EP0894235B1 - Firing mixtures - Google Patents

Firing mixtures Download PDF

Info

Publication number
EP0894235B1
EP0894235B1 EP97921748A EP97921748A EP0894235B1 EP 0894235 B1 EP0894235 B1 EP 0894235B1 EP 97921748 A EP97921748 A EP 97921748A EP 97921748 A EP97921748 A EP 97921748A EP 0894235 B1 EP0894235 B1 EP 0894235B1
Authority
EP
European Patent Office
Prior art keywords
igniter
agent according
mixtures
agents
ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97921748A
Other languages
German (de)
French (fr)
Other versions
EP0894235A1 (en
Inventor
Rainer Hagel
Dieter Hofmann
Bodo Preis
Klaus Redecker
Wolfram Seebeck
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 EP0894235A1 publication Critical patent/EP0894235A1/en
Application granted granted Critical
Publication of EP0894235B1 publication Critical patent/EP0894235B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 igniter mixtures, their preparation as well as their use.
  • Ignition mixtures or primers serve to ignite pyrotechnic Mixtures or sets and of propellant charges.
  • the pyrotechnic Mixtures or sentences can be the sole charge or a Boost charge of the ignition or a gas generating set.
  • Propellant charges / gas charges are made up of predominantly gaseous components, the for triggering fast-running operations such as e.g. the acceleration of Shot, the driving of fastening materials, for example, with the help from bolt guns or the inflation of airbags or be used to trigger belt tensioners in automotive safety can.
  • a variant is the use of liquid gas sets instead of Solid fuel gas sets dar. These use the reaction of liquid fuel with Oxidizing agents for gas production.
  • Ignition mixtures are usually triggered mechanically and must therefore be sensitive to friction and impact. They insist in the Usually from initial or primary explosives, such as leadriniterresorcinate or diazodinitrophenol, reducing agents such as metal powder and oxidizing agents such as barium nitrate or zinc peroxide. Sensitizers such as tetracene or Friction agents such as glass powder, which increase the sensitivity of the initial explosives, are also used. For electrically ignitable systems primarily the fast reacting initial explosives used. The for the proper function required high mechanical sensitivity of the components However, is disadvantageous in the handling of raw materials and mixtures. It requires special security measures. Other kind of lighting like that Igniting by thermal action or by coupling high-frequency electromagnetic waves do not solve this problem or are only for whole special, very limited applications suitable.
  • the object of the present invention was to ignite new ignitions provide.
  • the object is achieved by igniting mixtures, according to claim 1 which can be ignited by laser light.
  • the igniters according to the invention still contain per se conventional oxidizing and reducing agents. Binder, processing and / or pressing aids may optionally also be used.
  • oxidizing agents the peroxides of the alkali and alkaline earth metals, zinc peroxide, and the peroxodisulfates of said elements and of ammonium, Nitrates of the alkali and alkaline earth metals, in particular lithium, sodium, potassium or strontium nitrate and ammonium nitrate, oxo-halogen compounds of alkali metal or alkaline earth metals or ammonium, more preferably potassium perchlorate or ammonium perchlorate.
  • sulfur is suitable as an oxidizing agent sulfur is suitable.
  • the mentioned oxidizing agents can be used alone or as a mixture be used.
  • metals such as titanium, Zirconium, aluminum, magnesium, cerium used in finely pulverized form. Also Alloys of these metals such as titanium / aluminum or cerium / magnesium can used according to the invention. Further reducing agents are carbon or boron. The abovementioned reducing agents can be used alone or as a mixture become.
  • binders compounds from the group of polyesters or polyurethanes be used.
  • Compounds with binding properties that have a Contribute to the explosion heat and / or the oxygen balance for example Nitrocellulose or polynitropolyphenylene, may also be used as a binder be used.
  • Processing and pressing aids may be substances that, for example, the flowability increase, such as Aerosil or substances that prevent dust formation and improve the lubricity or meterability, such as graphite or boron nitride.
  • the igniter mixtures according to the invention optionally colored or with colored pigments be offset.
  • the thermal stability can, if necessary, by the addition be improved by stabilizers. As such, for example, substances come in Question, which are used to stabilize the nitrocellulose.
  • the igniter mixtures according to the invention can be influenced the burning rate Abbrandmoderatoren be added.
  • Moderators in the form of a heterogeneous Catalysis in the reaction are metals, metal oxides and / or metal carbonates and / or metal sulfides.
  • metals preferably boron, silicon, Copper, iron, titanium, zinc or molybdenum can be used. Also calcium carbonate can be used. Mixtures of these moderators can also be used.
  • Moderators who intervene in the implementation in the form of homogeneous catalysis, For example, sulfur, copper resorcylates or ferrocene and its Derivatives. These moderators are characterized by those occurring during the reaction Temperatures evaporate and can themselves or as secondary products in the Intervene reaction.
  • the igniter mixtures according to the invention if necessary, treated or coated with protective agents be.
  • the igniter mixtures according to the invention can be used in a variety of ways. Preferably, they are used to ignite pyrotechnic mixtures or propellant charges used to trigger fast-paced operations such as the acceleration of projectiles, the driving of fastening materials e.g. with the help of bolt guns or the Inflating airbags or releasing pretensioners in the airbag Automotive safety are used.
  • thermodynamic calculation program was used to determine the igniter mixtures according to the invention at constant volume and a charge density of 0, 1 g / cm 3 calculated an adiabatic reaction. Table 3 shows the most important data of the thermodynamic calculation. The ignition energy required to initiate a reaction was determined experimentally.
  • the igniter mixtures according to the invention are prepared by processes known per se.
  • the individual components are sieved in the mixing ratios indicated in Table 1 through a sieve with a clear 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 thus produced are ignited with a laser beam (wavelength 1,060 nm), a beam energy of about 200 mJ and a pulse length of 2.5 ms.
  • the ignition behavior is shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Air Bags (AREA)
  • Automotive Seat Belt Assembly (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrical Control Of Ignition Timing (AREA)

