WO1997041403A1 - Firing mixtures - Google Patents

Firing mixtures Download PDF

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Publication number
WO1997041403A1
WO1997041403A1 PCT/EP1997/002104 EP9702104W WO9741403A1 WO 1997041403 A1 WO1997041403 A1 WO 1997041403A1 EP 9702104 W EP9702104 W EP 9702104W WO 9741403 A1 WO9741403 A1 WO 9741403A1
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WO
WIPO (PCT)
Prior art keywords
mixture according
explosives
ignition
ignition mixture
mixtures
Prior art date
Application number
PCT/EP1997/002104
Other languages
German (de)
French (fr)
Inventor
Rainer Hagel
Dieter Hofmann
Bodo Preis
Klaus Redecker
Wolfram Seebeck
Original Assignee
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 Gmbh Explosivstoff- Und Systemtechnik filed Critical Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik
Priority to AT97921748T priority Critical patent/ATE304156T1/en
Priority to CA002253196A priority patent/CA2253196C/en
Priority to DE59712416T priority patent/DE59712416D1/en
Priority to EP97921748A priority patent/EP0894235B1/en
Publication of WO1997041403A1 publication Critical patent/WO1997041403A1/en
Priority to US09/873,422 priority patent/US20010054462A1/en

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B3/00—Blasting cartridges, i.e. case and explosive
    • F42B3/10—Initiators therefor
    • F42B3/113—Initiators therefor activated by optical means, e.g. laser, flashlight
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters

