EP1046626A1 - Rocket propellant - Google Patents

Rocket propellant Download PDF

Info

Publication number
EP1046626A1
EP1046626A1 EP00108297A EP00108297A EP1046626A1 EP 1046626 A1 EP1046626 A1 EP 1046626A1 EP 00108297 A EP00108297 A EP 00108297A EP 00108297 A EP00108297 A EP 00108297A EP 1046626 A1 EP1046626 A1 EP 1046626A1
Authority
EP
European Patent Office
Prior art keywords
insulation layer
rocket propellant
fuel
weight
binder
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
EP00108297A
Other languages
German (de)
French (fr)
Other versions
EP1046626B1 (en
Inventor
Klaus Dr. Menke
Gerhard Gunser
Werner Kuglstatter
Adrian Hüls
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1046626A1 publication Critical patent/EP1046626A1/en
Application granted granted Critical
Publication of EP1046626B1 publication Critical patent/EP1046626B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones

Definitions

  • the invention relates to a rocket propellant reduced smoke combustion, especially for forehead burners, with a fuel based on ammonium perchlorate with a binder made from isocyanate-bound, hydroxy-terminated Polybutadiene and one surrounding the fuel inhibiting insulation layer. Furthermore, the invention to a method for producing such a rocket propellant directed.
  • the inhibiting isolation When a rocket propellant that burns over 20, 40 or 60 s, the inhibiting isolation must be next good adhesion and compatibility with the fuel too perform a thermal protection function that the combustion chamber wall just like the inhibited non-burning Fuel surface before premature pyrolysis and ignition protects. With smoke-reduced composite fuels, that contain little or no particles in the exhaust gas the insulation must not release any particles. Likewise, at the high temperatures of the Do not generate soot clouds in the exhaust gas jet and only burn insignificantly, otherwise with small diameters the specific momentum of the fuel and thus reduces the power of the engine become. The sum of these properties is e.g.
  • the invention has for its object a rocket propellant to create a simpler and cheaper one Production with an improved connection of the Allows fuel to the insulation. Furthermore, a Process for producing such a rocket propellant be proposed.
  • this task is per se well-known smoke-reduced, polyurethane-bound composite fuel based on ammonium perchlorate and isocyanate-bound hydroxy-terminated polybutadiene solved in that for the inhibition of the fuel surface insulation is used that a Polyurethane binder and a filler combination of 2-8 % By weight, preferably 3-5% by weight silicon carbide, 18-16 % By weight, preferably 24-50% by weight of silica in the form of amorphous quartz powder and 2-20% by weight solid temperature-resistant Fibers with a length of 1-20mm are embedded in it contains.
  • the insulation according to the invention usually also has a good one without mechanical or chemical pretreatment Liability to the fuel. It shows at high and low Temperature equally good elasticity and is about the composition of the polyurethane binder by the Share of di- or triisocyanate or added crosslinking Triplets adjustable in their mechanical properties.
  • this isolation is advantageously based on hydroxy-terminated polybutadiene bonded with isophorone diisocyanate (IPDI) or dimeryl diisocyanate (DMDI) or with other diisocyanates.
  • IPDI isophorone diisocyanate
  • DMDI dimeryl diisocyanate
  • Another polyester polyol or polyether polyol, which is bound with di-, tri or polymeric isocyanate, can also be used as the base material for the insulation.
  • ultrafine silicon dioxide, ultrafine titanium dioxide and zirconium dioxide can also be added as further fillers. These fillers are used in a grain size in the range of 20-50 nm for silicon dioxide and 50-1000 nm for TiO 2 and ZrO 2 . They cause the ceramic layer formed during pyrolysis to solidify, thereby reducing its swelling and ablation without influencing the heat transfer.
  • Essential for the cohesion of the pyrolyzed layers is a proportion of 1-20% solid fibers in length from 1-20 mm in the form of high temperature resistant plastic fibers made of polyester, polyamide, polyimide or Polybenzimidazole fibers as well as on carbon fibers, glass or Silicate or ceramic fibers can be constructed.
  • the fibers can be mixed before into the prepolymeric insulation mixture with water desized or organic solvent and if necessary with be provided with an adhesion-promoting layer. This can be used for glass, silicate or ceramic fibers made of functional Silanes, advantageous for plastic or carbon fibers made of polyisocyanate and short-chain polyester polyol consist.
  • the fibers ensure the cohesion of the formed Slag and for the formation of a solid ceramized Layer.
  • the insulation can be made into a corresponding slurry as a prepolymer slurry by die-casting or vacuum pull-up Form associated with the fuel.
  • the insulation combines with the fuel for a fixed ready-to-install propellant block.
  • the insulation can also be in the prepolymeric state in the combustion chamber or a non-stick coated Tube of the same inner diameter and ejected be cured.
  • the propellant is then poured in of the fuel slurries in the finished, if necessary through mechanical roughening or chemical bonding agents pre-treated insulation jacket with subsequent hardening Made at 60-65 ° C.
  • the fuel can be in the smoke-reduced version in addition to ammonium perchlorate (AP) in proportions of 50-90 %
  • AP ammonium perchlorate
  • nitramines such as hexogen or octogen
  • ferric oxide or ferrocene derivatives as Combustion catalysts in proportions of 0 to 15% by weight
  • the binder is advantageously composed of 8-20% by weight hydroxy-terminated polybutadiene with isophorone diisocyanate (IPDI) or dimeryl diisocyanate (DMDI) in equivalents Proportions was bound, as well as 2-8% by weight plasticizer, 0.1-0.5% by weight of antioxidant, optionally 0.1-0.3% by weight of processing aids, 50-500ppm curing catalyst, preferably triphenyl bismuth and 0.1-1% coupling agent for AP, preferably based on cyanoethylated polyamines or cyanoethylated polyamino alcohols.
  • IPDI isophorone diisocyanate
  • DMDI dimeryl diisocyanate
  • HTPB Hydroxy-terminated polybutadiene
  • IPDI Isophorone diisocyanate
  • Antioxidant 0.20%
  • Plasticizer diisooctyl adipate
  • Adhesion promoter triphenyl bismuth
  • Silicon carbide 4.53% SiO 2 powder quartz 33.79% TiO 2 super fine 1.90% Carbon fiber 3.65%
  • the practical impulse of the fuel is about 93% the theoretical value, the weight loss of the insulation when burned up about 2%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Ammonium perchlorate-based fuel for low-smoke rocket propellant is surrounded by an inhibiting insulation layer comprising polyurethane binder and a mixture of 2-8 wt.% silicon carbide, 20-60 wt.% silicon dioxide and 2-20 wt.% heat-resistant carbon, polymer, silicate or ceramic fibers. Low-smoke rocket propellant, especially for end burners, comprises an ammonium perchlorate (AP)-based fuel containing an isocyanate-bonded, hydroxy-terminated polybutadiene binder, in which the fuel is surrounded by an inhibiting insulation layer comprising a polyurethane binder and a filler combination containing 2-8 wt.% silicon carbide, 20-60 wt.% silicon dioxide and 2- wt.% heat-resistant carbon, polymer, silicate or ceramic fibres with a length of 1-20 mm. An Independent claim is also included for a process for the production of rocket propellant by homogenizing the fillers and binder in a kneader and then processing the mixture to form the insulating layer by hardening the binder.