Abstract

A firing mixture which contains explosives, oxidizing and reducing agents is characterized 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

Gegenstand der vorliegenden Erfindung sind Anzündmischungen, deren Herstellung sowie deren Verwendung.The present invention relates to igniter mixtures, their preparation as well as their use.

Anzündmischungen oder auch Anzündsätze dienen der Anzündung von pyrotechnischen Gemischen oder Sätzen sowie von Treibladungen. Die pyrotechnischen Gemische oder Sätze können dabei die alleinige Aufladung oder aber eine Verstärkungsladung der Anzündung oder ein gaserzeugender Satz sein. Treibladungen/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.Ignition mixtures or primers serve to ignite pyrotechnic Mixtures or sets and of propellant charges. The pyrotechnic Mixtures or sentences can be the sole charge or a Boost charge of the ignition or a gas generating set. Propellant charges / gas charges are made up of predominantly gaseous components, the for triggering fast-running operations such as e.g. the acceleration of Shot, the driving of fastening materials, for example, with the help from bolt guns or the inflation of airbags or be used to trigger belt tensioners in automotive safety can. A variant is the use of liquid gas sets instead of Solid fuel gas sets dar. These use the reaction of liquid fuel with Oxidizing agents for gas production.

Anzündmischungen werden in der Regel mechanisch ausgelöst und müssen daher empfindlich gegenüber Reib- und Schlageinwirkung sein. Sie bestehen in der Regel aus Initial- oder Primärexplosivstoffen wie beispielsweise Bleitrinitroresorcinat oder Diazodinitrophenol, Reduktionsmitteln wie Metallpulver sowie Oxidationsmitteln wie Bariumnitrat oder Zinkperoxid. Sensibilisatoren wie Tetrazen oder Friktionsmittel wie Glaspulver, die die Empfindlichkeit der Initialexplosivstoffe erhöhen, 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 Bestandteile 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 friction and impact. They insist in the Usually from initial or primary explosives, such as leadriniterresorcinate or diazodinitrophenol, reducing agents such as metal powder and oxidizing agents such as barium nitrate or zinc peroxide. Sensitizers such as tetracene or Friction agents such as glass powder, which increase the sensitivity of the initial explosives, are also used. For electrically ignitable systems primarily the fast reacting initial explosives used. The for the proper function required high mechanical sensitivity of the components However, is disadvantageous in the handling of raw materials and mixtures. It requires special security measures. Other kind of lighting like that Igniting by thermal action or by coupling high-frequency electromagnetic waves do not solve this problem or are only for whole special, very limited applications suitable.