Definitions

  • the present invention relates to ignition mixtures, their preparation and their use.
  • Firing mixtures or firing sets serve to ignite pyro-technical mixtures or sets as well as propellant charges.
  • the pyrotechnic mixtures or sets can be the sole charge or an intensifying charge of the ignition or a gas-generating set.
  • Propellant charges / gas sets convert into predominantly gaseous components that are used to trigger fast-running processes such as the acceleration of projectiles, the driving in of fastening materials, for example with the aid of bolt-setting devices or also the inflation of gas bags (airbags) or for triggering belt tensioners in motor vehicle safety.
  • a variant is the use of liquid gas sets instead of solid gas sets. These use the reaction of liquid fuel with oxidizing agents to generate gas.
  • Ignition mixtures are usually triggered mechanically and must therefore be sensitive to the effects of friction and impact. They generally consist of initial or primary explosives, such as lead trinitroresorcinate or diazodinitrophenol, reducing agents such as metal powder and oxidizing agents such as barium nitrate or zinc peroxide. Sensitizers such as tetrazene or friction agents such as glass powder, which increase the sensitivity of the initial explosives, are also used. The rapidly reacting initial explosives are primarily used for electrically ignitable systems. However, the high mechanical sensitivity of the components required for proper functioning is disadvantageous when handling the raw materials and mixtures. It requires special security measures. Other types of ignition, such as ignition by thermal action or by coupling high-frequency Electromagnetic waves do not solve this problem or are only suitable for very special, highly restricted applications.
  • the object of the present invention was to provide new ignition mixtures.
  • the object is achieved by ignition mixtures which can be ignited by laser light.
  • the ignition mixtures according to the invention may contain primary or initial explosives, secondary explosives or mixtures of these explosives as explosives.
  • Primary or initial explosives which can be used are, for example, lead nitro resorcinate, diazodinitrophenol, tetrazene or potassium dinitrobenzofuroxanate or mixtures of these explosives.
  • Suitable secondary explosives are selected from nitrocellulose, hexanitrostilbene, nitrated aromatic compounds and / or nitrated aromatic compounds with a polymeric structure such as polynitropolyphenyl ether or the polynitropolyphenylenes, from certain heterocycles such as nitrotriazolone, from the derivatives of the tetrazoles such as aminotetrazolotole or diaminotetrazolezol as well as from hexogen or octogen.
  • the secondary explosives derived from urea and its derivatives can also be used.
  • Examples include the urea derivatives biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, thiourea, triaminoguanidine nitrate, aminoguanidine hydrogen carbonate, azodicarboxylic acid diamide, tetrazene, dericarboxylic acid, and dicarbarbide urethane, and their derivatives, as well as the carbonic acid urethane and the carbonic acid urethane and the urethane urethane and their derivatives.
  • the explosives mentioned can be used alone or as a mixture.
  • the secondary explosives are preferred, particularly preferably the nitrated aromatic compounds with a polymer structure, in particular the polynipropolyphenyl ethers and the polynitropolyphenylenes or mixtures of these secondary explosives.
  • the igniters according to the invention also contain oxidizing and reducing agents which are customary per se. Binder, processing and / or pressing aids can optionally also be used.
  • the peroxides of the alkali and alkaline earth metals, zinc peroxide, and the peroxodisulfates of the elements mentioned and of ammonium, nitrates of the alkali and alkaline earth metals, in particular lithium, sodium, potassium or strontium nitrate and ammonium nitrate, oxohalogen compounds of the alkali can be used as oxidizing agents or alkaline earth metals or ammonium, particularly preferably potassium perchlorate or ammonium perchlorate. Sulfur is also suitable as an oxidizing agent.
  • the oxidizing agents mentioned can be used alone or as a mixture.
  • metals such as titanium, zirconium, aluminum, magnesium and cerium are used as reducing agents in finely powdered form. Alloys of these metals such as titanium / aluminum or cerium / magnesium can also be used according to the invention.
  • Other reducing agents are carbon or boron. The reducing agents mentioned can be used alone or as a mixture.
  • binders Compounds from the group of polyesters or poly urethanes can be used as binders.
  • Processing and pressing aids can be substances which, for example, increase the flowability, such as Aerosil or substances which prevent dust formation and improve the lubricity or metering capacity, such as graphite or boron nitride.
  • the ignition mixtures according to the invention can optionally be colored or with colored pigments be transferred.
  • the thermal stability can be improved if necessary by adding stabilizers.
  • substances that are used to stabilize the nitrocellulose are suitable as such.
  • combustion moderators can be added to the ignition mixtures according to the invention to influence the rate of combustion.
  • Moderators who intervene in the implementation in the form of heterogeneous catalysis are metals, metal oxides and / or metal carbonates and / or metal sulfides. Boron, silicon, copper, iron, titanium, zinc or molybdenum can preferably be used as metals. Calcium carbonate can also be used. Mixtures of these moderators can also be used.
  • Moderators who intervene in the implementation in the form of homogeneous catalysis are, for example, sulfur, copper resorcylates or ferrocene and its derivatives. These moderators are evaporated by the temperatures occurring during the reaction and can intervene in the reaction itself or as secondary products.
  • the ignition mixtures according to the invention can optionally be treated or coated with protective agents.
  • the ignition mixtures according to the invention can be used in a variety of ways. They are preferably used to ignite pyrotechnic mixtures or sets as well as propellant charges, which are used to trigger fast-moving processes such as the acceleration of projectiles, the driving in of fastening materials, for example with the aid of bolt-setting tools, or that Inflating gas bags (airbags) or triggering belt tensioners can be used in automotive safety.
  • propellant charges such as the acceleration of projectiles, the driving in of fastening materials, for example with the aid of bolt-setting tools, or that Inflating gas bags (airbags) or triggering belt tensioners can be used in automotive safety.
  • the ignition mixtures according to the invention were used with a thermodynamic computer program at constant volume and a charge density of 0.1 g / cm 3 an adiabatic reaction is expected. Table 3 shows the most important data of the thermodynamic calculation. The ignition energy required to trigger a reaction was determined experimentally.
  • the ignition mixtures according to the invention are produced by methods known per se.
  • the individual components are sieved in the mixing ratios given in Table 1 through a sieve with a mesh size of 0.2 mm and mixed in a tumble mixer for 30 minutes.
  • Each 200 mg of these mixtures are pressed with a pressing force of 71 N / mm 2 into tablets with a diameter of 6 mm.
  • the tablets produced in this way are irradiated with a laser beam (wavelength 1,060 nm) approx. 200 mJ and a pulse length of 2.5 ms ignited.
  • the ignition behavior is shown in Table 1.
  • Ti titanium metal powder ⁇ 40 ⁇ m ZnO 2 zinc peroxide, average grain size 6.5 ⁇ m, oxygen content 13.5%

Abstract

A firing mixture which contains explosives, oxidising and reducing agents is characterised in that it contains one or several explosives which can be fired by laser light. Also disclosed is a process for producing the same and its use.

