EP1242338A2 - Ignition means for propellant powders - Google Patents

Ignition means for propellant powders

Info

Publication number
EP1242338A2
EP1242338A2 EP00987340A EP00987340A EP1242338A2 EP 1242338 A2 EP1242338 A2 EP 1242338A2 EP 00987340 A EP00987340 A EP 00987340A EP 00987340 A EP00987340 A EP 00987340A EP 1242338 A2 EP1242338 A2 EP 1242338A2
Authority
EP
European Patent Office
Prior art keywords
igniter
propellant
powder
mixtures
propellant charge
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
EP00987340A
Other languages
German (de)
French (fr)
Other versions
EP1242338B1 (en
Inventor
Klaus Redecker
Ulrich Bley
Rainer Hagel
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.)
RWS GmbH
Original Assignee
Dynamit Nobel AG
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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 Dynamit Nobel AG, Dynamit Nobel GmbH Explosivstoff und Systemtechnik filed Critical Dynamit Nobel AG
Publication of EP1242338A2 publication Critical patent/EP1242338A2/en
Application granted granted Critical
Publication of EP1242338B1 publication Critical patent/EP1242338B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters
    • 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
    • C06B45/14—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones a layer or zone containing an inorganic explosive or an inorganic explosive or an inorganic thermic component

Definitions

  • the present invention relates to an igniter for propellant powder and their use.
  • Cartridges filled with propellant powder are mainly used in the civil sector, particularly in bolt-setting tools or for stunning animals. They can be made of metal or plastic.
  • the propellant charge powder is usually ignited by a mechanically or electrically initiated reaction of an ignition charge, which consists of at least one primary explosive. This generally ensures safe ignition.
  • the igniter according to the invention is a primary explosive-free ignition for propellant charge powder, which contains at least one oxidizing agent, at least one reducing agent and at least one binder. When ignited, the igniter according to the invention produces particles which ignite the propellant charge powder.
  • the present invention therefore makes it possible for the first time to safely ignite propellant powder without the use of primary explosives.
  • the igniter according to the invention can be used, for example, to safely ignite propellant powder located in cartridges that are used, for example, in bolt-setting devices.
  • propellant powder made from nitrocellulose can be used.
  • it can also consist of components that are used, for example, in propellant powders to provide low-CO reaction vapors (for example, so-called SINCO ® propellant powders).
  • SINCO ® propellant powders for example, so-called SINCO ® propellant powders.
  • EP 0 809 616 A1 Such cartridges are described for example in DE 198 24 122 A1. They can be covered by a foil, for example made of aluminum.
  • the present invention offers the possibility of treating such cover films with the igniter according to the invention, and thereby, after appropriate initiation, to act as an ignition for the propellant charge powder.
  • the film for example an aluminum film
  • the ignition agent according to the invention is coated on the inside of the cartridge with the ignition agent according to the invention, dried and applied to the cartridge filled with propellant charge powder, for example by gluing. If the cartridge cover is quickly heated from the outside, for example by an electrical discharge, the aluminum can react with the applied components and burning particles are formed, which ignite the propellant charge powder.
  • the invention therefore also relates to coatings which can be applied to foils and which, when burned, produce particles which can ignite powder and the films coated with the igniter according to the invention.
  • the igniter according to the invention can consist of the following components or mixtures of these components:
  • Nitrocellulose cellulose and their derivatives such as cellulose acetates, cellulose buterates, cellulose acetobutyrates, polyvinyl butyrals, polyvinyl butyrates, polynitropolyphenylene or polynitropolyphenyl ether and mixtures thereof.
  • oxidants examples include:
  • Nitrates of the alkali or alkaline earth elements or of ammonium for example sodium nitrate, potassium nitrate or ammonium nitrate, the perchlorates of the alkali or alkaline earth elements or of ammonium, the peroxides of the alkaline earth elements or zinc, for example zinc peroxide or mixtures thereof.
  • reducing agents which can be used are:
  • urea derivatives such as centralite or acardite
  • Ferrocene and its derivatives or oxidizing agents that pass through different valence levels can be used as combustion moderators, for example.
  • additional additives for example, high-energy substances can be added to improve the burn-up, the energy and the thermal stability of the applied paint.
  • Such supplements are secondary explosives such. B. octogen, hexogen etc.
  • the amount of the individual components depends essentially on the respective intended use.
  • the oxidizing agent can preferably be used in a range from 5 to 50% by weight, the reducing agent preferably in a range from 5 to 50% by weight and the binder preferably in a range from 1 to 40% by weight.
  • the oxidizing agent is particularly preferably used in a range from 10 to 40% by weight, the reducing agent in a range from 10 to 40% by weight and the binder in a range from 5 to 20% by weight.
  • stabilizers, combustion moderators and other additives also depends on the intended use. The type and quantity can be easily determined.
  • the ignition according to the invention is produced by methods known per se, for example by mixing the components and applying them by brushing, or else using the screen printing method.
  • the table below shows the composition of igniters according to the invention, which can be used in the form of coatings.
  • the coatings can be produced as follows:
  • the binder defined according to the invention is dissolved in a known and suitable solvent, preferably methyl acetate, and the individual components are added with stirring.
  • a known and suitable solvent preferably methyl acetate
  • the amount of solvent depends on the laboratory method and the required viscosity.