Die Aufgabe der vorliegenden Erfindung bestand darin, neue Anzündmischungen bereitzustellen.The object of the present invention was to ignite new ignitions provide.

In einer ersten Ausführungsform der Erfindung wird die Aufgabe gelöst durch Anzündmischungen, gemäß Anspruch 1 die durch Laserlicht anzündbar sind. In a first embodiment of the invention the object is achieved by igniting mixtures, according to claim 1 which can be ignited by laser light.

Neben den Explosivstoffen enthalten die erfindungsgemäßen Anzündmittel noch an sich übliche Oxidations- und Reduktionsmittel. Binder, Verarbeitungs- und/oder Preßhilfsmittel können gegebenenfalls ebenfalls eingesetzt werden.Besides the explosives, the igniters according to the invention still contain per se conventional oxidizing and reducing agents. Binder, processing and / or pressing aids may optionally also be used.

Als Oxidationsmittel können die Peroxide der Alkali- und Erdalkalimetalle, Zinkperoxid, 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 Kaliumperchlorat oder Ammoniumperchlorat eingesetzt werden. Ebenfalls als Oxidationsmittel geeignet ist Schwefel. Die genannten Oxidationsmittel können allein oder als Mischung eingesetzt werden.As oxidizing agents, the peroxides of the alkali and alkaline earth metals, zinc peroxide, and the peroxodisulfates of said elements and of ammonium, Nitrates of the alkali and alkaline earth metals, in particular lithium, sodium, potassium or strontium nitrate and ammonium nitrate, oxo-halogen compounds of alkali metal or alkaline earth metals or ammonium, more preferably potassium perchlorate or ammonium perchlorate. Also as an oxidizing agent sulfur is suitable. The mentioned oxidizing agents can be used alone or as a mixture be used.

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 eingesetzt werden.As a reducing agent according to the invention metals such as titanium, Zirconium, aluminum, magnesium, cerium used in finely pulverized form. Also Alloys of these metals such as titanium / aluminum or cerium / magnesium can used according to the invention. Further reducing agents are carbon or boron. The abovementioned reducing agents can be used alone or as a mixture become.

Als Binder können Verbindungen aus der Gruppe der Polyester oder der Polyurethane eingesetzt werden. Verbindungen mit bindenden Eigenschaften, die einen Beitrag zur Explosionswärme und/oder zur Sauerstoffbilanz beitragen, beispielsweise Nitrocellulose oder Polynitropolyphenylen, können ebenfalls als Binder eingesetzt werden.As binders, compounds from the group of polyesters or polyurethanes be used. Compounds with binding properties that have a Contribute to the explosion heat and / or the oxygen balance, for example Nitrocellulose or polynitropolyphenylene, may also be used as a binder be used.

Verarbeitungs- und Preßhilfen können Stoffe sein, die beispielsweise die Rieselfähigkeit erhöhen, wie Aerosil oder Stoffe, die die Staubbildung verhindern und die Gleit- oder Dosierfähigkeit verbessern, wie Graphit oder Bornitrid.Processing and pressing aids may be substances that, for example, the flowability increase, such as Aerosil or substances that prevent dust formation and improve the lubricity or meterability, such as graphite or boron nitride.

Zur besseren Absorption des Laserlichtes können die erfindungsgemäßen Anzündmischungen 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 igniter mixtures according to the invention optionally colored or with colored pigments be offset. The thermal stability can, if necessary, by the addition be improved by stabilizers. As such, for example, substances come in Question, which are used to stabilize the nitrocellulose.

Des weiteren können den erfindungsgemäßen Anzündmischungen zur Beeinflussung der Abbrandgeschwindigkeit Abbrandmoderatoren zugesetzt werden.Furthermore, the igniter mixtures according to the invention can be influenced the burning rate Abbrandmoderatoren be added.