Description

Anzündmischungen Kindling mixtures
Gegenstand der vorliegenden Erfindung sind Anzündmischungen, deren Herstel- lung sowie deren Verwendung.The present invention relates to ignition mixtures, their preparation and their use.
Anzündmischungen oder auch Anzündsätze dienen der Anzündung von pyro- technischen Gemischen oder Sätzen sowie von Treibladungen. Die pyrotechni- schen Gemische oder Sätze können dabei die alleinige Aufladung oder aber eine Verstärkungsladung der Anzündung oder ein gaserzeugender Satz sein. Treibla¬ dungen/Gassätze setzen sich in überwiegend gasförmige Bestandteile um, die zur Auslösung schnell ablaufender Vorgänge wie z.B. die Beschleunigung von Geschossen, das Eintreiben von Befestigungsmaterialien, beispielsweise mit Hilfe von Bolzensetzgeräten oder auch das Aufblasen von Gassäcken (Airbags) oder zum Auslösen von Gurtstraffern in der Kraftfahrzeugsicherheit eingesetzt werden können. Eine Variante stellt die Verwendung von Flüssig-Gassätzen anstelle der Feststoff-Gassätze dar. Diese nutzen die Reaktion von flüssigem Brennstoff mit Oxidationsmitteln zur Gaserzeugung aus.Firing mixtures or firing sets serve to ignite pyro-technical mixtures or sets as well as propellant charges. The pyrotechnic mixtures or sets can be the sole charge or an intensifying charge of the ignition or a gas-generating set. Propellant charges / gas sets convert into predominantly gaseous components that are used to trigger fast-running processes such as the acceleration of projectiles, the driving in of fastening materials, for example with the aid of bolt-setting devices or also the inflation of gas bags (airbags) or for triggering belt tensioners in motor vehicle safety. A variant is the use of liquid gas sets instead of solid gas sets. These use the reaction of liquid fuel with oxidizing agents to generate gas.
Anzündmischungen werden in der Regel mechanisch ausgelöst und müssen da¬ her empfindlich gegenüber Reib- und Schlageinwirkung sein. Sie bestehen in der Regel aus Initial- oder Primärexplosivstoffen wie beispielsweise Bleitrinitroresor- cinat oder Diazodinitrophenol, Reduktionsmitteln wie Metallpulver sowie Oxidati¬ onsmitteln wie Bariumnitrat oder Zinkperoxid. Sensibilisatoren wie Tetrazen oder Friktionsmittel wie Glaspulver, die die Empfindlichkeit der Initialexplosivstoffe er¬ höhen, werden ebenfalls eingesetzt. Für elektrisch anzündbare Systeme werden in erster Linie die schnell reagierenden Initialexplosivstoffe eingesetzt. Die für die einwandfreie Funktion erforderliche hohe mechanische Empfindlichkeit der Be¬ standteile ist jedoch bei der Handhabung der Rohstoffe und Gemische nachteilig. Sie erfordert besondere Sicherheitsmaßnahmen. Andere Anzündarten wie das Anzünden durch thermische Einwirkung oder durch Einkopplung hochfrequenter elektromagnetischer Wellen lösen dieses Problem nicht oder sind nur für ganz spezielle, stark eingeschränkte Anwendungen geeignet.Ignition mixtures are usually triggered mechanically and must therefore be sensitive to the effects of friction and impact. They generally consist of initial or primary explosives, such as lead trinitroresorcinate or diazodinitrophenol, reducing agents such as metal powder and oxidizing agents such as barium nitrate or zinc peroxide. Sensitizers such as tetrazene or friction agents such as glass powder, which increase the sensitivity of the initial explosives, are also used. The rapidly reacting initial explosives are primarily used for electrically ignitable systems. However, the high mechanical sensitivity of the components required for proper functioning is disadvantageous when handling the raw materials and mixtures. It requires special security measures. Other types of ignition, such as ignition by thermal action or by coupling high-frequency Electromagnetic waves do not solve this problem or are only suitable for very special, highly restricted applications.
Die Aufgabe der vorliegenden Erfindung bestand darin, neue Anzündmischungen bereitzustellen.The object of the present invention was to provide new ignition mixtures.