Abstract

Ignition means for propellant powders include at least one oxidation means, at least one reduction means and at least one binder, and are free from primary explosives.

Description

Anzündmittel für Treibladungspulver Igniter for propellant powder
Gegenstand der vorliegenden Erfindung ist ein Anzündmittel für Treibladungspulver sowie deren Verwendung.The present invention relates to an igniter for propellant powder and their use.
Mit Treibladungspulver gefüllte Kartuschen finden vorwiegend im zivilen Bereich, ins- besondere in Bolzensetzgeräten oder zur Viehbetäubung Verwendung. Sie können aus Metall oder Kunststoff bestehen.Cartridges filled with propellant powder are mainly used in the civil sector, particularly in bolt-setting tools or for stunning animals. They can be made of metal or plastic.
Üblicherweise wird das Treibladungspulver durch eine mechanisch oder elektrisch initiierte Reaktion eines Anzündsatzes, der aus mindestens einem Primärexplosivstoff besteht, angezündet. Damit ist im allgemeinen eine sichere Anzündung gewährlei- stet.The propellant charge powder is usually ignited by a mechanically or electrically initiated reaction of an ignition charge, which consists of at least one primary explosive. This generally ensures safe ignition.
Fertigung und Einsatz von Anzündsätzen mit Primärexplosivstoffen sind jedoch aufgrund sicherheitstechnischer Forderungen nur unter besonderen Auflagen erlaubt. Hinzu kommen Erschwernisse beim Transport als Gefahrgut sowie bei Lagerung und Handhabung, wozu speziell ausgebildetes und unterwiesenes Personal benötigt wird.Due to safety requirements, the manufacture and use of primer sets with primary explosives are only permitted under special conditions. In addition, there are difficulties with the transport as dangerous goods as well as with storage and handling, for which purpose specially trained and instructed personnel are required.
Eine Aufgabe der vorliegenden Erfindung bestand daher darin, eine Anzündung für Treibladungspulver bereitzustellen, die diese Nachteile nicht aufweist.It was therefore an object of the present invention to provide an ignition for propellant powder which does not have these disadvantages.
Gelöst wurde diese Aufgabe erfindungsgemäß durch die Merkmale des Hauptanspruchs. Vorzugsweise Ausgestaltungen sind in den Unteransprüchen definiert.This object was achieved according to the invention by the features of the main claim. Refinements are preferably defined in the subclaims.
Im wesentlichen handelt es sich bei dem erfindungsgemäßen Anzündmittel um eine primärexplosivstofffreie Anzündung für Treibladungspulver, die mindestens ein Oxi- dationsmittel, mindestens ein Reduktionsmittel und mindestens ein Bindemittel enthält. Das erfindungsgemäße Anzündmittel erzeugt beim Verbrennen Partikel, die das Treibladungspulver anzünden.Essentially, the igniter according to the invention is a primary explosive-free ignition for propellant charge powder, which contains at least one oxidizing agent, at least one reducing agent and at least one binder. When ignited, the igniter according to the invention produces particles which ignite the propellant charge powder.
Durch die vorliegende Erfindung ist es damit erstmals möglich, Treibladungspulver ohne den Einsatz von Primärexplosivstoffen sicher anzuzünden.The present invention therefore makes it possible for the first time to safely ignite propellant powder without the use of primary explosives.
Eingesetzt werden kann das erfindungsgemäße Anzündmittel beispielsweise zur sicheren Anzündung von Treibladungspulver, das sich in Kartuschen befindet, die beispielsweise in Bolzensetzgeräten eingesetzt werden. Als Treibladungspulver kann beispielsweise solches aus Nitrocellulose eingesetzt werden. Es kann jedoch auch aus Komponenten bestehen, die beispielsweise in Treibladungspulvern zur Bereitstel- lung von CO-armen Reaktionsschwaden verwendet werden (beispielsweise sog. SINCO®-Treibladungspulver). Verwiesen sei in diesem Zusammenhang auf die EP 0 809 616 A1. Solche Kartuschen sind beispielsweise in der DE 198 24 122 A1 beschrieben. Sie können durch eine Folie, beispielsweise aus Aluminium abgedeckt sein.The igniter according to the invention can be used, for example, to safely ignite propellant powder located in cartridges that are used, for example, in bolt-setting devices. For example, propellant powder made from nitrocellulose can be used. However, it can also consist of components that are used, for example, in propellant powders to provide low-CO reaction vapors (for example, so-called SINCO ® propellant powders). In this connection, reference is made to EP 0 809 616 A1. Such cartridges are described for example in DE 198 24 122 A1. They can be covered by a foil, for example made of aluminum.