Als Abbrandmoderatoren werden Stoffe oder ihre Gemische eingesetzt, die geeignet 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 Metallkarbonate und/oder Metallsulfide. Als Metalle können vorzugsweise Bor, Silicium, Kupfer, Eisen, Titan, Zink oder Molybdän eingesetzt werden. Auch Kalziumkarbonat kann eingesetzt werden. Mischungen dieser Moderatoren können ebenfalls verwendet werden.As Abbrandmoderatoren substances or their mixtures are used, which are suitable are, by heterogeneous or homogeneous catalysis, the burnup and its To influence speed. Moderators in the form of a heterogeneous Catalysis in the reaction, are metals, metal oxides and / or metal carbonates and / or metal sulfides. As metals, preferably boron, silicon, Copper, iron, titanium, zinc or molybdenum can be used. Also calcium carbonate can 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, For example, sulfur, copper resorcylates or ferrocene and its Derivatives. These moderators are characterized by those occurring during the reaction Temperatures evaporate and can themselves or as secondary products in the Intervene reaction.

Zum Schutz gegen Umwelteinflüsse können die erfindungsgemäßen Anzündmischungen gegegebenfalls mit schützenden Mitteln behandelt oder beschichtet sein.To protect against environmental influences, the igniter mixtures according to the invention if necessary, treated or coated with protective agents be.

Die erfindungsgemäßen Anzündmischungen können vielfältig eingesetzt werden. Vorzugsweise werden sie verwendet zur Anzündung pyrotechnischer Gemische oder Sätze sowie von Treibladungen, die zur Auslösung schnellablaufender Vorgänge 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 igniter mixtures according to the invention can be used in a variety of ways. Preferably, they are used to ignite pyrotechnic mixtures or propellant charges used to trigger fast-paced operations such as the acceleration of projectiles, the driving of fastening materials e.g. with the help of bolt guns or the Inflating airbags or releasing pretensioners in the airbag Automotive safety are used.

Die sicherheitstechnischen Kenndaten einiger der erfindungsgemäßen Anzündmischungen 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 insbesondere die Reib- und Schlagempfindlichkeit deutlich verbessert.The safety characteristics of some of the primer mixtures according to the invention are shown in Table 2. The data were collected according to the methods of Federal Institute for Materials Testing. Compared to the primary explosive Bleitrinitroresorcinat be in the igniter according to the invention in particular the friction and impact sensitivity significantly improved.

Zur Abschätzung wichtiger Kenngrößen der erfindungsgemäßen Anzündmischungen, wie die bei der Reaktion freiwerdende 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.In order to estimate important parameters of the igniter 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, a thermodynamic calculation program was used to determine the igniter mixtures according to the invention at constant volume and a charge density of 0, 1 g / cm 3 calculated an adiabatic reaction. Table 3 shows the most important data of the thermodynamic calculation. The ignition energy required to initiate a reaction was determined experimentally.

Die nachfolgenden Beispiele bzw. Vergleichsbeispiele sollen die Erfindung erläutern, ohne sie einzuschränken.The following examples and comparative examples are intended to illustrate the invention without restricting it.

Beispiele 1 bis 16:Examples 1 to 16:

Hergestellt werden die erfindungsgemäßen Anzündmischungen nach an sich bekannten Verfahren. Die einzelnen Komponenten werden in den in Tabelle 1 angegebenen Mischungsverhältnissen durch ein Sieb mit einer lichten Maschenweite 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.

