratortreibsatzes entsteht, der als Treibstoff mindestens eine Tetrazol- oder Triazolverbin- dung enthält und dieses Primärgemisch wird durch Vermischen mit Umgebungsluft derart verdünnt, daß der Gehalt an toxischen gasförmigen Abbrandprodukten aus dem Primärgas- gemisch auf ein toxikologisch akzeptables Maß gesenkt wird.Airbags described, in which a primary gas mixture is initially created by the ignition of a gas generator propellant, which contains at least one tetrazole or triazole compound as fuel, and this primary mixture is diluted by mixing with ambient air in such a way that the content of toxic gaseous combustion products from the primary gas mixture is reduced to a toxicologically acceptable level.
Das Vermischen mit der Umgebungsluft führt zu einer Verkomplizierung (Größe, Aufbau, etc.) des gesamten Airbag- Systems. Problematisch ist die Geschwindigkeit, mit der der Air- bag aufgeblasen werden muß (10-50 ms), wenn zusätzlich noch Umgebungsluft angesaugt werden muß.Mixing with the ambient air leads to a complication (size, structure, etc.) of the entire airbag system. The speed at which the airbag has to be inflated (10-50 ms) is problematic if ambient air also has to be sucked in.
Aus der DE-C-44 01 213 sind gaserzeugende Mischungen aus einem Brennstoff, einem Oxi- dator, einem "Katalysator" und einem Kühlmittel, dadurch gekennzeichnet, daß der Oxidator Cu(NO3)2-3Cu(OH)2 und der Katalysator ein Metalloxid oder eine Metalloxidmischung oder ein Metallmischoxid ist, bekannt.DE-C-44 01 213 describes gas-generating mixtures of a fuel, an oxidizer, a "catalyst" and a coolant, characterized in that the oxidizer Cu (NO 3 ) 2 -3Cu (OH) 2 and the catalyst a metal oxide or a metal oxide mixture or a metal mixed oxide is known.
Aus der DE-C-44 01 214 sind zudem gaserzeugende Mischungen ähnlicher Zusammensetzungen bekannt, bei denen der Katalysator aus einem Metall oder einer Metallegierung, vorzugsweise einem pyrophoren Metall oder einer pyrophoren Metallegierung auf einem Träger besteht. Bei dem Träger handelt es sich um ein Silikat, vorzugsweise ein Schicht- oder Gerüstsilikat. Als Metall hat sich insbesondere Ag bewährt. Zu den bekannten verwendeten Brennstoffen zählen Triaminoguanidinnitrat (TAGN), Nitroguanidin (NIGU bzw. NQ), 3- Nitro-l,2,3-triazol-5-on und insbesondere Diguanidinium-5,5'-azotetrazolat (GZT).DE-C-44 01 214 also discloses gas-generating mixtures of similar compositions in which the catalyst consists of a metal or a metal alloy, preferably a pyrophoric metal or a pyrophoric metal alloy on a support. The carrier is a silicate, preferably a layered or framework silicate. Ag has proven particularly useful as a metal. The known fuels used include triaminoguanidine nitrate (TAGN), nitroguanidine (NIGU or NQ), 3-nitro-l, 2,3-triazol-5-one and especially diguanidinium-5,5'-azotetrazolate (GZT).
Der wesentliche Vorteil der in den beiden vorstehenden deutschen Patentschriften beschriebenen gaserzeugenden Mischungen soll in der Herabsetzung der Verbrennungstemperatur und in der Erhöhung der Abbrandgeschwindigkeit liegen.The main advantage of the gas-generating mixtures described in the two above-mentioned German patents is said to be the lowering of the combustion temperature and the increase in the rate of combustion.
Die in der DE-C-44 01 213 und DE-C-44 01 214 beschriebenen gaserzeugenden Mischungen enthalten keine niedrig- und hochschmelzenden Schlackenbildner bzw. keine erfindungsgemäßen Schlackenfänger, vielmehr wird dort behauptet, daß auf Schlackenbildner verzichtet werden kann. Entgegen dieser Behauptung haben die Erfinder der vorliegenden Erfindung gefunden, daß die Verwendung von niedrig- und hochschmelzenden Schlackenbildnern, insbesondere der erfindungsgemäßen Schlackenfänger eine deutliche Reduzierung von toxischen gasförmigen Abbrandprodukten bewirkt. Ein Teil des hochschmelzenden erindungsgemäßen Schlackenfängers kann hierbei als Träger für ein Platinmetall bzw. für eine Metallegierung aus Platinmetallen und somit als Katalysatorbestandteil fungieren.The gas-generating mixtures described in DE-C-44 01 213 and DE-C-44 01 214 do not contain any low- or high-melting slag formers or slag scavengers according to the invention; rather, it claims that there is no need for slag formers. Contrary to this claim, the inventors of the present invention have found that the use of low-melting and high-melting slag formers, in particular the slag trap according to the invention, brings about a significant reduction in toxic gaseous combustion products. Part of the high-melting slag catcher according to the invention can act as a carrier for a platinum metal or for a metal alloy made of platinum metals and thus as a catalyst component.
In den beiden vorstehend genannten deutschen Patentschriften wird der Begriff "Katalysator" in einem erweiterten Sinn verwendet und stellt einen aktiven Reaktionsbestandteil dar, der selbst umgesetzt werden kann und reaktionslenkend und/oder reaktionsbeschleunigend wirkt.In the two German patents mentioned above, the term "catalyst" is used in a broader sense and represents an active component of the reaction which can itself be implemented and has a reaction-directing and / or reaction-accelerating effect.
Es handelt sich demnach nicht um einen Katalysator im eigentlichen Sinn, da ein Katalysator bei einer Umsetzung keinen Reaktionsbestandteil darstellt. Ein Katalysator im eigentlichen Sinn wird bei Umsetzungen nicht verbraucht, d.h. nicht umgesetzt.It is therefore not a catalyst in the actual sense, since a catalyst is not a component of the reaction in a reaction. A catalyst in the actual sense is not used in the implementation, i.e. Not translated.
Zur Definition des Katalysators gehört ferner, daß dieser in einer nur sehr geringen Konzentration dem Reaktionsgemsich beigemengt wird. In den beiden deutschen Patentschriften beträgt jedoch der Anteil an "Katalysator" in der gaserzeugenden Mischung bis zu 30 Mas- sen-% und ist damit wesentlicher, auch anteilsmäßig, Bestandteil der gaserzeugenden Mischung.The definition of the catalyst also means that it is added to the reaction mixture in only a very low concentration. In the two German patents, however, the proportion of "catalyst" in the gas-generating mixture is up to 30% by mass and is therefore an essential, also proportionate, component of the gas-generating mixture.
Aus dem zuvor gesagten ergibt sich, daß in der DE-C-44 01 213 und DE-C-44 01 214 zwar der Begriff "Katalysator" verwendet wird, aber, wie dies auch in den beiden Patentschriften angedeutet ist, die Bedeutung nicht mit der herkömmlichen Definition eines Katalysators übereinstimmt.It follows from the foregoing that in DE-C-44 01 213 and DE-C-44 01 214 the term "catalyst" is used but, as is also indicated in the two patents, the meaning is not included corresponds to the conventional definition of a catalyst.
Der vorliegenden Erfindung liegt gegenüber dem Stand der Technik die Aufgabe zugrunde, verbesserte Gasgeneratortreibstoffe, insbesondere für Airbags bereitzustellen, deren Abbrandverhalten sich gezielt einstellen läßt und die insbesondere die Entstehung von 6Compared to the prior art, the present invention is based on the object of providing improved gas generator fuels, in particular for airbags, the combustion behavior of which can be set in a targeted manner and which in particular the formation of 6
toxischen Gasen und von lungengängigen, staubförmigen Anteilen, die aus dem Gasgeneratorgehäuse austreten können, auf ein Minimum beschränken.Keep toxic gases and respirable, dust-like components that can escape from the gas generator housing to a minimum.
Die aus den Gasgeneratortreibstoffen hergestellten Gasgeneratortreibsätze sollen thermisch stabil, gut anzündbar, schnell - auch bei niedriger Temperatur - brennend und gut lagerfähig sein und eine hohe Gasausbeute gewährleisten. Zudem sollen diese Gasgeneratortreibsätze eine Verkleinerung, Reduzierung der Anzahl der Komponenten oder Vereinfachung der Gasgeneratorgehäuse und somit deren Gewichtsverminderung im Vergleich zu bekannten Generatoren ermöglichen.The gas generator propellants made from the gas generator fuels should be thermally stable, easy to ignite, quick - even at low temperature - to be flammable and storable and ensure a high gas yield. In addition, these gas generator propellants should make it possible to downsize, reduce the number of components or simplify the gas generator housing and thus reduce their weight in comparison to known generators.
Erfindungsgemäß werden diese Aufgaben durch einen Gasgeneratortreibstoff gelöst, umfassendAccording to the invention, these objects are achieved by a gas generator fuel, comprising
(A) mindestens einen Brennstoff aus der Gruppe umfassend Guanidiniumnitrat (GUNI; GuNO3), Dicyanamid, Ammoniumdicyanamid, Natriumdicyanamid (Na-DCA),(A) at least one fuel from the group comprising guanidinium nitrate (GUNI; GuNO 3 ), dicyanamide, ammonium dicyanamide, sodium dicyanamide (Na-DCA),
Kupferdicyanamid, Zinndicyanamid, Calciumdicyanamid (Ca-DCA),Copper dicyanamide, tin dicyanamide, calcium dicyanamide (Ca-DCA),
Guanidiniumdicyanamid (GDCA), Aminoguanidiniumbicarbonat (AGB),Guanidinium dicyanamide (GDCA), aminoguanidinium bicarbonate (AGB),
A inoguanidiniumnitrat (AGN), Triaminoguanidiniumnitrat (TAGN), Nitroguanidin (NIGU), Dicyandiamid (DCD), Azodicarbonamid (ADCA) sowie Tetrazol (HTZ), 5- Aminotetrazol (ATZ), 5-Nitro-l,2,4-triazol-3-on (NTO), deren Salze und deren Gemische,A inoguanidinium nitrate (AGN), triaminoguanidinium nitrate (TAGN), nitroguanidine (NIGU), dicyandiamide (DCD), azodicarbonamide (ADCA) as well as tetrazole (HTZ), 5-aminotetrazole (ATZ), 5-nitro-l, 2,4-triazole- 3-one (NTO), its salts and their mixtures,
(B) mindestens ein Alkali- oder Erdalkalinitrat oder Ammoniumnitrat, -chlorat oder -perchlorat,(B) at least one alkali or alkaline earth nitrate or ammonium nitrate, chlorate or perchlorate,
(C) mindestens einen hochschmelzenden, im wesentlichen chemisch inerten Schlackenfänger, ausgewählt aus der Gruppe umfassend Al2O3, TiO2 und ZrO2 in hochdisperser Form oder Gemische davon, und(C) at least one high-melting, essentially chemically inert slag catcher selected from the group comprising Al 2 O 3 , TiO 2 and ZrO 2 in highly dispersed form or mixtures thereof, and
gegebenenfalls (D) mindestens einen Schlackenbildner, ausgewählt aus Alkali- und Erdal- kalimetallcarbonaten und -oxiden, Silikaten, Aluminaten und Aluminiumsilikaten, Eisen(III)oxid sowie Siliciumnitrid (Si3N4), das beim Abbrand Stickstoff (N2) und Siliciumdioxid (SiO2) zur Weiterreaktion liefert und 7optionally (D) at least one slag former selected from alkali and alkaline earth metal carbonates and oxides, silicates, aluminates and aluminum silicates, iron (III) oxide and silicon nitride (Si 3 N 4 ), which burns nitrogen (N 2 ) and silicon dioxide (SiO 2 ) for further reaction and 7
gegebenenfalls (E) mindestens ein in Wasser bei Raumtemperatur lösliches Bindemittel.optionally (E) at least one binder soluble in water at room temperature.