Die vorliegende Erfindung bietet die Möglichkeit, solche Abdeckfolien mit dem erfindungsgemäßen Anzündmittel zu behandeln, und dadurch, nach entsprechender Initiierung, als Anzündung für das Treibladungspulver zu wirken.The present invention offers the possibility of treating such cover films with the igniter according to the invention, and thereby, after appropriate initiation, to act as an ignition for the propellant charge powder.
Dazu wird die Folie, beispielsweise eine Aluminiumfolie, an der Innenseite der Kartusche mit dem erfindungsgemäßen Anzündmittel bestrichen, getrocknet und auf die mit Treibladungspulver gefüllte Kartusche aufgebracht, beispielsweise durch Verkleben. Wird nun die Kartuschenabdeckung von außen schnell aufgeheizt, beispielsweise durch eine elektrische Entladung, kann das Aluminium mit den aufgebrachten Komponenten reagieren und es bilden sich brennende Partikel, die das Treibladungspulver anzünden.For this purpose, the film, for example an aluminum film, is coated on the inside of the cartridge with the ignition agent according to the invention, dried and applied to the cartridge filled with propellant charge powder, for example by gluing. If the cartridge cover is quickly heated from the outside, for example by an electrical discharge, the aluminum can react with the applied components and burning particles are formed, which ignite the propellant charge powder.
Gegenstand der Erfindung sind daher auch Beschichtungen, die auf Folien aufgebracht werden können und beim Verbrennen Partikel erzeugen, die das Treibla- dungspulver anzünden kann, sowie die mit dem erfindungsgemäßen Anzündmittel beschichteten Folien.The invention therefore also relates to coatings which can be applied to foils and which, when burned, produce particles which can ignite powder and the films coated with the igniter according to the invention.
Die erfindungsgemäßen Anzündmittel können aus folgenden Komponenten oder Mischungen dieser Komponenten bestehen:The igniter according to the invention can consist of the following components or mixtures of these components:
Als Bindemittel können beispielsweise eingesetzt werden:The following can be used as binders:
- Nitrocellulose, Cellulose sowie deren Derivate wie Celluloseacetate, Cellulosebuty- rate, Celluloseacetobutyrate, Polyvinylbutyrale, Polyvinylbutyrate, Polynitropoly- phenylen oder Polynitropolyphenylether sowie deren Mischungen.- Nitrocellulose, cellulose and their derivatives such as cellulose acetates, cellulose buterates, cellulose acetobutyrates, polyvinyl butyrals, polyvinyl butyrates, polynitropolyphenylene or polynitropolyphenyl ether and mixtures thereof.
Als Oxidationsmittel können beispielsweise eingesetzt werden:Examples of oxidants that can be used are:
- Nitrate der Alkali- oder Erdalkalielemente oder des Ammoniums, beispielsweise Natriumnitrat, Kaliumnitrat oder Ammoniumnitrat, den Perchloraten der Alkali- oder Erdalkalielemente oder des Ammoniums, den Peroxiden der Erdalkalielemente oder des Zinks, beispielsweise Zinkperoxid oder deren Mischungen.Nitrates of the alkali or alkaline earth elements or of ammonium, for example sodium nitrate, potassium nitrate or ammonium nitrate, the perchlorates of the alkali or alkaline earth elements or of ammonium, the peroxides of the alkaline earth elements or zinc, for example zinc peroxide or mixtures thereof.
Als Reduktionsmittel können beispielsweise eingesetzt werden:Examples of reducing agents which can be used are:
- Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkoniumhydrid, Graphit oder Ruß sowie deren Mischungen.- Aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, graphite or carbon black and mixtures thereof.
Als Stabilisatoren können beispielsweise die bei der thermischen Zersetzung von Salpetersäureestern bewährten Komponenten eingesetzt werden, beispielsweise Harnstoffderivate wie Centralite oder Akardite.The components which have proven themselves in the thermal decomposition of nitric acid esters, for example urea derivatives such as centralite or acardite, can be used as stabilizers.