Description

Die Erfindung betrifft einen Raketentreibsatz mit rauchreduziertem Abbrand, insbesondere für Stirnbrenner, mit einem Treibstoff auf der Basis von Ammoniumperchlorat mit einem Binder aus isocyanatgebundenen, hydroxyterminierten Polybutadien und einer den Treibstoff umgebenden inhibierenden Isolationsschicht. Ferner ist die Erfindung auf ein Verfahren zur Herstellung eines solchen Raketentreibsatzes gerichtet.The invention relates to a rocket propellant reduced smoke combustion, especially for forehead burners, with a fuel based on ammonium perchlorate with a binder made from isocyanate-bound, hydroxy-terminated Polybutadiene and one surrounding the fuel inhibiting insulation layer. Furthermore, the invention to a method for producing such a rocket propellant directed.

Beim Abbrand eines Raketentreibsatzes, der über 20, 40 oder 60 s abläuft, muß die inhibierende Isolation neben guter Haftung und Verträglichkeit zum Treibstoff auch eine thermische Schutzfunktion erfüllen, die die Brennkammerwand ebenso wie die inhibierte nichtbrennende Treibstoffoberfläche vor vorzeitiger Pyrolyse und Anzündung schützt. Bei rauchreduzierten Composittreibstoffen, die im Abgas keine oder nur wenig Partikel enthalten dürfen, darf auch die Isolation keine Partikel freisetzen. Ebenso darf sie bei den hohen Temperaturen des Treibstoffabbrands keine Rußwolken im Abgasstrahl erzeugen und nur unwesentlich mitverbrennen, da sonst bei kleinen Durchmessern der spezifische Impuls des Treibstoffs und damit die Leistung des Triebwerks reduziert werden. Die Summe dieser Eigenschaften wird z.B. bei Unterwasserantrieben, die beim Abbrand keine heißen Partikel ausschleudern dürfen, und bei Marschtriebwerken von aktiv über Laser oder Radar gelenkten Flugkörpern gefordert. Für diesen Zweck werden bisher stets schwierig herzustellende und teure Isolierungen auf Silikonharzbasis mit silikatischen Füllstoffen verwendet, die in aufwendigen Verfahren aufgerauht und chemisch vorbehandelt werden müssen, um die für die Anbindung des Treibstoffs an die Isolationsschicht notwendige Haftung zu erreichen.When a rocket propellant that burns over 20, 40 or 60 s, the inhibiting isolation must be next good adhesion and compatibility with the fuel too perform a thermal protection function that the combustion chamber wall just like the inhibited non-burning Fuel surface before premature pyrolysis and ignition protects. With smoke-reduced composite fuels, that contain little or no particles in the exhaust gas the insulation must not release any particles. Likewise, at the high temperatures of the Do not generate soot clouds in the exhaust gas jet and only burn insignificantly, otherwise with small diameters the specific momentum of the fuel and thus reduces the power of the engine become. The sum of these properties is e.g. at Underwater drives that are not called hot when they burn up Permitted to eject particles, and with march engines of missiles actively guided by laser or radar required. So far, this has always been difficult Manufactured and expensive insulation based on silicone resin with silicate fillers used in complex processes roughened and chemically pretreated need to be in order to bind the fuel necessary liability to the insulation layer to reach.

Der Erfindung liegt die Aufgabe zugrunde, einen Raketentreibsatz zu schaffen, der eine einfachere und kostengünstigere Herstellung bei einer verbesserten Anbindung des Treibstoffs an die Isolation erlaubt. Ferner soll ein Verfahren zur Herstellung eines solchen Raketentreibsatzes vorgeschlagen werden.The invention has for its object a rocket propellant to create a simpler and cheaper one Production with an improved connection of the Allows fuel to the insulation. Furthermore, a Process for producing such a rocket propellant be proposed.