Bevorzugte Brennstoffe (Komponente (A)) sind Nitroguanidin (NIGU), 5-Aminotetrazol (ATZ), Dicyandiamid (DCD), Dicyanamid, deren Salze, insbesondere Natrium- und Calciumdicyanamid und Guanidiniumnitrat, und deren Gemische. Diese sind praktisch ungiftig, nicht hygroskopisch, wenig wasserlöslich, thermisch stabil, bei niedriger Temperatur verbrennend und von geringer Schlag- und Reibempfmdlichkeit. Die Gasausbeute bei der Verbrennung ist hoch, wobei ein großer Anteil an Stickstoffgas entsteht.Preferred fuels (component (A)) are nitroguanidine (NIGU), 5-aminotetrazole (ATZ), dicyandiamide (DCD), dicyanamide, their salts, in particular sodium and calcium dicyanamide and guanidinium nitrate, and mixtures thereof. These are practically non-toxic, not hygroscopic, not very soluble in water, thermally stable, they burn at low temperatures and are not sensitive to impact and friction. The gas yield during combustion is high, with a large proportion of nitrogen gas being generated.
Alkali- (Li, Na, K) und Erdalkalisalze (Mg, Ca, Sr, Ba) sind Beispiele für geeignete Salze von 5-Aminotetrazol.Alkali (Li, Na, K) and alkaline earth salts (Mg, Ca, Sr, Ba) are examples of suitable salts of 5-aminotetrazole.
Als Oxidationsmittel, Komponente (B), können Alkali- oder Erdalkalinitrate (wie Lithiumnitrat, Natriumnitrat, Kaliumnitrat, Magnesiumnitrat, Calciumnitrat, Strontiumnitrat oder Bari- umnitrat), Ammoniumnitrat, Alkali- oder Erdalkalichlorate oder -perchlorate (wie Lithium- Natrium-, Kalium-, Magnesium-, Calcium-, Strontium- oder Bariumchlorat und Lithium-, Natrium-, Kalium-, Magnesium-, Calcium-, Strontium- oder Bariumperchlorat) sowie Ammoniumperchlorat und deren Gemische verwendet werden. Vorzugsweise wird Kaliumnitrat und Strontiumnitrat verwendet. Strontiumnitrat ist nicht hygroskopisch, nicht toxisch und ermöglicht beim Abbrand eine hohe Gasausbeute. Kaliumnitrat weist zusätzlich eine niedrige Abbrandtemperatur auf.As the oxidizing agent, component (B), alkali metal or alkaline earth metal nitrates (such as lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate or barium nitrate), ammonium nitrate, alkali metal or alkaline earth metal chlorates or perchlorates (such as lithium, sodium or potassium , Magnesium, calcium, strontium or barium chlorate and lithium, sodium, potassium, magnesium, calcium, strontium or barium perchlorate) and ammonium perchlorate and mixtures thereof. Potassium nitrate and strontium nitrate are preferably used. Strontium nitrate is non-hygroscopic, non-toxic and enables a high gas yield when burned. Potassium nitrate also has a low burning temperature.
Als hochschmelzende, im wesentlichen chemisch inerte Schlackenfänger, Komponente (C), können z.B. Al,O3, TiO2 und ZrO, in hochdisperser Form oder Gemische davon verwendet werden. Besonders bevorzugt sind Al2O3 mit einer BET-Oberfläche (in Anlehnung an DIN 66131) von 100 +/- 15 m2/g (Smp-Punkt ca. 2050°C), TiO2 mit einer BET-Oberfläche von 50 +/- 15 m2/g (Smp-Punkt ca. 1850°C) und ZrO2 mit einer BET-Oberfläche von 40 +/- 10 m2/g (Smp-Punkt ca. 2700°C). Diese hochdispersen Oxide sind z.B. unter den Handelsnamen Aluminiumoxid C, Titanoxid P25 und VP Zirkonoxid (Degussa AG) im Handel erhältlich.Al, O 3 , TiO 2 and ZrO, in highly dispersed form or mixtures thereof, can be used as high-melting, essentially chemically inert slag catchers, component (C). Al 2 O 3 with a BET surface area (based on DIN 66131) of 100 +/- 15 m 2 / g (mp point approx. 2050 ° C.), TiO 2 with a BET surface area of 50+ are particularly preferred / - 15 m 2 / g (melting point approx. 1850 ° C) and ZrO 2 with a BET surface area of 40 +/- 10 m 2 / g (melting point approx. 2700 ° C). These highly disperse oxides are commercially available, for example, under the trade names aluminum oxide C, titanium oxide P25 and VP zirconium oxide (Degussa AG).
Diese pyrogenen Oxide werden durch Umsetzung der Metallchloride mit H2 und O2 im entsprechenden Molverhältnis durch Gasphasenreaktion (Flammenhydrolyse) hergestellt. Sie 8These pyrogenic oxides are produced by reacting the metal chlorides with H 2 and O 2 in the appropriate molar ratio by means of a gas phase reaction (flame hydrolysis). she 8th
haben keine Poren und definierte Agglomerate, wie dies sonst bei der Herstellung im Naßverfahren der Fall ist.have no pores and defined agglomerates, as is otherwise the case in the wet process.
Unter Schlackenfänger (Komponente (C)) im Sinne der vorliegenden Erfindung versteht man hochschmelzende, im wesentlichen chemisch inerte Metalloxide in hochdisperser Form, d.h. diese Oxide weisen eine gegenüber den Oxiden in ihrer herkömmlichen Form sehr viel größere Oberfläche auf.Slag scavenger (component (C)) for the purposes of the present invention is understood to mean high-melting, essentially chemically inert metal oxides in highly disperse form, i.e. these oxides have a much larger surface area than the oxides in their conventional form.
Zum Beispiel weisen herkömmliches Al2O3 als α-Oxid eine BET-Oberfläche von nur 5-10 m2/g, herkömmliches Pigment-TiO2 eine BET-Oberfläche von nur 5-10 m2/g und herkömmliches ZrO, eine BET-Oberfläche von nur 3-8 m2/g (für Feuerfest-Produkte) auf, wohingegen die in den Gasgeneratortreibsätzen der vorliegenden Erfindung verwendeten Metalloxide BET-Oberflächen von etwa 40 bis etwa 100 m2/g, besonders bevorzugt etwa 50 bis etwa 100 m2/g und insbesondere etwa 100 m2/g aufweisen.For example, conventional Al 2 O 3 as the α-oxide has a BET surface area of only 5-10 m 2 / g, conventional pigment TiO 2 has a BET surface area of only 5-10 m 2 / g and conventional ZrO, a BET Surface area of only 3-8 m 2 / g (for refractory products), whereas the metal oxides BET surfaces used in the gas generator propellant sets of the present invention range from about 40 to about 100 m 2 / g, particularly preferably about 50 to about 100 have m 2 / g and in particular about 100 m 2 / g.
Ferner zeichnen sich die Schlackenfänger der vorliegenden Erfindung durch ihren hohen Schmelzpunkt von etwa 1850 bis etwa 2700°C aus. Diese hohen Schmelzpunkte führen dazu, daß die Schlackenfänger während der Umsetzung nicht schmelzen und somit als Feststoffe fungieren.Furthermore, the slag catchers of the present invention are distinguished by their high melting point of approximately 1850 to approximately 2700 ° C. These high melting points mean that the slag catchers do not melt during the reaction and thus act as solids.
Des weiteren handelt es sich bei den Schlackenfängern der vorliegenden Erfindung um im wesentlichen chemisch inerte Verbindungen, d.h. die Schlackenfänger der vorliegenden Erfindung beteiligen sich nicht bei der Verbrennungsreaktion der Gasgeneratortreibsätze an chemischen Umsetzungen oder nur in einem geringen Maß an der Oberfläche der als Schlackenfänger dienenden Metalloxide. Die hochaufgelösten Raumgitter, d.h. die große innere Oberfläche von z.B. Al2O3, TiO2 oder ZrO2 bewirkt einerseits durch ihre Inaktivität die Abkühlung der Verbrennungsprodukte und lagert andererseits speziell flüssige und/oder feste Schlackenteile bzw. Partikel an, die bei der Verbrennung entstehen. Auf diese Weise bleibt die Tablettenform, in der die Gasgeneratortreibsätze verwendet werden, während und nach dem Abbrand erhalten bzw. es lassen sich eventuell entstandene Bruchstücke leicht filtern. Das heißt, es bilden sich kaum Stäube, die bei der Verbrennung aus dem Gasgeneratortreibsatz und somit aus dem Gasgeneratorgehäuse austreten könnten. Die Schlackenfänger wirken 9Furthermore, the slag scavengers of the present invention are essentially chemically inert compounds, ie the slag scavengers of the present invention do not participate in the combustion reaction of the gas generator propellants in chemical reactions or only to a small extent on the surface of the metal oxides serving as slag scavengers. The high-resolution room grids, ie the large inner surface of Al 2 O 3 , TiO 2 or ZrO 2 , on the one hand, cause the combustion products to cool down due to their inactivity and, on the other hand, specifically store liquid and / or solid slag parts or particles that arise during combustion . In this way, the tablet form in which the gas generator propellants are used is preserved during and after the burn-up, or fragments that may have formed can be easily filtered. This means that there is hardly any dust that could escape from the gas generator propulsion unit and thus from the gas generator housing during combustion. The slag catchers work 9
somit als internes Filter in den Gasgeneratortreibsätzen selbst, und verhindern somit weitgehend die Entstehung und den Austritt von staubförmigen Schlackenteilen aus dem Gasgeneratorgehäuse, wodurch auch eine wesentliche Filtervereinfachung des Gasgeneratorgehäuses erreicht wird, da auf zusätzliche (mechanische) Feinfilter im Gasgeneratorgehäuse teilweise verzichtet werden kann. Dies führt auch zu einer vorteilhaften Gewichtseinsparung beim Airbag-Gasgenerator.thus as an internal filter in the gas generator propulsion units themselves, and thus largely prevent the formation and leakage of dust-like slag parts from the gas generator housing, which also considerably simplifies the filter of the gas generator housing, since additional (mechanical) fine filters in the gas generator housing can be partially dispensed with. This also leads to an advantageous weight saving in the airbag gas generator.