In einer ersten Ausführungsform der Erfindung wird die Aufgabe gelöst durch An¬ zündmischungen, die durch Laserlicht anzündbar sind. Als Explosivstoffe können die erfindungsgemäßen Anzündmischungen Primär- oder Initialexplosivstoffe, Se- kundärexplosivstoffe oder Mischungen dieser Explosivstoffe enthalten. Als Pri¬ mär- oder Initialexplosivstoffe können beispielsweise Bleithnitroresorcinat, Di- azodinitrophenol, Tetrazen oder Kaliumdinitrobenzofuroxanat oder Mischungen dieser Explosivstoffe eingesetzt werden. Geeignete Sekundärexplosivstoffe sind ausgewählt aus Nitrocellulose, Hexanitrostilben, nitrierten aromatischen Verbin- düngen und/oder nitrierten aromatischen Verbindungen mit polymerem Aufbau wie Polynitropolyphenylether oder den Polynitropolyphenylenen, aus bestimmten Heterocyclen wie Nitrotriazolon, aus den Derivaten der Tetrazole wie Amino- tetrazol, Ditetrazol oder Diaminoguanidin-azotetrazol sowie aus Hexogen oder Oktogen. Weiterhin einsetzbar sind die vom Harnstoff und seinen Derivaten abge- leiteten Sekundärexplosivstoffe. Beispielhaft genannt seien hier die Harnstoffderi¬ vate Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminogua- nidinnitrat, Thioharnstoff, Triaminoguanidinnitrat, Aminoguanidinhydrogencar- bonat, Azodicarbonsäurediamid, Tetrazen, Semicarbazidnitrat, sowie die Ure- thane, die Ureide wie Barbitursäure und ihre Derivate. Die genannten Explosiv- Stoffe können allein oder als Mischung eingesetzt werden. Erfindungsgemäß be¬ vorzugt sind die Sekundärexplosivstoffe, besonders bevorzugt die nitrierten aro¬ matischen Verbindungen mit einem polymeren Aufbau, insbesondere die Polyni¬ tropolyphenylether und die Polynitropolyphenylene oder Mischungen dieser Se¬ kundärexplosivstoffe. Neben den Explosivstoffen enthalten die erfindungsgemäßen Anzündmittel noch an sich übliche Oxidations- und Reduktionsmittel. Binder, Verarbeitungs¬ und/oder Preßhilfsmittel können gegebenenfalls ebenfalls eingesetzt werden.In a first embodiment of the invention, the object is achieved by ignition mixtures which can be ignited by laser light. The ignition mixtures according to the invention may contain primary or initial explosives, secondary explosives or mixtures of these explosives as explosives. Primary or initial explosives which can be used are, for example, lead nitro resorcinate, diazodinitrophenol, tetrazene or potassium dinitrobenzofuroxanate or mixtures of these explosives. Suitable secondary explosives are selected from nitrocellulose, hexanitrostilbene, nitrated aromatic compounds and / or nitrated aromatic compounds with a polymeric structure such as polynitropolyphenyl ether or the polynitropolyphenylenes, from certain heterocycles such as nitrotriazolone, from the derivatives of the tetrazoles such as aminotetrazolotole or diaminotetrazolezol as well as from hexogen or octogen. The secondary explosives derived from urea and its derivatives can also be used. Examples include the urea derivatives biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, thiourea, triaminoguanidine nitrate, aminoguanidine hydrogen carbonate, azodicarboxylic acid diamide, tetrazene, dericarboxylic acid, and dicarbarbide urethane, and their derivatives, as well as the carbonic acid urethane and the carbonic acid urethane and the urethane urethane and their derivatives. The explosives mentioned can be used alone or as a mixture. According to the invention, the secondary explosives are preferred, particularly preferably the nitrated aromatic compounds with a polymer structure, in particular the polynipropolyphenyl ethers and the polynitropolyphenylenes or mixtures of these secondary explosives. In addition to the explosives, the igniters according to the invention also contain oxidizing and reducing agents which are customary per se. Binder, processing and / or pressing aids can optionally also be used.
Als Oxidationsmittel können die Peroxide der Alkali- und Erdalkalimetalle, Zink¬ peroxid, sowie die Peroxodisulfate der genannten Elemente und des Ammoniums, Nitrate der Alkali- und Erdalkalimetalle, insbesondere Lithium-, Natrium-, Kalium¬ oder Strontiumnitrat sowie Ammoniumnitrat, Oxohalogenverbindungen der Alkali¬ oder Erdalkalimetalle oder des Ammoniums, besonders bevorzugt Kaliumperchlo- rat oder Ammoniumperchlorat eingesetzt werden. Ebenfalls als Oxidationsmittel geeignet ist Schwefel. Die genannten Oxidationsmittel können allein oder als Mi¬ schung eingesetzt werden.The peroxides of the alkali and alkaline earth metals, zinc peroxide, and the peroxodisulfates of the elements mentioned and of ammonium, nitrates of the alkali and alkaline earth metals, in particular lithium, sodium, potassium or strontium nitrate and ammonium nitrate, oxohalogen compounds of the alkali can be used as oxidizing agents or alkaline earth metals or ammonium, particularly preferably potassium perchlorate or ammonium perchlorate. Sulfur is also suitable as an oxidizing agent. The oxidizing agents mentioned can be used alone or as a mixture.
Als Reduktionsmittel werden erfindungsgemäß Metalle wie beispielsweise Titan, Zirkon, Aluminium, Magnesium, Cer in feinpulverisierter Form eingesetzt. Auch Legierungen dieser Metalle wie Titan/Aluminium oder Cer/Magnesium können erfindungsgemäß eingesetzt werden. Weitere Reduktionsmittel sind Kohlenstoff oder Bor. Die genannten Reduktionsmittel können allein oder als Mischung ein¬ gesetzt werden.According to the invention, metals such as titanium, zirconium, aluminum, magnesium and cerium are used as reducing agents in finely powdered form. Alloys of these metals such as titanium / aluminum or cerium / magnesium can also be used according to the invention. Other reducing agents are carbon or boron. The reducing agents mentioned can be used alone or as a mixture.