Erfindungsgemäß wird diese Aufgabe bei einem an sich bekannten rauchreduzierten, polyurethangebundenen Composittreibstoff auf der Basis von Amnmoniumperchlorat und isocyanatgebundenem hydroxyterminiertem Polybutadien dadurch gelöst, daß für die Inhibierung der Treibstoffoberfläche eine Isolation verwendet wird, die einen Polyurethanbinder und eine Füllstoffkombination aus 2-8 Gew.%, vorzugsweise 3-5 Gew.% Siliciumcarbid, 18-16 Gew.%, vorzugsweise 24-50 Gew.% Siliciumdioxid in Gestalt von amorphen Quarzpulver und 2-20 Gew.% feste temperaturbeständige Fasern mit einer Länge von 1-20mm darin eingebettet enthält.According to the invention, this task is per se well-known smoke-reduced, polyurethane-bound composite fuel based on ammonium perchlorate and isocyanate-bound hydroxy-terminated polybutadiene solved in that for the inhibition of the fuel surface insulation is used that a Polyurethane binder and a filler combination of 2-8 % By weight, preferably 3-5% by weight silicon carbide, 18-16 % By weight, preferably 24-50% by weight of silica in the form of amorphous quartz powder and 2-20% by weight solid temperature-resistant Fibers with a length of 1-20mm are embedded in it contains.

Die erfindungsgemäße Isolation besitzt in der Regel auch ohne mechanische oder chemische Vorbehandlung eine gute Haftung zum Treibstoff. Sie zeigt bei hoher und tiefer Temperatur gleichermaßen gute Elastizität und ist über die Zusammensetzung des Polyurethanbinders durch den Anteil an Di- oder Triisocyanat oder beigefügten vernetzenden Triolen in ihren mechanischen Eigenschaften einstellbar.The insulation according to the invention usually also has a good one without mechanical or chemical pretreatment Liability to the fuel. It shows at high and low Temperature equally good elasticity and is about the composition of the polyurethane binder by the Share of di- or triisocyanate or added crosslinking Triplets adjustable in their mechanical properties.

Beim Treibstoffabbrand bewirkt die endotherm ablaufende Reaktion von SiC und SiO2 zusammen mit dem Anteil an Kohlenstoff-, Kunststoff- oder Keramikfasern die Ausbildung einer zusammenhängenden keramisierten Schlacke, die im Brennkammerraum verbleibt und weder Partikel noch Rußwolken im Abgas erzeugt. Die endotherm verlaufende Reaktion der Füllstoffe bewirkt ebenso wie die langsame Pyrolyse des Bindermaterials eine effektive Wärmeschutzwirkung gegenüber dem Brennkammergehäuse und nicht aktiviertem Treibsatzteil. Da zudem nur sehr wenig von dieser Isolationsschicht verbrennt -nach 20 s. Brenndauer treten nur etwa 2% Gewichtsverlust auf- wird der spezifische Impuls des Treibstoffs und damit die Leistung des Triebwerks nicht beeinträchtigt.When fuel is burned off, the endothermic reaction of SiC and SiO 2 together with the proportion of carbon, plastic or ceramic fibers leads to the formation of a coherent, ceramized slag which remains in the combustion chamber and does not produce any particles or soot clouds in the exhaust gas. The endothermic reaction of the fillers, like the slow pyrolysis of the binder material, has an effective thermal protection effect against the combustion chamber housing and the inactivated propellant part. Since only very little of this insulation layer burns - after 20 s. Burning time occurs only about 2% weight loss - the specific impulse of the fuel and thus the performance of the engine is not affected.

Erfindungsgemäß ist diese Isolation vorteilhaft auf der Basis von mit Isophorondiisocyanat (IPDI) oder Dimeryldiisocyanat (DMDI) oder mit anderen Diisocyanaten gebundenem hydroxyterminiertem Polybutadien aufgebaut. Ebenso kann aber auch ein anderes Polyesterpolyol oder Polyetherpolyol, das mit Di-, Tri oder polymerem Isocyanat gebunden wird, als Grundmaterial für die Isolation eingesetzt werden. Als weitere Füllstoffe können erfindungsgemäß auch ultrafeines Siliciumdioxid, ultrafeines Titandioxid und Zirkoniumdioxid zugesetzt werden. Diese Füllstoffe werden in einer Korngröße im Bereich von 20-50 nm für Siliciumdioxid sowie 50-1000 nm für TiO2 und ZrO2 verwendet. Sie bewirken eine Verfestigung der bei der Pyrolyse gebildeten Keramikschicht und vermindern dadurch deren Aufquellung und Ablation, ohne den Wärmedurchgang zu beeinflussen.According to the invention, this isolation is advantageously based on hydroxy-terminated polybutadiene bonded with isophorone diisocyanate (IPDI) or dimeryl diisocyanate (DMDI) or with other diisocyanates. Another polyester polyol or polyether polyol, which is bound with di-, tri or polymeric isocyanate, can also be used as the base material for the insulation. According to the invention, ultrafine silicon dioxide, ultrafine titanium dioxide and zirconium dioxide can also be added as further fillers. These fillers are used in a grain size in the range of 20-50 nm for silicon dioxide and 50-1000 nm for TiO 2 and ZrO 2 . They cause the ceramic layer formed during pyrolysis to solidify, thereby reducing its swelling and ablation without influencing the heat transfer.