Als Abbrandmoderatoren können beispielsweise Ferrocen und seine Derivate oder Oxidationsmittel, die verschiedene Wertigkeitsstufen durchlaufen, verwendet werden. Als weitere Zuschläge können beispielsweise energiereiche Stoffe zur Verbesserung des Abbrandes, der Energie und der thermischen Stabilität des aufgebrachten Lak- kes zugefügt werden. Solche Zuschläge sind Sekundärexplosivstoffe wie z. B. Okto- gen, Hexogen usw..Ferrocene and its derivatives or oxidizing agents that pass through different valence levels can be used as combustion moderators, for example. As additional additives, for example, high-energy substances can be added to improve the burn-up, the energy and the thermal stability of the applied paint. Such supplements are secondary explosives such. B. octogen, hexogen etc.
Zur Erkennung verschiedener Rezepturen kann es sinnvoll sein, farbgebende Komponenten hinzufügen.To identify different recipes, it can be useful to add coloring components.
Zur Verbesserung der Geruchseigenschaften der Schwaden ist die Zugabe von Duftstoffen zweckmäßig.It is advisable to add fragrances to improve the smell properties of the steam.
Zur Erkennung von mißbräuchlicher Verwendung kann die Zugabe von Stoffen, die eine nachträgliche Zuordnung zum Hersteller erlauben, angezeigt sein.In order to detect misuse, the addition of substances that allow subsequent assignment to the manufacturer may be indicated.
Die Menge der einzelnen Komponenten richtet sich im wesentlichen nach dem jeweiligen Verwendungszweck. Das Oxidationsmittel kann vorzugsweise in einem Bereich von 5 bis 50 Gew.-%, das Reduktionsmittel vorzugsweise in einem Bereich von 5 bis 50 Gew.-% und das Bindemittel vorzugsweise in einem Bereich von 1 bis 40 Gew.-% eingesetzt werden. Besonders bevorzugt wird das Oxidationsmittel in einem Bereich von 10 bis 40 Gew.-%, das Reduktionsmittel in einem Bereich von 10 bis 40 Gew.-% und das Bindemittel in einem Bereich von 5 bis 20 Gew.-% eingesetzt. Zugabe von Stabilisatoren, Abbrandmoderatoren und anderen Zuschlägen richtet sich ebenfalls nach dem jeweiligen Verwendungszweck. Die Art und die Menge kann leicht ermittelt werden.The amount of the individual components depends essentially on the respective intended use. The oxidizing agent can preferably be used in a range from 5 to 50% by weight, the reducing agent preferably in a range from 5 to 50% by weight and the binder preferably in a range from 1 to 40% by weight. The oxidizing agent is particularly preferably used in a range from 10 to 40% by weight, the reducing agent in a range from 10 to 40% by weight and the binder in a range from 5 to 20% by weight. The addition of stabilizers, combustion moderators and other additives also depends on the intended use. The type and quantity can be easily determined.
Die Herstellung der erfindungsgemäßen Anzündung erfolgt nach an sich bekannten Verfahren beispielsweise durch Mischen der Komponenten und Aufbringen mittels Streichen oder auch nach dem Siebdruckverfahren.The ignition according to the invention is produced by methods known per se, for example by mixing the components and applying them by brushing, or else using the screen printing method.
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern, ohne sie einzu- schränken: BeispieleThe following examples are intended to explain the invention in more detail without restricting it: Examples
Die nachfolgende Tabelle gibt die Zusammensetzung von erfindungsgemäßen Anzündmitteln an, die in Form von Beschichtungen eingesetzt werden können.The table below shows the composition of igniters according to the invention, which can be used in the form of coatings.
Die Beschichtungen können folgendermaßen hergestellt werden:The coatings can be produced as follows:
Der erfindungsgemäß definierte Binder wird in einem an sich bekannten und geeigneten Lösungsmittel, vorzugsweise Methylacetat, gelöst und die Einzelkomponenten unter Rühren zugeben. Die Lösemittelmenge richtet sich nach der Laboriermethode und der geforderten Viskosität.The binder defined according to the invention is dissolved in a known and suitable solvent, preferably methyl acetate, and the individual components are added with stirring. The amount of solvent depends on the laboratory method and the required viscosity.