Als Binder können Verbindungen aus der Gruppe der Polyester oder der Poly¬ urethane eingesetzt werden. Verbindungen mit bindenden Eigenschaften, die ei¬ nen Beitrag zur Explosionswärme und/oder zur Sauerstoffbiianz beitragen, bei¬ spielsweise Nitrocellulose oder Polynitropolyphenylen, können ebenfalls als Bin- der eingesetzt werden.Compounds from the group of polyesters or poly urethanes can be used as binders. Compounds with binding properties that contribute to the heat of explosion and / or to the oxygen balance, for example nitrocellulose or polynitropolyphenylene, can also be used as binders.
Verarbeitungs- und Preßhilfen können Stoffe sein, die beispielsweise die Riesel¬ fähigkeit erhöhen, wie Aerosil oder Stoffe, die die Staubbildung verhindern und die Gleit- oder Dosierfähigkeit verbessern, wie Graphit oder Bornitrid.Processing and pressing aids can be substances which, for example, increase the flowability, such as Aerosil or substances which prevent dust formation and improve the lubricity or metering capacity, such as graphite or boron nitride.
Zur besseren Absorption des Laserlichtes können die erfindungsgemäßen An¬ zündmischungen gegebenenfalls eingefärbt werden oder mit Farbpigmenten versetzt werden. Die thermische Stabilität kann falls erforderlich durch den Zusatz von Stabilisatoren verbessert werden. Als solche kommen beispielsweise Stoffe in Frage, die zur Stabilisierung der Nitrocellulose eingesetzt werden.For better absorption of the laser light, the ignition mixtures according to the invention can optionally be colored or with colored pigments be transferred. The thermal stability can be improved if necessary by adding stabilizers. For example, substances that are used to stabilize the nitrocellulose are suitable as such.
Des weiteren können den erfindungsgemäßen Anzündmischungen zur Beeinflus¬ sung der Abbrandgeschwindigkeit Abbrandmoderatoren zugesetzt werden.Furthermore, combustion moderators can be added to the ignition mixtures according to the invention to influence the rate of combustion.
Als Abbrandmoderatoren werden Stoffe oder ihre Gemische eingesetzt, die ge¬ eignet sind, durch heterogene oder homogene Katalyse den Abbrand und seine Geschwindigkeit zu beeinflussen. Moderatoren, die in Form einer heterogenen Katalyse in die Umsetzung eingreifen, sind Metalle, Metalloxide und/oder Metall¬ karbonate und/oder Metallsulfide. Als Metalle können vorzugsweise Bor, Silicium, Kupfer, Eisen, Titan, Zink oder Molybdän eingesetzt werden. Auch Kalziumkarbo¬ nat kann eingesetzt werden. Mischungen dieser Moderatoren können ebenfalls verwendet werden.Substances or their mixtures are used as combustion moderators which are suitable for influencing the combustion and its speed by heterogeneous or homogeneous catalysis. Moderators who intervene in the implementation in the form of heterogeneous catalysis are metals, metal oxides and / or metal carbonates and / or metal sulfides. Boron, silicon, copper, iron, titanium, zinc or molybdenum can preferably be used as metals. Calcium carbonate can also be used. Mixtures of these moderators can also be used.
Moderatoren, die in Form einer homogenen Katalyse in die Umsetzung eingreifen, sind beispielsweise Schwefel, Kupfer-Resorcylate oder Ferrocen und seine Derivate. Diese Moderatoren werden durch die bei der Reaktion auftretenden Temperaturen verdampft und können so selbst oder als Folgeprodukte in die Reaktion eingreifen.Moderators who intervene in the implementation in the form of homogeneous catalysis are, for example, sulfur, copper resorcylates or ferrocene and its derivatives. These moderators are evaporated by the temperatures occurring during the reaction and can intervene in the reaction itself or as secondary products.
Zum Schutz gegen Umwelteinflüsse können die erfindungsgemäßen Anzündmi¬ schungen gegegebenfalls mit schützenden Mitteln behandelt oder beschichtet sein.To protect against environmental influences, the ignition mixtures according to the invention can optionally be treated or coated with protective agents.