Wesentlich für den Zusammenhalt der pyrolisierten Schichten ist ein Anteil von 1-20% festen Fasern in der Länge von 1-20 mm, die in Form hochtemperaturbeständiger Kunststoffasern aus Polyester, Polyamid-, Polyimid- oder Polybenzimidazolfasern sowie auf Kohlefasern, Glas- oder Silikat- oder Keramikfasern aufgebaut sein können. Dabei besitzen Kohlefasern oder aluminiumoxidhaltige Keramikfasern wegen ihrer Hochtemperaturbeständigkeit Vorteile gegenüber den anderen. Die Fasern können vor der Einmischung in die prepolymere Isolationsmischung mit Wasser oder organischem Lösemittel entschlichtet und ggf. mit einer haftvermittelnden Schicht versehen werden. Diese kann bei Glas-, Silikat- oder Keramikfasern aus funktionellen Silanen, bei Kunststoff- oder Kohlefasern vorteilhaft aus Polyisocyanat und kurzkettigem Polyesterpolyol bestehen.Essential for the cohesion of the pyrolyzed layers is a proportion of 1-20% solid fibers in length from 1-20 mm in the form of high temperature resistant plastic fibers made of polyester, polyamide, polyimide or Polybenzimidazole fibers as well as on carbon fibers, glass or Silicate or ceramic fibers can be constructed. Here have carbon fibers or ceramic fibers containing aluminum oxide advantages because of their high temperature resistance towards the others. The fibers can be mixed before into the prepolymeric insulation mixture with water desized or organic solvent and if necessary with be provided with an adhesion-promoting layer. This can be used for glass, silicate or ceramic fibers made of functional Silanes, advantageous for plastic or carbon fibers made of polyisocyanate and short-chain polyester polyol consist.

Bei der Pyrolyse der Isolation während des Treibstoffabbrandes sorgen die Fasern für den Zusammenhalt der gebildeten Schlacke und für die Ausbildung einer festen keramisierten Schicht.During the pyrolysis of the insulation during the burning of fuel the fibers ensure the cohesion of the formed Slag and for the formation of a solid ceramized Layer.

Die Isolation kann als prepolymerer Slurry durch Druckguß- oder im Vakuumaufziehverfahren in eine entsprechende Form mit dem Treibstoff verbunden werden. Bei der anschließenden Aushärtung, die vorteilhaft bei 60-65°C stattfindet, verbindet sich die Isolation mit dem Treibstoff zum festen montagebereiten Treibsatzblock.The insulation can be made into a corresponding slurry as a prepolymer slurry by die-casting or vacuum pull-up Form associated with the fuel. In the subsequent Curing, which is advantageous at 60-65 ° C takes place, the insulation combines with the fuel for a fixed ready-to-install propellant block.

Alternativ kann auch die Isolation im prepolymeren Zustand in der Brennkammer oder einem antihaftbeschichteten Rohr gleichen Innendurchmessers ausgeschleudert und ausgehärtet werden. Der Treibsatz wird dann durch Eingießen des Treibstoffslurries in den fertigen, ggf. durch mechanisches Aufrauhen oder über chemische Haftvermittler vorbehandelten Isolationsmantel mit anschließender Aushärtung bei 60-65°C hergestellt.Alternatively, the insulation can also be in the prepolymeric state in the combustion chamber or a non-stick coated Tube of the same inner diameter and ejected be cured. The propellant is then poured in of the fuel slurries in the finished, if necessary through mechanical roughening or chemical bonding agents pre-treated insulation jacket with subsequent hardening Made at 60-65 ° C.

Der Treibstoff kann in der rauchreduzierten Ausführung neben Ammoniumperchlorat (AP) in Anteilen von 50-90 Gew.%, Nitramine, wie Hexogen oder Oktogen, in Anteilen von 0-30 Gew.%, Eisen-III-oxid oder Ferrocenderivate als Abbrandkatalysatoren in Anteilen von 0 bis 15 Gew.% enthalten.The fuel can be in the smoke-reduced version in addition to ammonium perchlorate (AP) in proportions of 50-90 % By weight, nitramines, such as hexogen or octogen, in proportions from 0-30% by weight, ferric oxide or ferrocene derivatives as Combustion catalysts in proportions of 0 to 15% by weight contain.

Der Binder setzt sich vorteilhaft zusammen aus 8-20 Gew.% hydroxyterminiertem Polybutadien, das mit Isophorondiisocyanat (IPDI) oder Dimeryldiisocyanat (DMDI) in äquvalenten Anteilen gebunden wurde, sowie 2-8 Gew.% Weichmacher, 0,1-0,5 Gew.% Antioxidanz, wahlweise 0,1-0,3 Gew.% Verarbeitungshilfsstoffe, 50-500ppm Härtungskatalysator, vorzugsweise Triphenylwismut und 0,1-1% Haftvermittler für AP, vorzugsweise auf der Basis cyanethylierter Polyamine oder cyanethylierter Polyaminoalkohole.The binder is advantageously composed of 8-20% by weight hydroxy-terminated polybutadiene with isophorone diisocyanate (IPDI) or dimeryl diisocyanate (DMDI) in equivalents Proportions was bound, as well as 2-8% by weight plasticizer, 0.1-0.5% by weight of antioxidant, optionally 0.1-0.3% by weight of processing aids, 50-500ppm curing catalyst, preferably triphenyl bismuth and 0.1-1% coupling agent for AP, preferably based on cyanoethylated polyamines or cyanoethylated polyamino alcohols.