Gleichzeitig wird durch die Bildung von Schlacken das Entstehen von lungengängigen staubförmigen Anteilen vermindert, die aus dem Gasgenerator eines Airbags austreten könnten. Lungengängige staubförmige Teilchen haben einen Durchmesser von etwa 6 μm oder kleiner.At the same time, the formation of slag reduces the occurrence of pulmonary dust that can enter the air and could escape from the gas generator of an airbag. Respirable dust-like particles have a diameter of about 6 μm or smaller.
Wahlweise können als Schlackenbildner, Komponente (D) Alkalimetall- und Erdalkalime- tallcarbonate (wie Natriumcarbonat, Kaliumcarbonat, Magnesiumcarbonat, Calciumcarbonat, Strontiumcarbonat oder Bariumcarbonat), Alkalimetall- oder Erdalkalimetalloxide (wie Natrium-, Kalium-, Magnesium-, Calcium-, Strontium- oder Bariumoxid), Silikate (wie Hectorit), Aluminate (wie Natrium-beta-aluminat (NajOnALjOj) oder Tricalciumaluminat (Ca3Al2O6)) oder Aluminiumsilikate (wie Bentonite oder Zeolithe) oder Eisen(III)oxid oder deren Gemische verwendet werden.Optionally, as slag formers, component (D) alkali metal and alkaline earth metal carbonates (such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate or barium carbonate), alkali metal or alkaline earth metal oxides (such as sodium, potassium, magnesium, calcium, strontium or barium oxide), silicates (such as hectorite), aluminates (such as sodium beta-aluminate (NajOnALjOj) or tricalcium aluminate (Ca 3 Al 2 O 6 )) or aluminum silicates (such as bentonites or zeolites) or iron (III) oxide or mixtures thereof become.
Komponente (D) dient dazu, beim Abbrand des Gasgeneratortreibstoffs eine leicht filtrierbare Schlacke zu bilden.Component (D) is used to form an easily filterable slag when the gas generator fuel burns.
Die Schlackenbildner, Komponente (D), können zusätzlich noch als Kühlmittel wirken. Die Silikate, Aluminate und Aluminiumsilikate reagieren mit den Alkalimetall- und Erdalkalimetalloxiden, die beim Abbrand entstehen.The slag formers, component (D), can also act as a coolant. The silicates, aluminates and aluminum silicates react with the alkali metal and alkaline earth metal oxides that are formed during the combustion.
Die Erfindung betrifft ferner die Verwendung von Katalysatoren auf der Basis von Platinmetallen (Ru, Os, Rh, Ir, Pd, Pt) oder Metallegierungen aus Platinmetallen oder Kupfer auf den hochdispersen Schlackenfängern als Träger, in den festen Gasgeneratortreibstoffen der vorliegenden Erfindung, insbesondere die Verwendung in festen Gasgeneratortreibsätzen für Airbags. 10The invention further relates to the use of catalysts based on platinum metals (Ru, Os, Rh, Ir, Pd, Pt) or metal alloys made of platinum metals or copper on the highly disperse slag traps as carriers, in the solid gas generator fuels of the present invention, in particular the use in fixed gas generator propellants for airbags. 10
Ein Teil des Schlackenfängers (Komponente (C)) kann als Träger dienen, auf dem ein Platinmetall oder eine Metallegierung aus Platinmetallen oder Kupfer in einer katalytisch wirksamen Schichtdicke aufgebracht ist.A part of the slag catcher (component (C)) can serve as a support on which a platinum metal or a metal alloy made of platinum metals or copper is applied in a catalytically effective layer thickness.
Platinmetalle sind Ruthenium (Ru), Osmium (Os), Rhodium (Rh), Iridium (Ir), Palladium (Pd) und Platin (Pt). Die Katalysatoren, die in der vorliegenden Erfindung verwendet werden, basieren vorzugsweise auf Rh, Pd oder Pt und insbesondere auf Pt.Platinum metals are ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt). The catalysts used in the present invention are preferably based on Rh, Pd or Pt and in particular Pt.
Beispiele für Metallegierungen aus Platinmetallen sind alle katalytisch wirksamen Metalle- gierungen der vorstehend genannten Platinmetalle, vorzugsweise Pt/Pd- und Pt/Rh-Legierun- gen.Examples of metal alloys made of platinum metals are all catalytically active metal alloys of the platinum metals mentioned above, preferably Pt / Pd and Pt / Rh alloys.
Die Metalle oder Metallegierungen aus Platinmetallen sind in einer katalytisch wirksamen Schichtdicke, vorzugsweise in einer einatomigen Schicht ("monolayer") auf dem Träger auf- gebracht.The metals or metal alloys made of platinum metals are applied to the support in a catalytically effective layer thickness, preferably in a one-atom layer (“monolayer”).
Die Katalysatoren sind in nur katalytischen Mengen im Gasgeneratortreibsatz enthalten. Ihr Gewichtsanteil an der Komponente (C) beträgt 0,1-5 Gew.-%, vorzugsweise 0,2-1,2 Gew.-% der Komponente (C).The catalytic converters are only contained in catalytic quantities in the gas generator propulsion unit. Their weight fraction in component (C) is 0.1-5% by weight, preferably 0.2-1.2% by weight of component (C).
Bevorzugte Katalysatoren sind die, bei denen der hochdisperse Träger A1203 und das Metall Pt, Pd oder Cu, insbesondere Pt ist.Preferred catalysts are those in which the highly disperse support A1 2 0 3 and the metal is Pt, Pd or Cu, in particular Pt.
Geeignete Katalysatoren sind von der Degussa AG erhältlich, z.B. 1% Pt auf gamma-Al203 oder 1% Pd + Pt auf gamma-Al2O3.Suitable catalysts are available from Degussa AG, for example 1% Pt on gamma-Al 2 0 3 or 1% Pd + Pt on gamma-Al 2 O 3 .
Die Katalysatoren dienen dazu, die Reaktion dahingehend zu steuern, daß kaum toxische gasförmige Abbrandprodukte, wie Kohlenmonoxid (CO), Stickoxide (NOx) und Ammoniak (NH3) gebildet werden.The catalysts serve to control the reaction so that hardly toxic gaseous combustion products such as carbon monoxide (CO), nitrogen oxides (NO x ) and ammonia (NH 3 ) are formed.
Die vorstehend genannten Katalysatoren sind besonders gut für die Verwendung in Gasgeneratortreibsätzen in Airbags geeignet. 11The catalysts mentioned above are particularly well suited for use in gas generator propellants in airbags. 11
Zusätzlich zu den Vorteilen, die sich aus der Verwendung der hochdispersen Metalloxide ergeben (Verringerung der festen Staubteilchen, d.h. von Grob- und Feinstaub) wird hier der ohnehin geringe Anteil an toxischen Gasen weiter reduziert.In addition to the advantages that result from the use of the highly disperse metal oxides (reduction of the solid dust particles, i.e. of coarse and fine dust), the already low proportion of toxic gases is further reduced here.
Die Katalysatoren können aus ausgelösten, d.h. gebrauchten Airbags, als auch aus nicht ausgelösten, d.h. aus Airbags aus Alt-Kraftfahrzeugen nach bereits bekannten Verfahren recycelt werden. Dies führt zu einer Abfallentlastung der Umwelt und ermöglicht die Wiederverwendung der Katalysatormetalle. Das Katalysatormetall bzw. die Metallegierung wird während des Abbrands nicht oxidiert.The catalysts can be triggered, i.e. used airbags, as well as from non-deployed, i.e. can be recycled from airbags from old motor vehicles according to already known methods. This leads to less pollution of the environment and enables the catalyst metals to be reused. The catalyst metal or the metal alloy is not oxidized during the combustion.
Der Katalysator muß nicht als zusätzlicher Bestandteil dem Gasgeneratortreibsatz zugesetzt werden, sondern der Katalysator ist Bestandteil einer ohnehin im Gasgeneratortreibsatz vorhandenen Komponente (Komponente C)).The catalyst does not have to be added to the gas generator propulsion unit as an additional component, but the catalyst is part of a component (component C) which is already present in the gas generator propulsion unit.
Komponente (A) liegt in einer Menge von etwa 20 bis 60 Gew.-%, vorzugsweise von etwa 28 bis 52 Gew.-% und insbesondere von etwa 45 bis 51 Gew.-% vor, Komponente (B) in einer Menge von etwa 38 bis etwa 63 Gew.-%, vorzugsweise von etwa 38 bis etwa 55 Gew.-% und insbesondere von etwa 39 bis 45 Gew.-% vor, Komponente (C) in einer Menge von etwa 5 bis 22 Gew.-%, vorzugsweise von etwa 8 bis 20 Gew.-% und insbesondere von etwa 9 bis 11 Gew.-% und Komponente (D), sofern enthalten, in einer Menge von etwa 2 bis 12 Gew.-%, vorzugsweise von etwa 4 bis 10 Gew.-% vor, jeweils bezogen auf die Gesamtzusammensetzung des Gasgeneratortreibsatzes.Component (A) is present in an amount of approximately 20 to 60% by weight, preferably approximately 28 to 52% by weight and in particular approximately 45 to 51% by weight, component (B) in an amount of approximately 38 to about 63% by weight, preferably from about 38 to about 55% by weight and in particular from about 39 to 45% by weight, component (C) in an amount of from about 5 to 22% by weight, preferably from about 8 to 20% by weight and in particular from about 9 to 11% by weight and component (D), if present, in an amount of from about 2 to 12% by weight, preferably from about 4 to 10% by weight .-% before, each based on the total composition of the gas generator propellant.
Wahlweise kann der Gasgeneratortreibstoff femer als Komponente (E) ein in Wasser bei Raumtemperatur lösliches Bindemittel enthalten. Bevorzugte Bindemittel sind Cellulosever- bindungen oder Polymerisate aus einem oder mehreren polymerisierbaren olefmisch ungesättigten Monomeren. Beispiele für Celluloseverbindungen sind Celluloseether, wie Carboxy- methylcellulose, Methylcelluloseether, insbesondere Methylhydroxyethylcellulose. Eine gut verwendbare Methylhydroxyethylcellulose ist CULMINAL® MHEC 30000 PR der Firma Aqualon. Geeignete Polymerisate mit Bindewirkung sind Polyvinylpyrrolidon, Polyvinylace- 12Optionally, the gas generator fuel may also contain, as component (E), a binder which is soluble in water at room temperature. Preferred binders are cellulose compounds or polymers made from one or more polymerizable olefinically unsaturated monomers. Examples of cellulose compounds are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose ethers, in particular methyl hydroxyethyl cellulose. A usable methylhydroxyethyl cellulose is CULMINAL® MHEC 30000 PR from Aqualon. Suitable polymers with binding action are polyvinylpyrrolidone, polyvinyllace- 12
tat, Polyvinylalkohol und Polyvinylbutyral, z.B. Pioloform® B (Firma Wacker Chemie, Burghausen).tat, polyvinyl alcohol and polyvinyl butyral, e.g. Pioloform® B (from Wacker Chemie, Burghausen).