Die erfindungsgemäßen Anzündmischungen können vielfältig eingesetzt werden. Vorzugsweise werden sie verwendet zur Anzündung pyrotechnischer Gemische oder Sätze sowie von Treibladungen, die zur Auslösung schnellablaufender Vor- gänge wie beispielsweise die Beschleunigung von Geschossen, das Eintreiben von Befestigungsmaterialien z.B. mit Hilfe von Bolzensetzgeräten oder auch das Aufblasen von Gassäcken (Airbags) oder zum Auslösen von Gurtstraffern in der Kraftfahrzeugsicherheit eingesetzt werden.The ignition mixtures according to the invention can be used in a variety of ways. They are preferably used to ignite pyrotechnic mixtures or sets as well as propellant charges, which are used to trigger fast-moving processes such as the acceleration of projectiles, the driving in of fastening materials, for example with the aid of bolt-setting tools, or that Inflating gas bags (airbags) or triggering belt tensioners can be used in automotive safety.
Die sicherheitstechnischen Kenndaten einiger der erfindungsgemäßen Anzündmi- schungen sind in Tabelle 2 dargestellt. Die Daten wurden nach den Methoden der Bundesanstalt für Materialprüfung ermittelt. Im Vergleich zum Primärexplosivstoff Bleitrinitroresorcinat werden bei den erfindungsgemäßen Anzündmitteln insbe¬ sondere die Reib- und Schlagempfindlichkeit deutlich verbessert.The safety characteristics of some of the ignition mixtures according to the invention are shown in Table 2. The data were determined using the methods of the Federal Institute for Materials Testing. Compared to the primary explosive lead trinitroresorcinate, in particular the sensitivity to friction and impact are significantly improved in the igniters according to the invention.
Zur Abschätzung wichtiger Kenngrößen der erfindungsgemäßen Anzündmischun¬ gen, wie die bei der Reaktion freiwerdeπde Energie (Explosionswärme), der Druck, die Explosionstemperatur und die bei dieser Temperatur entstandenen Reaktionsprodukte wurde mit Hilfe eines thermodynamischen Rechenprogramms von den erfindungsgemäßen Anzündmischungen bei konstantem Volumen und einer Ladedichte von 0,1 g/cm3 eine adiabatisch ablaufende Reaktion gerechnet. Tabelle 3 zeigt die wichtigsten Daten der thermodynamischen Berechnung. Die für die Auslösung einer Reaktion erforderliche Zündenergie wurde experimentell ermittelt.To estimate important parameters of the ignition mixtures according to the invention, such as the energy released during the reaction (heat of explosion), the pressure, the explosion temperature and the reaction products formed at this temperature, the ignition mixtures according to the invention were used with a thermodynamic computer program at constant volume and a charge density of 0.1 g / cm 3 an adiabatic reaction is expected. Table 3 shows the most important data of the thermodynamic calculation. The ignition energy required to trigger a reaction was determined experimentally.
Die nachfolgenden Beispiele sollen die Erfindung erläutern, ohne sie einzu¬ schränken.The following examples are intended to explain the invention without restricting it.
Beispiele 1 bis 16:Examples 1 to 16:
Hergestellt werden die erfindungsgemäßen Anzündmischungen nach an sich be¬ kannten Verfahren. Die einzelnen Komponenten werden in den in Tabelle 1 an¬ gegebenen Mischungsverhältnissen durch ein Sieb mit einer lichten Maschen¬ weite von 0,2 mm gesiebt und in einem Taumelmischer 30 Minuten gemischt. Je 200 mg dieser Mischungen werden mit einer Preßkraft von 71 N/mm2 zu Tabletten mit einem Durchmesser von 6 mm verpreßt. Die so hergestellten Tabletten werden mit einem Laserstrahl (Wellenlänge 1.060 nm), einer Strahlenenergie von ca. 200 mJ und einer Pulslänge von 2,5 ms angezündet. Das Anzündverhalten ist in Tabelle 1 wiedergegeben. The ignition mixtures according to the invention are produced by methods known per se. The individual components are sieved in the mixing ratios given in Table 1 through a sieve with a mesh size of 0.2 mm and mixed in a tumble mixer for 30 minutes. Each 200 mg of these mixtures are pressed with a pressing force of 71 N / mm 2 into tablets with a diameter of 6 mm. The tablets produced in this way are irradiated with a laser beam (wavelength 1,060 nm) approx. 200 mJ and a pulse length of 2.5 ms ignited. The ignition behavior is shown in Table 1.
Tabelle 1Table 1
-4-4
OO
Figure imgf000009_0001
Figure imgf000009_0001
+ = Anzündung+ = Ignition
++ = gute Anzündung++ = good ignition
+++ = sehr gute Anzündung eingesetzte Komponenten:+++ = very good ignition used components:
KNO3 Kaliumnitrat < 200 μm NPE PolynitropolyphenyletherKNO 3 potassium nitrate <200 μm NPE polynitropolyphenyl ether
B Bor amorph PNP Polynitropolyphenylen nB boron amorphous PNP polynitropolyphenylene n
Ti Titanmetallpulver < 40 μm ZnO2 Zinkperoxid, mittlere Korngröße 6,5 μm, Sauerstoffgehalt 13,5 %Ti titanium metal powder <40 μm ZnO 2 zinc peroxide, average grain size 6.5 μm, oxygen content 13.5%
Binder Polyurethan -4Binder polyurethane -4
O O
Tabelle 2Table 2
Figure imgf000010_0001
Tabelle 3
Figure imgf000010_0001
Table 3
Figure imgf000011_0001
Figure imgf000011_0001