Beispiele:Examples:

  • 1. Für die Herstellung eines Stirnbrennertreibsatzes für Unterwasserantriebe wird als Treibstoff folgende Formulierung verwendet: Ammoniumperchlorat (AP) 200 m 48% Ammoniumperchlorat (AP) 30 m 24% Oktogen (HMX) 5 m 14% Ferrocenderivat 1% = 2,2-Bisethylferrocenylpropan 1. The following formulation is used as the fuel for the manufacture of a forehead torch propellant for underwater drives: Ammonium perchlorate (AP) 200 m 48% Ammonium perchlorate (AP) 30 m 24% Octogen (HMX) 5 m 14% Ferrocene derivative 1% = 2,2-bisethylferrocenylpropane

    • Binder:Binder:

    Hydroxyterminiertes Polybutadien (HTPB)Hydroxy-terminated polybutadiene (HTPB) 8,29% 8.29% Isophorondiisocyanat (IPDI)Isophorone diisocyanate (IPDI) 0,67%0.67% AntioxidanzAntioxidant 0,20%0.20% Weichmacher (Diisooctyladipat)Plasticizer (diisooctyl adipate) 3,70%3.70% Haftvermittler (Triphenylwismut)Adhesion promoter (triphenyl bismuth) 200ppm200ppm

    Als inhibierende Isolation (ISO 1) dient eine Mischung von: Hydroxyterminiertes Polybutadien 49,42% Isophorondiisocyanat (IPDI) 5,94% 1,2,4-Butantriol 0,57% Antioxidanz 0,20% Eisenacetylacetonat (Härtungsbeschleuniger) 0,006% A mixture of: Hydroxy-terminated polybutadiene 49.42% Isophorone diisocyanate (IPDI) 5.94% 1,2,4-butanetriol 0.57% Antioxidant 0.20% Iron acetylacetonate (hardening accelerator) 0.006%

    FüllstoffeFillers

    SiliciumcarbidSilicon carbide 4,53%4.53% SiO2-Pulver QuarzgutSiO 2 powder quartz 33,79%33.79% TiO2 superfeinTiO 2 super fine 1,90%1.90% KohlefaserCarbon fiber 3,65%3.65%

    Treibstoff und Isolation bilden ein gut funktionierendes System, das beim Abbrand eines Treibsatzes von 165 mm Durchmesser und 5 mm inhibierender Isolationsschicht über 20 s. keine Partikel und keinen schwarzen Rauch erzeugt. Der praktische Impuls des Treibstoffs beträgt etwa 93% des theoretischen Wertes, der Gewichtsverlust der Isolation beim Abbrand etwa 2%.Fuel and insulation form a well-functioning one System that burns a propellant charge of 165 mm Diameter and 5 mm inhibiting insulation layer over 20 s. no particles and no black smoke. The practical impulse of the fuel is about 93% the theoretical value, the weight loss of the insulation when burned up about 2%.

    Die Ummantelung des Treibsatzes mit inhibierender Isolation erfolgt vorteilhaft durch nachträgliches Umgießen des ausgehärteten Treibstoffblocks.

  • 2. Andere Treibstoff/Isolationsverbunde mit geringer Ablationsrate sind auf folgenden Isolationsformulierungen (in Gew.%) augebaut: Binder: Iso 2 Iso 3 Iso 4 Iso 5 Iso 6 HTPB 54,16 43,21 47,76 44,14 - IPDI 6,51 5,19 5,74 5,30 9,44 Butantriol 0,63 0,50 0,55 0,51 1,50 Polyesterdiol - - - - 39,06 FeAc 0,003 0,006 0,005 0,005 0,001 Antioxidanz 0,15 0,20 0,19 0,18 - Füllstoffe SiC 4,18 3,99 4,38 4,05 4,15 SiO2 29,99 39,93 32,66 30,18 42,15 SiO2 ultrafein 1,02 - - - - ZrO2 - 3,79 - - - TiO2 - - 1,83 1,69 - Fasern C-Faser 3,36 3,19 - - 3,34 SiO2/Al2O3-Faser - - 6,89 ZrO2-Faser - - - 13,95 -
    • The propellant charge is encased with inhibiting insulation, advantageously by subsequently pouring the hardened fuel block.
  • 2. Other fuel / insulation composites with a low ablation rate are based on the following insulation formulations (in% by weight): Binder: Iso 2 Iso 3 Iso 4 Iso 5 Iso 6 HTPB 54.16 43.21 47.76 44.14 - IPDI 6.51 5.19 5.74 5.30 9.44 Butanetriol 0.63 0.50 0.55 0.51 1.50 Polyester diol - - - - 39.06 FeAc 0.003 0.006 0.005 0.005 0.001 Antioxidant 0.15 0.20 0.19 0.18 - Fillers SiC 4.18 3.99 4.38 4.05 4.15 SiO 2 29.99 39.93 32.66 30.18 42.15 SiO 2 ultra fine 1.02 - - - - ZrO 2 - 3.79 - - - TiO 2 - - 1.83 1.69 - Fibers C fiber 3.36 3.19 - - 3.34 SiO 2 / Al 2 O 3 fiber - - 6.89 ZrO 2 fiber - - - 13.95 -

    • Claims (21)