Als Bindemittel, Komponente (E), kann auch ein in Wasser bei Raumtemperatur unlösliches Metallsalz der Stearinsäure, wie Aluminiumstearat, Magnesiumstearat, Calciumstearat oder Zinkstearat verwendet werden.A metal salt of stearic acid, such as aluminum stearate, magnesium stearate, calcium stearate or zinc stearate, which is insoluble in water at room temperature, can also be used as the binder, component (E).
Graphit ist ebenfalls als Bindemittel geeignet.Graphite is also suitable as a binder.
Komponente (E) liegt in einer Menge von 0 bis 2 Gew.-% und vorzugsweise von 0,3-0,8 Gew.-% vor.Component (E) is present in an amount of 0 to 2% by weight and preferably 0.3-0.8% by weight.
Das Bindemittel, Komponente (E), dient als Desensibilisierungsmittel und als Verarbeitungshilfe bei der Herstellung von Granulat oder Tabletten (Pellets) aus dem Gasgenerator- treibstoff Es dient femer zur Verminderung der Hydrophilie und zur Stabilisierung der Gasgeneratortreibsätze.The binder, component (E), serves as a desensitizing agent and as a processing aid in the production of granules or tablets (pellets) from the gas generator fuel. It also serves to reduce the hydrophilicity and to stabilize the gas generator propellants.
Herstellungsvorschrift:Manufacturing instructions:
Allgemein erfolgte die Herstellung der Gasgeneratortreibstoffe (Beispiele 1 bis 57 der nachstehenden Tabelle I) und Gasgeneratortreibsätze nach folgendem Vorgehen:In general, the gas generator fuels (Examples 1 to 57 of Table I below) and gas generator propellants were produced according to the following procedure:
Die grob vorgemischten Rohstoffe (Komponenten (A), (B), (C) und gegebenenfalls (D) undThe roughly premixed raw materials (components (A), (B), (C) and optionally (D) and
(E)) wurden mittels einer Kugelmühle gemahlen bzw. vorverdichtet. Das Granulieren der Gasgeneratortreibstoffmischung erfolgte in einem Vertikalmischer durch(E)) were ground or pre-compacted using a ball mill. The gas generator fuel mixture was granulated in a vertical mixer
Zugabe von ca. 20 % Wasser beim Rühren und bei einer auf ca. 40°C erhöhten Temperatur.Add approx. 20% water while stirring and at a temperature raised to approx. 40 ° C.
Nach kurzem Ablüften wurde die erhaltene Mischmasse bei Raumtemperatur durch eineAfter briefly flashing off the mixture obtained at room temperature by a
Durchreibemaschine mit einem 1 mm-Sieb gerieben. Das auf diese Weise erhaltene Granulat wurde ca. 2 Stunden in einem Trockenofen bei 80°C getrocknet. Das fertige Granulat des Gasgeneratortreibstoffes (Komverteilung 0-1 mm) wurde anschließend mit einer Rundläuferpresse zu Tabletten (Pellets) verpreßt. DieseGrinder rubbed with a 1 mm sieve. The granules obtained in this way were dried in a drying oven at 80 ° C. for about 2 hours. The finished granulate of the gas generator fuel (grain size 0-1 mm) was then pressed into tablets using a rotary press. This
Gasgeneratortreibsatzpellets wurden bei 80°C im Trockenofen nachgetrocknet. 13Gas generator propellant pellets were post-dried at 80 ° C in a drying oven. 13
Die in den Gasgeneratoren verwendeten Tabletten oder Pellets aus dem Gasgeneratortreibstoff können nach bekannten Verfahren hergestellt werden, etwa durch Strangpressen, Extrudieren, in Rundläuferpressen oder Tablettiermaschinen. Die Größe der Pellets oder Tabletten hängt von der gewünschten Brennzeit im jeweiligen Anwendungsfall ab.The tablets or pellets from the gas generator fuel used in the gas generators can be produced by known processes, for example by extrusion, extrusion, in rotary presses or tableting machines. The size of the pellets or tablets depends on the desired burning time in the respective application.
Der erfindungsgemäße Gas generatortreibsto ff besteht aus nicht-toxischen, leicht herstellbaren und kostengünstigen Komponenten, deren Verarbeitung unproblematisch ist. Die Kompo- nente, die weniger kostengünstig ist, nämlich das Katalysatormetall, kann nach bekannten Verfahren recycelt werden. Die thermische Stabilität der Komponenten bewirkt eine gute Lagerfähigkeit. Die Anzündbarkeit der Gemische ist gut. Sie brennen schnell und liefern große Gasausbeuten mit sehr geringen CO-, NOx- und NH3-Anteilen, die unterhalb der zulässigen Höchstgrenze liegen. Die erfindungsgemäßen Gemische sind daher zur Verwen- düng als Gaserzeugungsmittel in den verschiedenen Airbag-Systemen, als Löschmittel oder Treibmittel besonders geeignet.The gas generator fuel according to the invention consists of non-toxic, easily manufactured and inexpensive components, the processing of which is unproblematic. The component that is less cost-effective, namely the catalyst metal, can be recycled using known methods. The thermal stability of the components results in a good shelf life. The mixtures are easy to ignite. They burn quickly and deliver large gas yields with very low CO, NO x and NH 3 contents, which are below the permissible maximum limit. The mixtures according to the invention are therefore particularly suitable for use as gas generants in the various airbag systems, as extinguishing agents or propellants.
Die nachstehenden Beispiele 1 bis 57 veranschaulichen die Erfindung, schränken diese jedoch nicht ein. Bei den Beispielen 15, 18 und 21 handelt es sich um Vergleichsbeispiele, bei denen herkömmliches ZrO2, TiO2 und Al2O3 verwendet wurde.Examples 1 to 57 below illustrate the invention but do not limit it. Examples 15, 18 and 21 are comparative examples in which conventional ZrO 2 , TiO 2 and Al 2 O 3 were used.
Tabelle I:Table I:
Die in der Tabelle angegebenen Indizes haben folgende Bedeutung:The indices given in the table have the following meaning:
1 Titandioxid P25, Degussa AG1 titanium dioxide P25, Degussa AG
2 Zirkonoxid VP, Degussa AG2 zirconium oxide VP, Degussa AG
3 Aluminiumoxid C, Degussa AG3 aluminum oxide C, Degussa AG
4 Titandioxid Kronos 3025, Kronos Titan-GmbH 5 Zirkonoxid, Merck4 Kronos 3025 titanium dioxide, Kronos Titan-GmbH 5 Zirconium oxide, Merck
6 Aluminiumoxid NO 615 -30 II 24, Nabaltec6 aluminum oxide NO 615 -30 II 24, Nabaltec
7 Oxid. Katalysator 1% Pt auf Gamma- Aluminiumoxid, Degussa AG7 oxide. 1% Pt catalyst on gamma alumina, Degussa AG
8 Oxid. Katalysator 1% Pd + Pt auf Gamma- Aluminiumoxid, Degussa AG8 oxide. Catalyst 1% Pd + Pt on gamma alumina, Degussa AG
9 Eisenoxid, Bayoxide E8710, Bayer AG 10 Bentone EW, Rheox, Inc.9 iron oxide, Bayoxide E8710, Bayer AG 10 Bentone EW, Rheox, Inc.