Claims

_ g _Patentansprüche _ g _Patent claims
1. Anzündmittel für Treibladungspulver, dadurch gekennzeichnet, dass es pri- märexplosivstoffrei ist und mindestens ein Oxidationsmittel, mindestens ein Reduktionsmittel und mindestens ein Bindemittel enthält.1. Igniter for propellant charge powder, characterized in that it is free of primary explosives and contains at least one oxidizing agent, at least one reducing agent and at least one binder.
2. Anzündmittel für Treibladungspulver nach Anspruch 1 , dadurch gekennzeichnet, dass es beim Verbrennen Partikel erzeugt, die das Treibladungspulver anzünden.2. Igniter for propellant charge according to claim 1, characterized in that it generates particles during combustion which ignite the propellant powder.
3. Anzündmittel für Treibladungspulver nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Oxidationsmittel ausgewählt ist aus den Nitraten der Alkali- oder Erdalkalielemente oder des Ammoniums, den Perchloraten der Alkali- oder3. igniter for propellant charge according to claim 1 or 2, characterized in that the oxidizing agent is selected from the nitrates of the alkali or alkaline earth elements or ammonium, the perchlorates of the alkali or
Erdalkalielemente oder des Ammoniums, den Peroxiden der Erdalkalielemente oder des Zinks oder deren Mischungen, das Reduktionsmittel ausgewählt ist aus Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkoniumhydrid, Graphit oder Ruß oder deren Mischungen und das Bindemittel ausgewählt ist aus Nitrocellulose, Cellulose oder deren Derivate wie Celluloseacetate, Cellulose- butyrate, Celluloseacetobutyrate, Polyvinylbutyrale, Polyvinylbutyrate, Polynitro- polyphenylen, Polynitropolyphenylether oder deren Mischungen.Alkaline earth elements or ammonium, the peroxides of the alkaline earth elements or zinc or their mixtures, the reducing agent is selected from aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, graphite or carbon black or their mixtures and the binder is selected from nitrocellulose, cellulose or their derivatives such as cellulose acetates, cellulose butyrates, cellulose acetobutyrates, polyvinyl butyrals, polyvinyl butyrates, polynitropolyphenylene, polynitropolyphenyl ether or mixtures thereof.
4. Anzündmittel für Treibladungspulver nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es zusätzlich mindestens einen Stabilisa- tor, mindestens einen Abbrandmoderator und/oder mindestens einen Zuschlag zur Verbesserung des Abbrandes, der Energie oder der thermischen Stabilität enthält.4. igniter for propellant charge according to one or more of claims 1 to 3, characterized in that it additionally contains at least one stabilizer, at least one combustion moderator and / or at least one supplement to improve the combustion, the energy or the thermal stability.