    Raketentreibsatz mit rauchreduziertem Abbrand, insbesondere für Stirnbrenner, mit einem Treibstoff auf der Basis von Ammoniumperchlorat mit einem Binder aus isocyanatgebundenem, hydroxyterminiertem Polybutadien und einer den Treibstoff umgebenden, inihibierenden Isolationsschicht, dadurch gekennzeichnet, daß die Isolationsschicht aus einem Polyurethan-Binder und einer Füllstoff-Kombination aus 2 bis 8 Gew.% Siliciumcarbid, 20 bis 60 Gew.% Siliciumdioxid und temperaturfesten Kohlenstoff-, Polymer-, Silikat- oder Keramikfasern mit einer Länge von 1 bis 20 mm und einem Gehalt von 2 bis 20 Gew.% besteht.Rocket propellant with reduced smoke combustion, especially for head torches, with a fuel based on ammonium perchlorate with a Binder made from isocyanate-bound, hydroxy-terminated Polybutadiene and a surrounding fuel inihibiting insulation layer, characterized in that the insulation layer from a polyurethane binder and a filler combination 2 to 8% by weight silicon carbide, 20 to 60% by weight silicon dioxide and temperature-resistant carbon, polymer, Silicate or ceramic fibers with a length of 1 to 20 mm and a content of 2 to 20% by weight consists. Raketentreibsatz nach Anspruch 1, dadurch gekennzeichnet, daß der Treibstoff neben 50 bis 90 Gew.% Ammoniumperchlorat 0 bis 30 Gew.% Nitramine, wie Hexogen oder Oktogen, und 0,5 bis 15 Gew.% Abbrandkatalysatoren, z.B. Eisen-III-oxid oder Ferrocenderivate, enthält. Rocket propellant according to claim 1, characterized in that that the fuel in addition to 50 to 90 wt.% Ammonium perchlorate 0 to 30 wt.% Nitramine, such as Hexogen or octogen, and 0.5 to 15% by weight combustion catalysts, e.g. Iron III oxide or ferrocene derivatives, contains. Raketentreibsatz nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Binder des Treibstoffs sich zusammensetzt aus 8 bis 20 Gew.% hydroxyterminiertem Polybutadien, das mit Isophorondiisocyanat oder Dimeryldiisocyanat in äquivalenten Anteilen gebunden ist, etwa 2 bis 8 Gew.% Weichmacher, 0,3 bis 0,5 Gew.% Antioxidantien, 0,1 bis 0,3 Gew.% Verarbeitungshilfsstoffe, 50 bis 500 ppm Härtungekatalysator und 0,1 bis 1 Gew.% Haftvermittler.Rocket propellant according to claim 1 or 2, characterized characterized in that the binder of the fuel itself is composed of 8 to 20 wt.% Hydroxy-terminated Polybutadiene with isophorone diisocyanate or Dimeryl diisocyanate bound in equivalent proportions is about 2 to 8% by weight plasticizer, 0.3 to 0.5 % By weight of antioxidants, 0.1 to 0.3% by weight of processing aids, 50 to 500 ppm curing catalyst and 0.1 to 1% by weight of adhesion promoter. Raketentreibsatz nach Anspruch 3, dadurch gekennzeichnet, daß der Härtungskatalysator Triphenylwismut ist.Rocket propellant according to claim 3, characterized in that that the curing catalyst triphenyl bismuth is. Raketentreibsatz nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß der Haftvermittler auf der Basis cyanethylierter Polyamine aufgebaut ist.Rocket propellant according to claim 3 or 4, characterized characterized that the adhesion promoter is based cyanoethylated polyamines. Raketentreibsatz nach einem der Ansprüche 3 bis 5, daduch gekennzeichnet, daß der Haftvermittler auf der Basis cyanethylierter Polyaminokohole aufgebaut ist.Rocket propellant according to one of claims 3 to 5, daduch characterized that the adhesion promoter on based on cyanoethylated polyamino alcohols is. Raketentreibsatz nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Isolationeschicht als Binder 30 bis 70 Gew.% hydroxyterminiertes Polybutadien, Polyester- oder Polyetherpolyol, das mit Di- oder Triisocyanat, wahlweise einem Triol in äquivalenten Anteilen gebunden ist, enthält.Rocket propellant according to one of claims 1 to 6, characterized in that the insulation layer 30 to 70% by weight of hydroxy-terminated binder Polybutadiene, polyester or polyether polyol, the with di- or triisocyanate, optionally a triol in equivalent shares is bound. Raketentreibsatz nach Anspruch 7, dadurch gekennzeichnet, daß der Binder der Isolationsschicht mit Anteilen von 40 bis 55 Gew.% vorgesehen ist.Rocket propellant according to claim 7, characterized in that that the binder of the insulation layer with Proportions of 40 to 55% by weight is provided. Raketentreibsatz nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Polymerfasern der Isolationsschicht aus Polyester, Polyamid, Polybenzimidazol oder anderen temperaturbeständigen Kunstharzen bestehen.Rocket propellant according to one of claims 1 to 8, characterized in that the polymer fibers of Insulation layer made of polyester, polyamide, polybenzimidazole or other temperature-resistant synthetic resins consist. Raketentreibsatz nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Isolationsschicht Glasfasern enthält.Rocket propellant according to one of claims 1 to 9, characterized in that the insulation layer Contains glass fibers. Raketentreibsatz nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Füllstoff-Kombination der Isolationsschicht zusätzlich 0,5 bis 5 Gew.% ultrafeines Titandioxid, Siliciumdioxid oder Zirkondioxid mit einer Korngröße von 20 bis 1000 nm enthält.Rocket propellant according to one of claims 1 to 10, characterized in that the filler combination the insulation layer additionally 0.5 to 5 % By weight of ultrafine titanium dioxide, silicon dioxide or Zirconia with a grain size of 20 to 1000 nm contains. Raketentreibsatz nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die Isolationsschicht beim Abbrand des Treibstoffs und der dabei erfolgenden Pyrolyse der organischen Bestandteile eine nicht ablatierende, thermische Isolierung der Brennkammerwand bildet.Rocket propellant according to one of claims 1 to 11, characterized in that the insulation layer when the fuel burns down and the fuel that occurs Pyrolysis of the organic components is not ablating, thermal insulation of the combustion chamber wall forms. Raketentreibsatz nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Isolationsschicht beim Abbrand des Treibstoffs eine keramisierte Schicht bildet.Rocket propellant according to one of claims 1 to 12, characterized in that the insulation layer ceramized when the fuel burns Layer forms. Verfahren zur Herstellung eines Raketentreibsatzes nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß die Füllstoffe der Füllstoff-Kombination und der Binder in einem Knetprozeß homogenisiert werden und anschließend zu der Isolationsschicht unter Aushärten des Binders verarbeitet werden.Method of making a rocket propellant according to one of claims 1 to 13, characterized in that that the fillers of the filler combination and the binder is homogenized in a kneading process and then to the insulation layer processed with hardening of the binder become. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Fasern vor dem Einarbeiten in den Binder in Wasser oder Lösungsmitteln entschlichtet und anschließend mit einer Haftvermittlerlösung behandelt werden.A method according to claim 14, characterized in that the fibers in before the incorporation into the binder Desized and then water or solvents treated with an adhesion promoter solution become. Verfahren nach Anspruch 15, dadurch gekennzeichnet, daß für Silikat-, Glas- oder Keramikfasern eine Haftvermittlerlösung auf der Basis funktionalisierter Silane eingesetzt wird.A method according to claim 15, characterized in that for silicate, glass or ceramic fibers Adhesion promoter solution based on functionalized Silanes is used. Verfahren nach Anspruch 15, dadurch gekennzeichnet, daß für Polymer- oder Kohlenstoffasern eine Haftvermittlerlösung aus einem Gemisch von Polyisocyanat und kurzkettigem Polyester- oder Polyetherpolyol eingesetzt wird.A method according to claim 15, characterized in that an adhesion promoter solution for polymer or carbon fibers from a mixture of polyisocyanate and short chain polyester or polyether polyol is used. Verfahren nach einem der Ansprüche 14 bis 17, dadurch gekennzeichnet, daß der Treibstoff als Formkörper in eine Gießform oder in die Brennkammer eingesetzt und mit der Mischung der Isolationsschicht umgossen wird und die Mischung anschließend zur Isolationsschicht ausgehärtet wird.Method according to one of claims 14 to 17, characterized characterized in that the fuel as a shaped body in a mold or in the combustion chamber used and with the mixture of the insulation layer is poured over and then the mixture is cured to the insulation layer. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß die Mischung der Isolationsschicht in der Brennkammer oder einer entsprechenden Form durch Zentrifugieren zu einer Isolationsschicht mit einer Dicke von 1 bis 10 mm geformt und nach dem Aushärten mit dem Treibstoff in Form eines Slurry ausgegossen wird.Method according to one of claims 1 to 17, characterized characterized in that the mixture of the insulation layer in the combustion chamber or equivalent Form by centrifugation into an insulation layer molded with a thickness of 1 to 10 mm and after Harden with the fuel in the form of a slurry is poured out. Verfahren nach Anspruch 19, dadurch gekennzeichnet, daß die Isolationsschicht während oder nach dem Aushärten innenseitig mit einer aufgerauhten Oberfläche versehen wird. A method according to claim 19, characterized in that the insulation layer during or after Harden inside with a roughened surface is provided. Verfahren nach Anspruch 19 oder 20, dadurch gekennzeichnet, daß die Isolationsschicht nach dem Aushärten mit einem Haftvermittler für den Treibstoff versehen wird.A method according to claim 19 or 20, characterized in that that the insulation layer after curing with an adhesion promoter for the fuel is provided.
    EP00108297A 1999-04-19 2000-04-14 Rocket propellant Expired - Lifetime EP1046626B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19917672 1999-04-19
    DE19917672A DE19917672A1 (en) 1999-04-19 1999-04-19 Rocket propellant