11 CULMINAL MHEC 30000 PR, Aqualon 1411 CULMINAL MHEC 30000 PR, Aqualon 14
Tabelle ITable I
Beispiel Nr. 1 2 3 4 5 6Example No. 1 2 3 4 5 6
A = ATZ [%] 30,2 32,8 29,75 29J 29,75 29,7A = ATZ [%] 30.2 32.8 29.75 29J 29.75 29.7
NIGU [%] - - - - - -NIGU [%] - - - - - -
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuN03 [%] - - - - - -GuN0 3 [%] - - - - - -
B = KNO3 [%] 49,8 - 50,25 - 50,25 -B = KNO 3 [%] 49.8 - 50.25 - 50.25 -
Sr(N03)2 [%] - 57,2 - 54,8 - 54,8Sr (N0 3 ) 2 [%] - 57.2 - 54.8 - 54.8
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] - - 20,0 15,0 - -C = Ti0 2 1 [%] - - 20.0 15.0 - -
Zr02 2 [%] - - - - 20,0 15,0Zr0 2 2 [%] - - - - 20.0 15.0
AI2O3 3 [%] 10,0 10,0 - - - -AI 2 O 3 3 [%] 10.0 10.0 - - - -
AI2O3 + 1 %Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI2O3 + 1%(Pd+Pt) 8 [%] - - - - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - - - - -
D = Eisen(lll)oxid 9 [%] 10,0 - - - - -D = iron (III) oxide 9 [%] 10.0 - - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - - - - - -E = graphite [%] - - - - - -
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%} - - - 0,5 - 0,5Polyvinyl butyral [%} - - - 0.5 - 0.5
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 17,8 19,3 17,6 21 J 17,6 18,0Gas yield (V = constant) [mol / kg] 17.8 19.3 17.6 21 J 17.6 18.0
Temperatur (p=135*105Pa) [K] 1780 2420 1780 2370 1780 2520Temperature (p = 135 * 10 5 Pa) [K] 1780 2420 1780 2370 1780 2520
Gemessene Werte (in 60 dm3 Kanne. |Measured values (in 60 dm 3 jug. |
Kohlenmonoxid [ppm] 4000 2800 3000 3300 3000 3300Carbon monoxide [ppm] 4000 2800 3000 3300 3000 3300
Stickoxide [ppm] 150 300 200 350 200 250Nitrogen oxides [ppm] 150 300 200 350 200 250
Ammoniak [ppm] 150 0 0 0 100 100Ammonia [ppm] 150 0 0 0 100 100
Grobstaub in der Kanne [g] 1 ,2 0,6 1 ,2 1 ,0 1 ,1 1 ,2Coarse dust in the can [g] 1, 2 0.6 1, 2 1, 0 1, 1 1, 2
Feinstaub in der Kanne [g] 0,2 0,1 0,3 0,3 0,3 0,3 15Fine dust in the jug [g] 0.2 0.1 0.3 0.3 0.3 0.3 15
Beispiel Nr. 7 8 9 10 11 12Example No. 7 8 9 10 11 12
A = ATZ [%] 29,75 32,8 29,75 32,8 21 ,5 25,6A = ATZ [%] 29.75 32.8 29.75 32.8 21.5 25.6
NIGU [%] - - - - - -NIGU [%] - - - - - -
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuN03 [%] - - - - - -GuN0 3 [%] - - - - - -
B = KNO3 [%] 50,25 - 50,25 - 58,0 -B = KNO 3 [%] 50.25 - 50.25 - 58.0 -
Sr(N03)2 [%3 - 57,2 - 57,2 - 54,1Sr (N0 3 ) 2 [% 3 - 57.2 - 57.2 - 54.1
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] - - - - - -C = Ti0 2 1 [%] - - - - - -
Zr02 2 [%] - - - - - -Zr0 2 2 [%] - - - - - -
AI2O3 3 [%] 10,0 - 10,0 - 10,0 10,0AI 2 O 3 3 [%] 10.0 - 10.0 - 10.0 10.0
AI203 + 1 %Pt 7 [%] 10,0 10,0 - - - -AI 2 0 3 + 1% Pt 7 [%] 10.0 10.0 - - - -
AI203 + 1%(Pd+Pt) 8 [%] - - 10,0 10,0 - -AI 2 0 3 + 1% (Pd + Pt) 8 [%] - - 10.0 10.0 - -
D = Eisen(ll.l)oxid 9 [%] - - - - - 5,0D = iron (ll.l) oxide 9 [%] - - - - - 5.0
1010
Aluminiumsilikat [%] - - - - - -Aluminum silicate [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - 10,0 5,0Silicon nitride Si 3 N 4 [%] - - - - 10.0 5.0
E = Graphit [%] - - - - 0,5 -E = graphite [%] - - - - 0.5 -
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%] - - - - - 0,3Polyvinyl butyral [%] - - - - - 0.3
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 17,6 19,3 17,6 19,3 16,8 16,8Gas yield (V = constant) [mol / kg] 17.6 19.3 17.6 19.3 16.8 16.8
Temperatur (p=135*105Pa) [K] 1780 2420 1780 2420 2120 2420Temperature (p = 135 * 10 5 Pa) [K] 1780 2420 1780 2420 2120 2420
Gemessene Werte in 60 dm3 Kanne)Measured values in 60 dm 3 jug)
Kohlenmonoxid [ppm] 2500 2300 2300 2100 4500 4000Carbon monoxide [ppm] 2500 2300 2300 2100 4500 4000
Stickoxide [ppm] 200 250 200 250 400 250Nitrogen oxides [ppm] 200 250 200 250 400 250
Ammoniak [ppm] 0 0 0 0 200 150Ammonia [ppm] 0 0 0 0 200 150
Grobstaub in der Kanne [g] 07 0,6 07 07 0,9 1 ,3Coarse dust in the can [g] 07 0.6 07 07 0.9 1, 3
Feinstaub in der Kanne [g] 0,2 0,2 0,2 0,1 0,3 0,5 16Fine dust in the jug [g] 0.2 0.2 0.2 0.1 0.3 0.5 16
Beispiel Nr. 13 14 15 16 17 18Example No. 13 14 15 16 17 18
A = ATZ [%] - - - - - -A = ATZ [%] - - - - - -
NIGU [%] 48,2 47,0 47,0 48,5 47,0 47,0NIGU [%] 48.2 47.0 47.0 48.5 47.0 47.0
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuNO3 [%] - - - - - -GuNO 3 [%] - - - - - -
B = KN03 [%] 41 ,3 - - 41 ,0 - -B = KN0 3 [%] 41, 3 - - 41, 0 - -
Sr(N03)2 [%] - 42,5 42,5 - 42,5 42,5Sr (N0 3 ) 2 [%] - 42.5 42.5 - 42.5 42.5
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 0der 4 [%] 10,0 1 10,0 1 10,0 4 - - -C = Ti0 2 1 0 or 4 [%] 10.0 1 10.0 1 10.0 4 - - -
Zr02 2 oder 5 [%] - - - 10,0 2 10,0 2 10,0 5 Zr0 2 2 or 5 [%] - - - 10.0 2 10.0 2 10.0 5
AI2O3 3 [%] - - - - - -AI 2 O 3 3 [%] - - - - - -
AI2O3 + 1 %Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI2O3 + 1 %(Pd+Pt) 8 [%] - - - - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - - - - -
D = Eisen(lll)oxid 9 [%] - - - - - -D = iron (III) oxide 9 [%] - - - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - 0,5 0,5 - 0,5 0,5E = graphite [%] - 0.5 0.5 - 0.5 0.5
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%] 0,5 - - 0,5 - -Polyvinylbutyral [%] 0.5 - - 0.5 - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 23,8 23,1 23,1 23,9 23,1 23,1Gas yield (V = constant) [mol / kg] 23.8 23.1 23.1 23.9 23.1 23.1
Temperatur (p=135*105Pa) [K] 2030 2490 2490 2080 2550 2550Temperature (p = 135 * 10 5 Pa) [K] 2030 2490 2490 2080 2550 2550
Gemessene Werte (in 60 dm3 Kann e):Measured values (in 60 dm 3 can e):
Kohlenmonoxid [ppm] 8000 6500 8000 6500 6500 8000Carbon monoxide [ppm] 8000 6500 8000 6500 6500 8000
Stickoxide [ppm] 600 450 450 800 700 800Nitrogen oxides [ppm] 600 450 450 800 700 800
Ammoniak [ppm] 100 0 0 150 0 0Ammonia [ppm] 100 0 0 150 0 0
Grobstaub in der Kanne [g] 1 ,4 0,3 0,7 1 ,0 0,1 0,3Coarse dust in the can [g] 1, 4 0.3 0.7 1, 0 0.1 0.3
Feinstaub in der Kanne [g] 0,6 0,4 0,3 0,3 0,3 0,3 17Fine dust in the jug [g] 0.6 0.4 0.3 0.3 0.3 0.3 17
Beispiel Nr. 19 20 21 22 23 24Example No. 19 20 21 22 23 24
A = ATZ [%] - - - - - -A = ATZ [%] - - - - - -
NIGU [%] 50,6 46,0 46,0 46,5 50,6 46,5NIGU [%] 50.6 46.0 46.0 46.5 50.6 46.5
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuNO3 [%] - - - - - -GuNO 3 [%] - - - - - -
B = KN03 [%] 39,4 - - - 39,4 -B = KN0 3 [%] 39.4 - - - 39.4 -
Sr(N03)2 [%] - 43,5 43,5 38,5 - 38,5Sr (N0 3 ) 2 [%] - 43.5 43.5 38.5 - 38.5
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] - - - - - -C = Ti0 2 1 [%] - - - - - -
Zr02 [%] - - - - - -Zr0 2 [%] - - - - - -
Al203 30der 6 [%] 10,0 3 10,0 3 10,0 6 15,0 3 - -Al 2 0 3 30 or 6 [%] 10.0 3 10.0 3 10.0 6 15.0 3 - -
Al203 + 1 %Pt 7 [%] - - - - 10,0 15,0Al 2 0 3 + 1% Pt 7 [%] - - - - 10.0 15.0
AI203 + 1 %(Pd+Pt) 8 [%] - - - - - -AI 2 0 3 + 1% (Pd + Pt) 8 [%] - - - - - -
D = Eisen(lll)oxid 9 [%] - - - - - -D = iron (III) oxide 9 [%] - - - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - 0,5 0,5 - - -E = graphite [%] - 0.5 0.5 - - -
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%] - - - - - -Polyvinyl butyral [%] - - - - - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 24,3 22,8 22,8 22,4 24,3 22,4Gas yield (V = constant) [mol / kg] 24.3 22.8 22.8 22.4 24.3 22.4
Temperatur (p=135*105Pa) [K] 2050 2380 2380 2330 2430 2330Temperature (p = 135 * 10 5 Pa) [K] 2050 2380 2380 2330 2430 2330
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 5700 6000 8000 5000 4600 4200Carbon monoxide [ppm] 5700 6000 8000 5000 4600 4200
Stickoxide [ppm] 300 450 600 300 200 250Nitrogen oxides [ppm] 300 450 600 300 200 250
Ammoniak [ppm] 0 0 0 0 0 0Ammonia [ppm] 0 0 0 0 0 0
Grobstaub in der Kanne [g] 1 ,0 0,7 0,8 0,3 1 ,2 0,5Coarse dust in the can [g] 1.0 0.7 0.8 0.3 1.2 0.5
Feinstaub in der Kanne [g] 0,4 0,1 0,3 0,3 0,3 0,3 Beispiel Nr. 25 26 27 28 29 30Fine dust in the jug [g] 0.4 0.1 0.3 0.3 0.3 0.3 Example No. 25 26 27 28 29 30
A = ATZ [%] - - - - - -A = ATZ [%] - - - - - -
NIGU [%] 50,6 46,5 43,5 37,4 48,0 -NIGU [%] 50.6 46.5 43.5 37.4 48.0 -
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuN03 [%] - - - - - 51 ,7GuN0 3 [%] - - - - - 51, 7