Claims

Patentansprüche claims
1. Anzündmischung enthaltend Explosivstoffe, Oxidations- und Reduktions¬ mittel, dadurch gekennzeichnet, daß sie einen oder mehrere Explosivstoff/e enthält, der/die durch Laserlicht anzündbar ist/sind.1. ignition mixture containing explosives, oxidizing and reducing agents, characterized in that it contains one or more explosive (s) which can be ignited by laser light.
2. Anzündmischung gemäß Anspruch 1 , dadurch gekennzeichnet, daß der Ex¬ plosivstoff allein oder als Mischung ausgewählt ist aus den Primär- oder In- itialexplosivstoffen, beispielsweise aus Bleitrinitroresorcinat, Diazodinitro- phenol, Tetrazen oder Kaliumdinitrobenzofuroxanat oder aus Mischungen dieser Explosivstoffe.2. Ignition mixture according to claim 1, characterized in that the explosive alone or as a mixture is selected from the primary or initial explosives, for example from lead trinitroresorcinate, diazodinitrophenol, tetrazene or potassium dinitrobenzofuroxanate or from mixtures of these explosives.
3. Anzündmischung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Explosivstoff allein oder als Mischung ausgewählt ist aus den Sekun¬ därexplosivstoffen, beispielsweise aus Nitrocellulose, Hexanitrostilben, aus bestimmten Heterocyclen wie Nitrotriazolon, aus den Derivaten der Tetra- zole wie Aminotetrazol, Ditetrazol oder Diaminoguanidin-azotetrazol, aus Hexogen oder Oktogen, aus den vom Harnstoff und seinen Derivaten abge- leiteten Sekundärexplosivstoffen wie Biuret, Guanidin, Nitroguanidin, Gua- nidinnitrat, Aminoguanidin, Aminoguanidinnitrat, Thioharnstoff, Triamino- guanidinnitrat, Aminoguanidinhydrogencarbonat, Azodicarbonsäurediamid, Tetrazen, Semicarbazidnitrat, aus den Urethanen, aus den Ureiden wie Barbitursäure und ihrer Derivate, aus nitrierten aromatischen Verbindungen oder aus nitrierten aromatischen Verbindungen mit polymerem Aufbau wie die Polynitropolyphenylether oder die Polynitropolyphenylene oder aus Mi¬ schungen dieser Explosivstoffe.3. Ignition mixture according to claim 1 or 2, characterized in that the explosive is selected alone or as a mixture from the secondary explosives, for example from nitrocellulose, hexanitrostilbene, from certain heterocycles such as nitrotriazolone, from the derivatives of tetrazoles such as aminotetrazole, ditetrazole or diaminoguanidine-azotetrazole, from hexogen or octogen, from the secondary explosives derived from urea and its derivatives, such as biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, thiourea, triamino-guanidine nitrate, aminogenzidicarbonitride, aminogenzidicarbonitride from the urethanes, from the ureids such as barbituric acid and its derivatives, from nitrated aromatic compounds or from nitrated aromatic compounds with a polymeric structure such as the polynitropolyphenyl ethers or the polynitropolyphenylenes or from mixtures of these explosives.
4. Anzündmischung gemäß Anspruch 3, dadurch gekennzeichnet, daß der Se- kundärexplosivstoff ausgewählt ist aus nitrierten aromatischen Verbindun¬ gen mit polymerem Aufbau. 4. Ignition mixture according to claim 3, characterized in that the secondary explosive is selected from nitrated aromatic compounds with a polymeric structure.
5. Anzündmischung gemäß einem der Ansprüche 3 oder 4, dadurch gekenn¬ zeichnet, daß der Sekundärexplosivstoff ausgewählt ist aus den Polynitropo- lyphenylethern und/oder Polynitropolyphenylenen.5. ignition mixture according to one of claims 3 or 4, characterized gekenn¬ characterized in that the secondary explosive is selected from the polynitropolyphenyl ethers and / or polynitropolyphenylenes.
6. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 5 da¬ durch gekennzeichnet, daß das Oxidationsmittel ausgewählt ist aus Schwe¬ fel, aus den Peroxiden der Alkali- oder Erdalkalimetalle, aus Zinkperoxid, aus den Peroxodisulfaten der genannten Elemente und des Ammoniums, aus den Nitraten der Alkali- und Erdalkalimetalle, insbesondere aus Lithium-,6. ignition mixture according to one or more of claims 1 to 5 da¬ characterized in that the oxidizing agent is selected from sulfur, from the peroxides of alkali or alkaline earth metals, from zinc peroxide, from the peroxodisulfates of the elements mentioned and ammonium the nitrates of the alkali and alkaline earth metals, in particular of lithium,