5. Anzündmittel für Treibladungspulver nach Anspruch 4, dadurch gekennzeichnet, dass als Stabilisator eine bei der thermischen Zersetzung von Salpetersäuree- stern bewährte Komponente aus der Gruppe der Harnstoffderivate oder deren5. igniter for propellant charge according to claim 4, characterized in that as a stabilizer is a proven component in the thermal decomposition of nitric acid star from the group of urea derivatives or their
Mischungen, als Abbrandmoderator ein Oxidationsmittel, das verschiedene Wertigkeitsstufen durchläuft oder Ferrocen oder dessen Derivate oder deren Mischungen und als Zuschlag zur Verbesserung des Abbrandes, der Energie oder der thermischen Stabilität mindestens ein Sekundärexplosivstoff ausge- wählt ist.Mixtures, as a combustion moderator, an oxidizing agent that passes through various valence levels or ferrocene or its derivatives or their mixtures, and at least one secondary explosive is selected as an additive to improve the combustion, energy or thermal stability.
6. Verwendung des Anzündmittels gemäß einem oder mehreren der Ansprüche 1 bis 5 zum Beschichten von Treibladungspulver. _ _6. Use of the igniter according to one or more of claims 1 to 5 for coating propellant powder. _ _
7. Verwendung des Anzündmittels gemäß einem oder mehreren der Ansprüche 1 bis 5 zum Beschichten von Abdeckfolien für Treibladungspulver.7. Use of the igniter according to one or more of claims 1 to 5 for coating cover foils for propellant powder.
8. Verwendung des Anzündmittels gemäß einem oder mehreren der Ansprüche 1 bis 5 zum Beschichten von Kartuschenabdeckungen für Treibladungspulver.8. Use of the igniter according to one or more of claims 1 to 5 for coating cartridge covers for propellant powder.
9. Abdeckfolie für Treibladungspulver, dadurch gekennzeichnet, dass sie mit einem Anzündmittel gemäß einem oder mehreren der Ansprüche 1 bis 5 beschichtet ist. 9. Cover film for propellant charge powder, characterized in that it is coated with an igniter according to one or more of claims 1 to 5.
EP00987340A 1999-12-03 2000-12-04 Ignition means for propellant powders Expired - Lifetime EP1242338B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19958361 1999-12-03
DE19958361 2000-03-12
PCT/EP2000/012169 WO2001040144A2 (en) 1999-12-03 2000-12-04 Ignition means for propellant powders

Publications (2)

Publication Number Publication Date
EP1242338A2 true EP1242338A2 (en) 2002-09-25
EP1242338B1 EP1242338B1 (en) 2009-03-11

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Country Status (6)

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US (2) US20030034103A1 (en)
EP (1) EP1242338B1 (en)
AT (1) ATE425131T1 (en)
DE (2) DE50015593D1 (en)
WO (1) WO2001040144A2 (en)
ZA (1) ZA200204385B (en)

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Also Published As

Publication number Publication date
ATE425131T1 (en) 2009-03-15
DE10060320A1 (en) 2001-06-07
US20070204941A1 (en) 2007-09-06
ZA200204385B (en) 2003-10-29
EP1242338B1 (en) 2009-03-11
DE50015593D1 (en) 2009-04-23
WO2001040144A2 (en) 2001-06-07
US20030034103A1 (en) 2003-02-20
WO2001040144A3 (en) 2002-04-11
US8147627B2 (en) 2012-04-03

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