B = KNO3 [%] 39,4 - 45,9 - 41 ,4 -B = KNO 3 [%] 39.4 - 45.9 - 41, 4 -
Sr(N03)2 [%] - 38,5 - 52,1 - 37,8Sr (N0 3 ) 2 [%] - 38.5 - 52.1 - 37.8
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] - - - - - -C = Ti0 2 1 [%] - - - - - -
Zr02 2 [%] - - - - - -Zr0 2 2 [%] - - - - - -
AI2O3 3 [%] - - - - 5,0 5,0AI 2 O 3 3 [%] - - - - 5.0 5.0
AI203 + 1 %Pt 7 [%] - - - - - -AI 2 0 3 + 1% Pt 7 [%] - - - - - -
AI203 + 1 %(Pd+Pf) 8 [%] 10,0 15,0 - - - -AI 2 0 3 + 1% (Pd + Pf) 8 [%] 10.0 15.0 - - - -
D = Eisen(lll)oxid 9 [%] - - 5,0 - 5,0 5,0D = iron (III) oxide 9 [%] - - 5.0 - 5.0 5.0
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - 5,0 10,0 - -Silicon nitride Si 3 N 4 [%] - - 5.0 10.0 - -
E = Graphit [%] - - 0,6 0,5 0,6 -E = graphite [%] - - 0.6 0.5 0.6 -
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%] - - - - - 0,5Polyvinyl butyral [%] - - - - - 0.5
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 24,3 22,4 23,3 19,8 23,6 26,0Gas yield (V = constant) [mol / kg] 24.3 22.4 23.3 19.8 23.6 26.0
Temperatur (p=135*105Pa) [K] 2430 2330 2130 2820 1970 2100Temperature (p = 135 * 10 5 Pa) [K] 2430 2330 2130 2820 1970 2100
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 4500 4000 6300 6700 8000 5500Carbon monoxide [ppm] 4500 4000 6300 6700 8000 5500
Stickoxide [ppm] 250 250 400 450 150 900Nitrogen oxides [ppm] 250 250 400 450 150 900
Ammoniak [ppm] 0 0 0 0 250 10Ammonia [ppm] 0 0 0 0 250 10
Grobstaub in der Kanne [g] 1 ,1 0,4 1 ,3 1 ,3 1 ,5 0,6Coarse dust in the can [g] 1, 1 0.4 1, 3 1, 3 1, 5 0.6
Feinstaub in der Kanne [g] 0,2 0,3 0,4 0,5 0,3 0,4 19Fine dust in the jug [g] 0.2 0.3 0.4 0.5 0.3 0.4 19
Beispiel Nr. 31 32 33 34 35 36Example No. 31 32 33 34 35 36
A = ATZ [%] - - - - - -A = ATZ [%] - - - - - -
NIGU [%] - 43,0 17,7 9,0 18,1 16,0NIGU [%] - 43.0 17.7 9.0 18.1 16.0
Ca-DCA [%3 27,8 3,0 17,7 23,8 - -Ca-DCA [% 3 27.8 3.0 17.7 23.8 - -
Na-DCA [%] - - - - 18,1 16,0Na-DCA [%] - - - - 18.1 16.0
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuN03 [%] - - - - - -GuN0 3 [%] - - - - - -
B = KN03 [%] - - - 57,2 - 58,0B = KN0 3 [%] - - - 57.2 - 58.0
Sr(N03)2 [%] 62,2 45,5 54,6 - 53,8 -Sr (N0 3 ) 2 [%] 62.2 45.5 54.6 - 53.8 -
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] - - - - - -C = Ti0 2 1 [%] - - - - - -
ZrO2 2 [%] - - - - - -ZrO 2 2 [%] - - - - - -
AI2O3 3 [%] 10,0 8,0 10,0 10,0 10,0 10,0AI 2 O 3 3 [%] 10.0 8.0 10.0 10.0 10.0 10.0
AI2O3 + 1 %Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI2O3 + 1 %(Pd+Pt) 8 [%] - - '- - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - ' - - - -
D = Eisen(lll)oxid 9 [%] - - - - - -D = iron (III) oxide 9 [%] - - - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - - - - - -E = graphite [%] - - - - - -
Methylhydroxyethylcellulose11 [%] - 0,5 - - - -Methylhydroxyethylcellulose 11 [%] - 0.5 - - - -
Polyvinylbutyral [%] - - - - - -Polyvinyl butyral [%] - - - - - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 11 ,4 22,5 15,8 14,0 17,4 14,7Gas yield (V = constant) [mol / kg] 11.4 22.5 15.8 14.0 17.4 14.7
Temperatur (p=135*105Pa) [K] 2440 2470 2420 1780 2230 1780Temperature (p = 135 * 10 5 Pa) [K] 2440 2470 2420 1780 2230 1780
Gemessene Werte (in 60 dm3 Kanne 0:Measured values (in 60 dm 3 can 0:
Kohlenmonoxid [ppm] 2800 8000 3600 8000 10000 450Carbon monoxide [ppm] 2800 8000 3600 8000 10000 450
Stickoxide [ppm] 700 1000 800 500 800 100Nitrogen oxides [ppm] 700 1000 800 500 800 100
Ammoniak [ppm] 0 0 0 50 3 2Ammonia [ppm] 0 0 0 50 3 2
Grobstaub in der Kanne [g] 2,2 0,6 1 ,2 3,2 1 ,3 1 ,5Coarse dust in the can [g] 2.2 0.6 1, 2 3.2 1, 3 1, 5
Feinstaub in der Kanne [g] 0,5 0,3 0,4 0,4 0,2 0,3 20Fine dust in the jug [g] 0.5 0.3 0.4 0.4 0.2 0.3 20th
Beispiel Nr. 37 38 39 40 41 42Example No. 37 38 39 40 41 42
A = ATZ [%] - - - - - -A = ATZ [%] - - - - - -
NIGU [%] - - - - - -NIGU [%] - - - - - -
Ca-DCA [%] 26,0 28,7 - - - -Ca-DCA [%] 26.0 28.7 - - - -
Na-DCA [%] - - 28,5 28,5 - -Na-DCA [%] - - 28.5 28.5 - -
TAGN [%] - - - - 48,6 22,7TAGN [%] - - - - 48.6 22.7
GuNO3 [%] - - - - - 22,7GuNO 3 [%] - - - - - 22.7
B = KNO3 [%] - 61 ,3 - 61 ,0 41 ,4 34,6B = KNO 3 [%] - 61, 3 - 61, 0 41, 4 34.6
Sr(N03)2 [%] 59,6 - 61 ,5 - - -Sr (N0 3 ) 2 [%] 59.6 - 61, 5 - - -
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = Ti02 1 [%] 14,0 10,0 10,0 10,0 - -C = Ti0 2 1 [%] 14.0 10.0 10.0 10.0 - -
Zr02 2 [%] - - - - - -Zr0 2 2 [%] - - - - - -
Al203 3 [%] - - - - 10,0 20,0Al 2 0 3 3 [%] - - - - 10.0 20.0
AI2O3 + 1%Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI2O3 + 1 %(Pd+Pt) 8 [%] - - - - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - - - - -
D = Eisen(lll)oxid 9 [%] - - - - - -D = iron (III) oxide 9 [%] - - - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - - - - - -E = graphite [%] - - - - - -
Methylhydroxyethylcellulose11 [%] 0,4 - - - - -Methylhydroxyethylcellulose 11 [%] 0.4 - - - - -
Polyvinylbutyral [%] - - - 0,5 - -Polyvinylbutyral [%] - - - 0.5 - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 10,9 11 ,7 9,7 10,7 26,2 23,4Gas yield (V = constant) [mol / kg] 10.9 11.7 9.7 10.7 26.2 23.4
Temperatur (p=135*105Pa) [K] 2400 1780 2240 1780 2140 1800Temperature (p = 135 * 10 5 Pa) [K] 2400 1780 2240 1780 2140 1800
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 1500 1800 2000 2500 3000 2700Carbon monoxide [ppm] 1500 1800 2000 2500 3000 2700
Stickoxide [ppm] 300 800 500 1000 150 350Nitrogen oxides [ppm] 300 800 500 1000 150 350
Ammoniak [ppm] 10 5 15 3 160 24Ammonia [ppm] 10 5 15 3 160 24
Grobstaub in der Kanne [g] 1 ,0 17 1 ,1 1 ,5 1 ,4 0,8Coarse dust in the can [g] 1, 0 17 1, 1 1, 5 1, 4 0.8
Feinstaub in der Kanne lg] 0,4 0,5 0,3 0,4 0,3 0,2 21Fine dust in the jug lg] 0.4 0.5 0.3 0.4 0.3 0.2 21
Beispiel Nr. 43 44 45 46 47 48Example No. 43 44 45 46 47 48
A = ATZ [%] 17,7 - - - - -A = ATZ [%] 17.7 - - - - -
NIGU [%] - - - - - -NIGU [%] - - - - - -
Ca-DCA [%] - - 18,8 - - -Ca-DCA [%] - - 18.8 - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] 17,7 - - - - -TAGN [%] 17.7 - - - - -
GuN03 [%] - 54,2 18,8 50,0 50,0 51 ,5GuN0 3 [%] - 54.2 18.8 50.0 50.0 51.5
B = KNO3 [%] 44,6 35,8 52,4 - - -B = KNO 3 [%] 44.6 35.8 52.4 - - -
Sr(N03)2 [%] - - - 39,4 39,4 38,0Sr (N0 3 ) 2 [%] - - - 39.4 39.4 38.0
NaN03 [%] - - - - - -NaN0 3 [%] - - - - - -
C = TiO2 1 [%] - - - - 10,0 -C = TiO 2 1 [%] - - - - 10.0 -
ZrO2 2 [%] - - - - - 10,0ZrO 2 2 [%] - - - - - 10.0
AI2O3 3 [%] 20,0 5,0 10,0 10,0 - -AI 2 O 3 3 [%] 20.0 5.0 10.0 10.0 - -
AI2O3 + 1%Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI2O3 + 1%(Pd+Pt) 8 [%] - - - - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - - - - -
D = Eisen(lll)oxid 9 [%] - 5,0 - - - -D = iron (III) oxide 9 [%] - 5.0 - - - -
Aluminiumsilikat 10 [%] - - - - - -Aluminum silicate 10 [%] - - - - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - - - 0,6 0,6 -E = graphite [%] - - - 0.6 0.6 -
Methylhydroxyethylcellulose11 [%] - - - - - 0,5Methyl hydroxyethyl cellulose 11 [%] - - - - - 0.5
Polyvinylbutyral [%] - - - - - -Polyvinyl butyral [%] - - - - - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 20,0 26,6 16,9 25,1 25,1 25,7Gas yield (V = constant) [mol / kg] 20.0 26.6 16.9 25.1 25.1 25.7
Temperatur (p=135*105Pa) [K] 1810 1780 1780 2120 2130 2170Temperature (p = 135 * 10 5 Pa) [K] 1810 1780 1780 2120 2130 2170
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 1000 5000 7000 6000 4000 3500Carbon monoxide [ppm] 1000 5000 7000 6000 4000 3500
Stickoxide [ppm] 150 400 150 800 100 500Nitrogen oxides [ppm] 150 400 150 800 100 500
Ammoniak [ppm] 50 100 150 5 0 10Ammonia [ppm] 50 100 150 5 0 10
Grobstaub in der Kanne [g] 1 ,0 2,0 1 ,8 1 ,5 1 ,0 0,5Coarse dust in the can [g] 1, 0 2.0 1, 8 1, 5 1, 0 0.5
Feinstaub in der Kanne [g] 0,4 0,5 0,6 0,4 0,5 0,3 22Fine dust in the jug [g] 0.4 0.5 0.6 0.4 0.5 0.3 22
Beispiel Nr. 49 50 51 52 53 54Example No. 49 50 51 52 53 54
A = ATZ [%] 29,75 30,2 30,2 26,5 26,8 33,7A = ATZ [%] 29.75 30.2 30.2 26.5 26.8 33.7
NIGU [%] - - - 8,0 - -NIGU [%] - - - 8.0 - -
Ca-DCA [%] - - - - - -Ca-DCA [%] - - - - - -