Natrium-, Kalium- oder Strontiumπitrat sowie Ammoniumnitrat, aus den Oxohalogenverbindungen der Alkali- oder Erdalkalimetalle oder des Ammoniums, insbesondere aus Kaliumperchlorat oder Ammoniumperchlorat oder aus Mischungen der genannten Substanzen.Sodium, potassium or strontium nitrate and ammonium nitrate, from the oxohalogen compounds of the alkali or alkaline earth metals or ammonium, in particular from potassium perchlorate or ammonium perchlorate or from mixtures of the substances mentioned.
7. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 6, da¬ durch gekennzeichnet, daß das Reduktionsmittel ein Metall, ausgewählt aus Titan, Zirkon, Aluminium, Magnesium oder Cer, eine Mischung dieser Me¬ talle, eine Legierung dieser Metalle wie Titan/Aluminium oder Cer/Magnesium, daß es Kohlenstoff oder Bor oder daß es eine Mischung der genannten Mittel ist.7. ignition mixture according to one or more of claims 1 to 6, characterized in that the reducing agent is a metal selected from titanium, zirconium, aluminum, magnesium or cerium, a mixture of these metals, an alloy of these metals such as titanium / Aluminum or cerium / magnesium, that it is carbon or boron or that it is a mixture of the said agents.
8. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 7, da¬ durch gekennzeichnet, daß sie zusätzlich zu den Explosivstoffen, Oxidati- ons- und Reduktionsmitteln an sich übliche Binder und/oder Verarbeitungs¬ und/oder Preßhilfsmittel und /oder Abbrandmoderatoren enthält.8. Ignition mixture according to one or more of claims 1 to 7, characterized in that it contains, in addition to the explosives, oxidation and reducing agents, conventional binders and / or processing and / or pressing aids and / or combustion moderators.
9. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 8, da¬ durch gekennzeichnet, daß sie eingefärbt oder mit Farbpigmenten versetzt ist. 9. ignition mixture according to one or more of claims 1 to 8, da¬ characterized in that it is colored or mixed with color pigments.
10. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 9, da¬ durch gekennzeichnet, daß als Abbrandmoderatoren Stoffe oder ihre Gemi¬ sche eingesetzt werden, die geeignet sind, durch heterogene oder homo¬ gene Katalyse den Abbrand und seine Geschwindigkeit zu beeinflussen.10. Ignition mixture according to one or more of claims 1 to 9, characterized in that substances or their mixtures are used as combustion moderators which are suitable for influencing the combustion and its speed by heterogeneous or homogeneous catalysis.
11. Verfahren zur Herstellung der Aπzündmischung nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die einzelnen Kom¬ ponenten gemischt und anschließend verpreßt werden.11. A process for the preparation of the ignition mixture according to one or more of claims 1 to 10, characterized in that the individual components are mixed and then pressed.
12. Verwendung der Anzündmischung nach einem oder mehreren der Ansprü¬ che 1 bis 10 zur Anzündung pyrotechnischer Gemische oder Sätze sowie von Treibladungen.12. Use of the ignition mixture according to one or more of claims 1 to 10 for the ignition of pyrotechnic mixtures or sets as well as propellant charges.
13. Anzündmischung gemäß einem oder mehreren der Ansprüche 1 bis 10, da- durch gekennzeichnet, daß sie eine Mischung von Primär- und Sekun¬ därexplosivstoffen enthält. 13. Ignition mixture according to one or more of claims 1 to 10, characterized in that it contains a mixture of primary and secondary explosives.
PCT/EP1997/002104 1996-04-26 1997-04-24 Firing mixtures WO1997041403A1 (en)

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AT97921748T ATE304156T1 (en) 1996-04-26 1997-04-24 IGNITION MIXTURES
CA002253196A CA2253196C (en) 1996-04-26 1997-04-24 Firing mixtures
DE59712416T DE59712416D1 (en) 1996-04-26 1997-04-24 igniter
EP97921748A EP0894235B1 (en) 1996-04-26 1997-04-24 Firing mixtures
US09/873,422 US20010054462A1 (en) 1996-04-26 2001-06-05 Ignition Mixtures

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DE19616627.6 1996-04-26
DE19616627A DE19616627A1 (en) 1996-04-26 1996-04-26 Kindling mixtures

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US20100180787A1 (en) 2010-07-22
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ES2249799T3 (en) 2006-04-01
US20110162547A1 (en) 2011-07-07
EP0894235B1 (en) 2005-09-07
DE19616627A1 (en) 1997-11-06
DE59712416D1 (en) 2005-10-13
US20010054462A1 (en) 2001-12-27
US20070017612A1 (en) 2007-01-25

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