    Publications (2)

    Publication Number Publication Date
    EP1046626A1 true EP1046626A1 (en) 2000-10-25
    EP1046626B1 EP1046626B1 (en) 2004-08-18

    Family

    ID=7905106

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00108297A Expired - Lifetime EP1046626B1 (en) 1999-04-19 2000-04-14 Rocket propellant

    Country Status (3)

    Country Link
    EP (1) EP1046626B1 (en)
    AT (1) ATE273943T1 (en)
    DE (2) DE19917672A1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US20100255317A1 (en) * 2007-11-01 2010-10-07 Kuraray Co., Ltd. Polyurethane composition

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102005030437B4 (en) 2005-06-30 2007-09-13 Deutsches Zentrum für Luft- und Raumfahrt e.V. Drive device based on gel-type fuel and method for fuel delivery

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3643824A1 (en) * 1986-12-20 1988-06-30 Bayern Chemie Gmbh Flugchemie Liner layer for lining rocket combustion chambers
    EP0555008A2 (en) * 1992-01-29 1993-08-11 Thiokol Corporation Low smoke rocket motor liner compositions
    FR2727402A1 (en) * 1978-12-29 1996-05-31 Poudres & Explosifs Ste Nale Propulsion acceleration charge
    US5762746A (en) * 1989-08-16 1998-06-09 Thiokol Corporation Method of internally insulating a propellant combustion chamber

    Family Cites Families (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE1200184B (en) * 1963-11-16 1965-09-02 Nitrochemie G M B H Process for the production of solid propellants provided with an insulating layer
    DE2004472C1 (en) * 1970-01-31 1979-11-29 Wasagchemie Gmbh, 8000 Muenchen Process for applying insulating layers to solid propellants
    US3764420A (en) * 1971-01-06 1973-10-09 Us Army Suppression of combustion instability by means of pbi fibers
    BE791854A (en) * 1971-11-25 1973-05-24 Poudres & Explosifs Ste Nale SOLID PROPERGOL BLOCKS COMBUSTION INHIBITORS
    CA1056984A (en) * 1976-01-16 1979-06-19 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government Curable binding systems
    JPH08231291A (en) * 1994-12-27 1996-09-10 Daicel Chem Ind Ltd Gas generating agent composition
    DE19516528C1 (en) * 1995-05-05 1996-12-12 Fraunhofer Ges Forschung Solid composite fuel and process for its manufacture