Na-DCA [%] - - - - - -Na-DCA [%] - - - - - -
TAGN [%] - - - - - -TAGN [%] - - - - - -
GuN03 [%] - - - - 8,0 -GuN0 3 [%] - - - - 8.0 -
B = KN03 [%] 50,25 49,8 49,8 32,5 32,2 56,3B = KN0 3 [%] 50.25 49.8 49.8 32.5 32.2 56.3
Sr(N03)2 [%] - - - - - -Sr (N0 3 ) 2 [%] - - - - - -
NaN03 [%] - - - 15,0 15,0 -NaN0 3 [%] - - - 15.0 15.0 -
C = Ti02 1 [%] - - - - - 10,0C = Ti0 2 1 [%] - - - - - 10.0
Zr02 2 [%] 3,0 10,0 - - - -Zr0 2 2 [%] 3.0 10.0 - - - -
Al203 3 [%] 14,0 10,0 10,0 18,0 18,0 -Al 2 0 3 3 [%] 14.0 10.0 10.0 18.0 18.0 -
AI2O3 + 1 %Pt 7 [%] - - - - - -AI 2 O 3 + 1% Pt 7 [%] - - - - - -
AI203 + 1 %(Pd+Pt) 8 [%] 3,0 - - - - -AI 2 0 3 + 1% (Pd + Pt) 8 [%] 3.0 - - - - -
D = Eisen(lll)oxid 9 [%] - - - - - -D = iron (III) oxide 9 [%] - - - - - -
Aluminiumsilikat 10 [%] - - 10,0 - - -Aluminum silicate 10 [%] - - 10.0 - - -
Siliziumnitrid Si3N4 [%] - - - - - -Silicon nitride Si 3 N 4 [%] - - - - - -
E = Graphit [%] - - - - - -E = graphite [%] - - - - - -
Methylhydroxyethylcellulose11 [%] - - - - - -Methylhydroxyethylcellulose 11 [%] - - - - - -
Polyvinylbutyral [%] - - - - - -Polyvinyl butyral [%] - - - - - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 17,6 17,8 19,3 19,4 19,7 19,8Gas yield (V = constant) [mol / kg] 17.6 17.8 19.3 19.4 19.7 19.8
Temperatur (p=135*105Pa) [K] 1780 1780 1920 1800 1780 1820Temperature (p = 135 * 10 5 Pa) [K] 1780 1780 1920 1800 1780 1820
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 2600 3000 4500 3500 6500 8000Carbon monoxide [ppm] 2600 3000 4500 3500 6500 8000
Stickoxide [ppm] 300 200 300 800 500 250Nitrogen oxides [ppm] 300 200 300 800 500 250
Ammoniak [ppm] 23 50 50 0 5 300Ammonia [ppm] 23 50 50 0 5 300
Grobstaub in der Kanne [g] 1.0 1 ,1 1 ,2 0,8 1 ,0 0,8Coarse dust in the can [g] 1.0 1, 1 1, 2 0.8 1, 0 0.8
Feinstaub in der Kanne [g] 0,2 0,4 0,5 0,2 0,2 0,3 23Fine dust in the jug [g] 0.2 0.4 0.5 0.2 0.2 0.3 23
Beispiel Nr. 55 56 57Example No. 55 56 57
A = ATZ [%] 30,35 31 ,66 29,75A = ATZ [%] 30.35 31, 66 29.75
NIGU [%] - - -NIGU [%] - - -
Ca-DCA [%] - - -Ca-DCA [%] - - -
Na-DCA [%] - - -Na-DCA [%] - - -
TAGN [%] - - -TAGN [%] - - -
GuNO3 [%] - - -GuNO 3 [%] - - -
B = KN03 [%] 49,65 - 50,25B = KN0 3 [%] 49.65 - 50.25
Sr(N03)2 [%] - 56,34 -Sr (N0 3 ) 2 [%] - 56.34 -
NaN03 [%] - - -NaN0 3 [%] - - -
C = Ti02 1 [%] - - -C = Ti0 2 1 [%] - - -
ZrO2 2 [%] - - -ZrO 2 2 [%] - - -
Al2O3 3 [%] 10,0 9,0 20,0Al 2 O 3 3 [%] 10.0 9.0 20.0
AI203 + 1 %Pt 7 [%] - - -AI 2 0 3 + 1% Pt 7 [%] - - -
AI2O3 + 1%(Pd+Pt) 8 [%] - - -AI 2 O 3 + 1% (Pd + Pt) 8 [%] - - -
D = Eisen(lll)oxid 9 [%] 6,0 - -D = iron (III) oxide 9 [%] 6.0 - -
Aluminiumsilikat 10 [%] 4,0 3,0 -Aluminum silicate 10 [%] 4.0 3.0 -
Siliziumnitrid Si3N4 [%] - - -Silicon nitride Si 3 N 4 [%] - - -
E = Graphit [%] - - -E = graphite [%] - - -
Methylhydroxyethylcellulose11 [%] - - -Methylhydroxyethylcellulose 11 [%] - - -
Polyvinylbutyral [%] - - -Polyvinyl butyral [%] - - -
Theoretische Werte:Theoretical values:
Gasausbeute (V=konstant) [mol/kg] 18,2 18,8 17,6Gas yield (V = constant) [mol / kg] 18.2 18.8 17.6
Temperatur (p=135*105Pa) [K] 1780 2390 1780Temperature (p = 135 * 10 5 Pa) [K] 1780 2390 1780
Gemessene Werte (in 60 dm3 Kanne)Measured values (in 60 dm 3 jug)
Kohlenmonoxid [ppm] 6000 7500 3500Carbon monoxide [ppm] 6000 7500 3500
Stickoxide [ppm] 100 250 400Nitrogen oxides [ppm] 100 250 400
Ammoniak [ppm] 150 0 0Ammonia [ppm] 150 0 0
Grobstaub in der Kanne [g] 1 ,5 0,7 0,7Coarse dust in the can [g] 1, 5 0.7 0.7
Feinstaub in der Kanne [g] 0,4 0,3 0,3 24Fine dust in the jug [g] 0.4 0.3 0.3 24
Die Abbrände wurden in einem praxisnahen Gasgeneratorgehäuse für den 60 Liter Fahrer- Airbag durchgeführt, mit Originalabmessungen, -anzünder und Filterpaket aus Edelstahl.The burns were carried out in a practical gas generator housing for the 60 liter driver airbag, with original dimensions, lighter and filter package made of stainless steel.
Das eingesetzte Gasgeneratortreibsatzgewicht betrug 50 bis 55 g, je nach Gasausbeute der jeweiligen Gasgeneratortreibstoff-Rezeptur.The gas generator propellant weight used was 50 to 55 g, depending on the gas yield of the respective gas generator propellant formulation.
Die Pellets hatten je nach Abbrandeigenschaften einen Durchmesser von 4 bis 6 mm, bei einer Pellethöhe von 1,5 bzw. 2,1 mm.Depending on the burning properties, the pellets had a diameter of 4 to 6 mm, with a pellet height of 1.5 or 2.1 mm.
Die Gasausbeute und die Temperatur liegt im für Gasgeneratortreibstoffe für Airbags günstigen Bereich.The gas yield and the temperature are in the range favorable for gas generator fuels for airbags.
Bei der Angabe „Grobstaub" und „Feinstaub" in der Tabelle handelt es sich um den Schmutz in der Kanne nach der Verbrennung.The "coarse dust" and "fine dust" information in the table relates to the dirt in the jug after combustion.
Die in der vorstehenden Tabelle angegebenen gemessenen Werte für CO, NOx und NH3 beziehen sich auf eine 60 Liter-Kanne. Hierbei handelt es sich um gute Werte für einen nicht optimierten Versuchsgasgenerator.The measured values for CO, NO x and NH 3 given in the table above refer to a 60 liter jug. These are good values for a non-optimized test gas generator.
Aus dem Vergleich der Beispiele 14 mit 15, 17 mit 18 und 20 mit 21 ist der Effekt der hochdispersen Oxide im Vergleich zu den herkömmlichen Oxiden ersichtlich. Die Verringerung des Partikelausstoßes (Grob -und Feinstaub) betrug bei dem System Nitroguanidin/ Strontiumnitrat aufgrund der speziellen, erfindungsgemäß verwendeten hochdispersen Schlackenfänger (C) ca. 20 bis 40% im Vergleich zu den herkömmlichen Oxiden gleicher chemischer St kturformel, aber geringerer spezifischer Oberfläche. Ebenfalls ersichtlich ist die Verringerung der toxischen Gasanteile um ca. 10 bis 25% bedingt durch die Verbesserung der Verbrennung aufgrund der speziellen, erfindungsgemäß verwendeten Schlackenfänger (C) und deren Eigenschaften.The effect of the highly disperse oxides in comparison with the conventional oxides can be seen from the comparison of examples 14 with 15, 17 with 18 and 20 with 21. The reduction in particle emissions (coarse and fine dust) in the system nitroguanidine / strontium nitrate was approx. 20 to 40% in comparison to the conventional oxides of the same chemical structure formula but with a smaller specific surface due to the special, highly disperse slag catcher (C) used according to the invention. Also evident is the reduction in the toxic gas fractions by approx. 10 to 25% due to the improvement in the combustion due to the special slag trap (C) used according to the invention and their properties.
Weiterhin ist aus dem Vergleich, z.B. der Gasgeneratortreibstoffe der Beispiele 2 mit 8 und 10 der zusätzliche günstige Effekt bei der Verwendung von mit Katalysatoren dotierten hochdispersen Schlackenfängem (C) auf die Bildung von toxischen Gasanteilen ersichtlich. 25Furthermore, from the comparison, for example of the gas generator fuels of Examples 2 with 8 and 10, the additional favorable effect when using highly dispersed slag traps (C) doped with catalysts on the formation of toxic gas fractions can be seen. 25th
Der Anteil an CO und NOx liegt bei den Beispielen 8 und 10 (mit Katalysator) unter den in Beispiel 2 (ohne Katalysator, aber ansonsten mit gleicher Zusammensetzung) angegebenen Werte.The proportion of CO and NO x in Examples 8 and 10 (with catalyst) is below the values given in Example 2 (without catalyst, but otherwise with the same composition).
Besonders bevorzugte Zusammensetzungen sind die der Beispiele 14, 17 und 20.Particularly preferred compositions are those of Examples 14, 17 and 20.
Die thermodynamischen Daten der einzelnen Gasrezepturen wurden auf den Sauerstoffbilanzüberschuß hin berechnet, der möglichst wenig toxische Gasentwicklung beim Abbrand versprach. The thermodynamic data of the individual gas formulations were calculated based on the excess oxygen balance, which promised as little toxic gas development as possible on combustion.

Claims

Patentansprüche claims
1. Gasgeneratortreibstoff, umfassend1. Gas generator fuel comprising
(A) mindestens einen Brennstoff aus der Gruppe bestehend aus Guanidiniumnitrat (GUNI; GuNO3), Dicyanamid, Ammoniumdicyanamid, Natriumdicyanamid (Na-DCA), Kupferdicyanamid, Zinndicyanamid, Calciumdicyanamid (Ca-DCA), Guanidiniumdicyanamid (GDCA), Aminoguanidiniumbicarbonat (AGB),(A) at least one fuel from the group consisting of guanidinium nitrate (GUNI; GuNO 3 ), dicyanamide, ammonium dicyanamide, sodium dicyanamide (Na-DCA), copper dicyanamide, tin dicyanamide, calcium dicyanamide (Ca-DCA), guanidinium dicyanamide (GDCA), aminoganidinium ,
Aminoguanidiniumnitrat (AGN), Triaminoguanidiniumnitrat (TAGN), Nitroguanidin (NIGU), Dicyandiamid (DCD), Azodicarbonamid (ADCA) sowie Tetrazol (HTZ), 5- Aminotetrazol (ATZ), 5-Nitro-l,2,4-triazol-3-on (NTO), deren Salze und deren Gemische,Aminoguanidinium nitrate (AGN), triaminoguanidinium nitrate (TAGN), nitroguanidine (NIGU), dicyandiamide (DCD), azodicarbonamide (ADCA) as well as tetrazole (HTZ), 5-aminotetrazole (ATZ), 5-nitro-l, 2,4-triazol-3 -on (NTO), its salts and their mixtures,
(B) mindestens ein Alkali- oder Erdalkalinitrat oder Ammoniumnitrat, -chlorat oder -perchlorat,(B) at least one alkali or alkaline earth nitrate or ammonium nitrate, chlorate or perchlorate,
(C) mindestens einen hochschmelzenden, im wesentlichen chemisch inerten Schlackenfänger, ausgewählt aus der Gruppe umfassend Al2O3, TiO2 und ZrO2 in hochdisperser Form oder Gemische davon.(C) at least one high-melting, essentially chemically inert slag catcher, selected from the group comprising Al 2 O 3 , TiO 2 and ZrO 2 in highly dispersed form or mixtures thereof.
2. Gasgeneratortreibstoff nach Anspruch 1, wobei Komponente (A) in einer Menge von etwa 20 bis 60 Gew.-%, vorzugsweise von etwa 28 bis 52 Gew.-% und insbesondere von etwa 45 bis 51 Gew.-%, Komponente (B) in einer Menge von etwa 38 bis etwa 63 Gew.-%, vorzugsweise von etwa 38 bis etwa 55 Gew.-% und insbesondere von etwa 39 bis 45 Gew.- %, Komponente (C) in einer Menge von etwa 5 bis 22 Gew.-%, vorzugsweise von etwa 8 bis 20 Gew.-% und insbesondere von etwa 9 bis 11 Gew.-% vorliegt. 272. Gas generator fuel according to claim 1, wherein component (A) in an amount of about 20 to 60 wt .-%, preferably from about 28 to 52 wt .-% and in particular from about 45 to 51 wt .-%, component (B ) in an amount from about 38 to about 63% by weight, preferably from about 38 to about 55% by weight and in particular from about 39 to 45% by weight, component (C) in an amount from about 5 to 22 % By weight, preferably from about 8 to 20% by weight and in particular from about 9 to 11% by weight. 27
3. Gasgeneratortreibstoff nach Anspruch 1 oder 2, wobei Komponente (A) ausgewählt ist aus der Gruppe bestehend aus Nitroguanidin, 5-Aminotetrazol, Dicyandiamid, Dicyanamid, Natrium- und Calciumdicyanamid und Guanidiniumnitrat, und deren Gemische.3. Gas generator fuel according to claim 1 or 2, wherein component (A) is selected from the group consisting of nitroguanidine, 5-aminotetrazole, dicyandiamide, dicyanamide, sodium and calcium dicyanamide and guanidinium nitrate, and mixtures thereof.
4. Gasgenertortreibstoff nach einem der Ansprüche 1 bis 3, wobei Komponente (B) ausgewählt ist aus der Gruppe bestehend aus Natrium-, Kalium- oder Strontiumnitrat.4. Gas generator fuel according to one of claims 1 to 3, wherein component (B) is selected from the group consisting of sodium, potassium or strontium nitrate.
5. Gasgenertortreibstoff nach einem der Ansprüche 1 bis 4, wobei Komponente (C) ausgewählt ist aus der G ppe bestehend aus hochdispersem Al2O3, hochdispersem Ti02 oder hochdispersem ZrO2.5. Gas generator fuel according to one of claims 1 to 4, wherein component (C) is selected from the G ppe consisting of highly disperse Al 2 O 3 , highly disperse Ti0 2 or highly disperse ZrO 2 .
6. Gasgenertortreibstoff nach Anspruch 5, wobei Komponente (C) ausgewählt ist aus der Gmppe bestehend aus hochdispersem Al2O3 mit einer spezifischen Oberfläche von 100 +/- 15 m2/g, hochdispersem TiO2 mit einer spezifischen Oberfläche von 50 +/- 15 m2/g oder hochdispersem ZrO2 mit einer spezifischen Oberfläche von 40 +/- 10 m2/g.6. Gas generator fuel according to claim 5, wherein component (C) is selected from the group consisting of highly disperse Al 2 O 3 with a specific surface area of 100 +/- 15 m 2 / g, highly disperse TiO 2 with a specific surface area of 50 + / - 15 m 2 / g or highly disperse ZrO 2 with a specific surface of 40 +/- 10 m 2 / g.
7. Gasgenertortreibstoff nach Anspruch 5, wobei ein Teil der Komponente (C) als Träger dient, auf dem ein Platinmetall oder eine Metallegierung aus Platinmetallen oder Kupfer in einer katalytisch wirksamen Schichtdicke aufgebracht ist.7. Gas generator fuel according to claim 5, wherein a part of component (C) serves as a carrier on which a platinum metal or a metal alloy made of platinum metals or copper is applied in a catalytically active layer thickness.
8. Gasgenertortreibstoff nach Anspruch 7, wobei das Platinmetall ausgewählt ist aus Ruthenium (Ru), Osmium (Os), Rhodium (Rh), Iridium (Ir), Palladium (Pd) oder Platin (Pt).8. Gas generator fuel according to claim 7, wherein the platinum metal is selected from ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) or platinum (Pt).
9. Gasgenertortreibstoff nach Anspruch 7, wobei die Metallegierung aus Platinmetallen ausgewählt ist aus Pt/Pd- und Pt/Rh-Legierungen.9. Gas generator fuel according to claim 7, wherein the metal alloy is selected from platinum metals from Pt / Pd and Pt / Rh alloys.
10. Gasgenertortreibstoff nach einem der Ansprüche 7 bis 9, wobei der Gewichtsanteil des Katalysators an der Komponente (C) 0,1-5 Gew.-%, vorzugsweise 0,2-1,2 Gew.-% beträgt.10. Gas generator fuel according to one of claims 7 to 9, wherein the proportion by weight of the catalyst in component (C) is 0.1-5% by weight, preferably 0.2-1.2% by weight.
11. Gasgenertortreibstoff nach einem der Ansprüche 1 bis 10, wobei Komponente (A) Nitroguanidin ist, Komponente (B) Strontiumnitrat ist und Komponente (C) hochdisperses Al2O3, TiO2 oder ZrO2 ist. 11. Gas generator fuel according to one of claims 1 to 10, wherein component (A) is nitroguanidine, component (B) is strontium nitrate and component (C) is highly disperse Al 2 O 3 , TiO 2 or ZrO 2 .
12. Gasgenertortreibstoff nach Anspruch 11, wobei Komponente (A) in einer Menge von 45 bis 51 Gew.-% vorliegt, Komponente (B) in einer Menge von 39 bis 45 Gew.-% vorliegt und Komponente (C) in einer Menge von 9 bis 11 Gew.-% vorliegt, jeweils bezogen auf die Gesamtzusammensetzung.12. Gas generator fuel according to claim 11, wherein component (A) is present in an amount of 45 to 51% by weight, component (B) is present in an amount of 39 to 45% by weight and component (C) in an amount of 9 to 11% by weight is present, in each case based on the total composition.
13. Gasgenertortreibstoff nach einem der Ansprüche 1 bis 11, wobei zusätzlich Komponente (D) mindestens ein Schlackenbildner, ausgewählt aus Alkali- und Erdalkalimetallcarbonaten, Alkalimetall- oder Erdalkalimetalloxiden, Silikaten, Aluminaten, Aluminiumsilikaten, Siliciumnitrid (Si3N4) und Eisen(III)oxid anwesend ist.13. Gas generator fuel according to one of claims 1 to 11, wherein in addition component (D) at least one slag former selected from alkali and alkaline earth metal carbonates, alkali metal or alkaline earth metal oxides, silicates, aluminates, aluminum silicates, silicon nitride (Si 3 N 4 ) and iron (III ) oxide is present.
14. Gasgenertortreibstoff nach Anspruch 13, wobei Komponente (D) in einer Menge von etwa 2 bis 12 Gew.-%, vorzugsweise in einer Menge von etwa 4 bis 10 Gew.-% vorliegt.14. Gas generator fuel according to claim 13, wherein component (D) is present in an amount of approximately 2 to 12% by weight, preferably in an amount of approximately 4 to 10% by weight.
15. Gasgenertortreibstoff nach einem der Ansprüche 1 bis 14, wobei zusätzlich Komponente (E) mindestens ein in Wasser bei Raumtemperatur lösliches Bindemittel enthalten ist.15. Gas generator fuel according to one of claims 1 to 14, wherein component (E) is additionally contained at least one water-soluble binder at room temperature.
16. Gasgenertortreibstoff nach Anspruch 15, wobei das Bindemittel ausgewählt ist aus der Gmppe bestehend aus Celluloseverbmdungen, Polymerisaten aus einem oder mehreren polymerisierbaren olefmisch ungesättigten Monomeren, einem in Wasser bei Raumtemperatur unlöslichen Metallsalz der Stearinsäure oder Graphit.16. Gas generator fuel according to claim 15, wherein the binder is selected from the group consisting of cellulose compounds, polymers of one or more polymerizable olefinically unsaturated monomers, a metal salt of stearic acid or graphite which is insoluble in water at room temperature.
17. Gasgenertortreibstoff nach Anspruch 15 oder 16, wobei das Bindemittel in einer Menge von 0 bis 2 Gew.-%, vorzugsweise von 0,3-0,8 Gew.-% vorliegt.17. Gas generator fuel according to claim 15 or 16, wherein the binder is present in an amount of 0 to 2 wt .-%, preferably 0.3-0.8 wt .-%.
18. Verwendung des Gasgeneratortreibstoffs nach einem der Ansprüche 1 bis 17 als Gaserzeugungsmittel in Airbags, als Löschmittel oder Treibmittel. 18. Use of the gas generator fuel according to one of claims 1 to 17 as a gas generating agent in airbags, as an extinguishing agent or blowing agent.
EP99919100A 1998-03-20 1999-03-17 Propellants for gas generator Expired - Lifetime EP1064242B1 (en)

Applications Claiming Priority (3)

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DE19812372 1998-03-20
DE19812372A DE19812372C2 (en) 1998-03-20 1998-03-20 Gas generator fuels
PCT/DE1999/000782 WO1999048843A1 (en) 1998-03-20 1999-03-17 Propellants for gas generator

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