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2727402A1 (en) * 1978-12-29 1996-05-31 Poudres & Explosifs Ste Nale Propulsion acceleration charge
    DE3643824A1 (en) * 1986-12-20 1988-06-30 Bayern Chemie Gmbh Flugchemie Liner layer for lining rocket combustion chambers
    US5762746A (en) * 1989-08-16 1998-06-09 Thiokol Corporation Method of internally insulating a propellant combustion chamber
    EP0555008A2 (en) * 1992-01-29 1993-08-11 Thiokol Corporation Low smoke rocket motor liner compositions

    Non-Patent Citations (6)

    * Cited by examiner, † Cited by third party
    Title
    CHEMICAL ABSTRACTS, vol. 108, no. 4, 25 January 1988, Columbus, Ohio, US; abstract no. 24138a, M. PROEBSTER: "Smokeless combustible insulation for double-basepropellants" page 134; XP002142650 *
    CHEMICAL ABSTRACTS, vol. 122, no. 14, 3 April 1995, Columbus, Ohio, US; abstract no. 164861v, D.C. GUPTA ET AL.: "HTPB-based polyurethanes for inhibition of composite propellants." page 267; XP000665923 *
    CHEMICAL ABSTRACTS, vol. 123, no. 26, 25 December 1995, Columbus, Ohio, US; abstract no. 344937d, S.B. HASKA ET AL.: "Adhesion properties of liner to propellant and metal in HTPB based systems." page 290; XP000663353 *
    Int. Annu. Conf. ICT 1995, 26th(Pyrotechnics), 49/1-49/12 *
    Int. Jahrestag.- Fraunhofer-Inst. Treib- Explosivst. 1987, 18th(Technol. Energ. Mater.), 40/1-40/14 *
    J. APPL. POLYM. SCI., vol. 55, no. 8, 1995, pages 1151 - 1155 *

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US20100255317A1 (en) * 2007-11-01 2010-10-07 Kuraray Co., Ltd. Polyurethane composition

    Also Published As

    Publication number Publication date
    DE19917672A1 (en) 2000-10-26
    EP1046626B1 (en) 2004-08-18
    DE50007431D1 (en) 2004-09-23
    ATE273943T1 (en) 2004-09-15

    Similar Documents

    Publication Publication Date Title
    DE60307254T2 (en) PROTECTION OF COMPOSITE MATERIALS AGAINST OXIDATION
    DE69404456T2 (en) METHOD FOR PRODUCING PROFILES USING ORGANOMETALLIC, CERAMIC BINDING AGENTS
    CN109232848B (en) DDI lining layer for solid rocket engine medicine loading and application method thereof
    US4638735A (en) Combustion inhibitor based on an aliphatic polyurethane elastomer for a propellant, and block coated with this inhibitor
    DE1809360C3 (en) Composition for the production of synthetic resins and endothermic decomposing substances containing, optionally heat-curable insulation layers on solid rocket propellants and a method for isolating these propellants using this compound
    EP1046626B1 (en) Rocket propellant
    EP0878520A2 (en) Composition for refractory, pyrolitically ceramic forming coatings
    CN110423184A (en) A kind of solid propellant rocket propellant and preparation method thereof
    US5619011A (en) Process for producing a hybrid rocket fuel
    US6168677B1 (en) Minimum signature isocyanate cured propellants containing bismuth compounds as ballistic modifiers
    US3215028A (en) Means and method for restricting a solid propellant
    DE3528505C2 (en)
    US4375522A (en) Thixotropic restrictor, curable at room temperature, for use on solid propellant grains
    DE3643824C2 (en)
    DE2843477A1 (en) Solid propellant charge - contg. polymeric binder and reinforcing fibres, e.g. cellulosic fibres
    DE3643825C2 (en)
    DE3902130C1 (en) Intermediate layer between propellant charge and insulating layer, process for producing the intermediate layer, and its use
    DE2951997C1 (en) Acceleration propellant and process for its production
    KR100205832B1 (en) Solid propellant compositions having peg binder/nitramineoxydizers and manufacturing method threrof
    DE3704304C2 (en)
    RU2167903C2 (en) Fast-hardening strengthening composition for fixing fuel cells with bottom of rocket engine
    DE3632235C1 (en) Synthetic resin compound for the isolation of solid propellants
    DE3644239C2 (en)
    DE102022001613A1 (en) Propellants comprising polymeric adhesion promoters for ADN-based rocket propellants
    DE3706368C1 (en) Insulation composition for producing an insulating layer on a solid rocket propellent charge

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    AKX Designation fees paid
    17P Request for examination filed

    Effective date: 20010201

    RBV Designated contracting states (corrected)

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    17Q First examination report despatched

    Effective date: 20020913

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DERANGEWAND

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040818

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

    Effective date: 20040818

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040818

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040818

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    REF Corresponds to:

    Ref document number: 50007431

    Country of ref document: DE

    Date of ref document: 20040923

    Kind code of ref document: P

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041118

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041118

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041118

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041129

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20050114

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20050407

    Year of fee payment: 6

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050414

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050414

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050414

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20050419

    Year of fee payment: 6

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050430

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050430

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050430

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050430

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    ET Fr: translation filed
    26N No opposition filed

    Effective date: 20050519

    BERE Be: lapsed

    Owner name: *FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWAN

    Effective date: 20050430

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060414

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20060414

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20061230

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070625

    Year of fee payment: 8

    BERE Be: lapsed

    Owner name: *FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWAN

    Effective date: 20050430

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050118

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060502

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20081101