Figure 00070001
Probe Druck [atm] T [K] ExW. [cal/g] Kondensatanteil [%/mol] Zündenergie [mJ] NPE 1109 2932 686 0 ≈ 10 NPE/KNO3 66,7/33,3 907,4 3073,5 672 7,5 160 NPE/ZnO2/Ti 45/50/5 1198 4146 978 14,6 ≈ 200 Schwarzpulver/NPE 75/25 430 2290 -179 11,6 ≈ 200 AZM O 9531/NPE 75/25 622 3265 615 52 ≈ 200 NPE/KNO3/B 50/40/10 843 3374 673 29 ≈ 90 NPE/ZnO2 66,7/33,3 1341 4044 1016 7 > 200 NPE/ZnO2/B 64,8/32,3/2,9 1194 3731 991 14 > 200 NPE/KNO3/B 64,8/32,3/2,9 1002 3382 752 2 ≈ 100 NC/KNO3 66,7/33,3 872 3282 883 11 keine Anzündung Bleitrinitroresorcinat 683 3639 550 10 ≈ 5 Explosivstoff Reibempfindlichkeit [N] Schlagempfindlichkeit [J] Verpuffungspunkt [°C] Bleitrinitroresorcinat 2 ≤ 0,025 280 AZM O 2956 ≥ 360 5 > 400 AZM O 9531 ≥ 360 4 > 400 Schwarzpulver ≥ 360 5 > 400 HITP (Basis Aminotetrazol) ≥ 360 15 - 50 > 400 NPE ≥ 360 7,5 > 260 NPE/ZnO2/Ti ≥ 360 15 230 NPE/ZnO2 240 20 235 NPE/KNO3 + 3% B 160 4 Zersetzung ab 230 PNP/KNO3 ≥ 360 10 293 PNP/KNO3/B ≥ 360 10 293 The igniter mixtures according to the invention are prepared by processes known per se. The individual components are sieved in the mixing ratios indicated in Table 1 through a sieve with a clear 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 thus produced are ignited with a laser beam (wavelength 1,060 nm), a beam energy of about 200 mJ and a pulse length of 2.5 ms. The ignition behavior is shown in Table 1.
Figure 00070001
sample Pressure [atm] T [K] ExW. [cal / g] Condensate content [% / mol] Ignition energy [mJ] NPE 1109 2932 686 0 ≈ 10 NPE / KNO 3 66,7 / 33,3 907.4 3,073.5 672 7.5 160 NPE / ZnO 2 / Ti 45/50/5 1198 4146 978 14.6 ≈ 200 Black powder / NPE 75/25 430 2290 -179 11.6 ≈ 200 AZM O 9531 / NPE 75/25 622 3265 615 52 ≈ 200 NPE / KNO 3 / B 50/40/10 843 3374 673 29 ≈ 90 NPE / ZnO 2 66,7 / 33,3 1341 4044 1016 7 > 200 NPE / ZnO 2 / B 64.8 / 32.3 / 2.9 1194 3731 991 14 > 200 NPE / KNO 3 / B 64.8 / 32.3 / 2.9 1002 3382 752 2 ≈ 100 NC / KNO 3 66,7 / 33,3 872 3282 883 11 no ignition trinitroresorcinate 683 3639 550 10 ≈ 5 explosive Friction sensitivity [N] Blow sensitivity [J] Deflagration point [° C] trinitroresorcinate 2 ≤ 0.025 280 AZM O 2956 ≥ 360 5 > 400 AZM O 9531 ≥ 360 4 > 400 Black powder ≥ 360 5 > 400 HITP (base aminotetrazole) ≥ 360 15 - 50 > 400 NPE ≥ 360 7.5 > 260 NPE / ZnO 2 / Ti ≥ 360 15 230 NPE / ZnO 2 240 20 235 NPE / KNO 3 + 3% B 160 4 Decomposition from 230 PNP / KNO 3 ≥ 360 10 293 PNP / KNO 3 / B ≥ 360 10 293

Claims (8)

  1. Igniter agent containing conventional oxidising and reducing agents known per se, characterised in that it can be ignited by laser light and contains polynitropolyphenyl ether or polynitropolyphenylene or mixtures of these compounds.
  2. Igniter agent according to claim 1, characterised in that it additionally contains conventional oxidising agents, reducing agents, binders, combustion moderators, processing agents and/or compaction aids.
  3. Igniter agent according to claim 1 or 2, characterised in that the oxidising agent is selected from sulfur, from peroxides of alkali or alkaline earth metals, from zinc peroxide, from peroxodisulfates of the aforementioned elements and of ammonium, from nitrates of alkali and alkaline earth metals, in particular from lithium, sodium, potassium or strontium nitrate as well as ammonium nitrate, from oxohalogen compounds of alkali or alkaline earth metals or ammonium, in particular from potassium perchlorate or ammonium perchlorate or from mixtures of the aforementioned substances.
  4. Igniter agent according to one or more of claims 1 to 3, characterised in that the reducing agent is a metal selected from titanium, zirconium, aluminium, magnesium or cerium, a mixture of these metals, an alloy of these metals such as titanium/aluminium or cerium/magnesium, that it is carbon or boron, or that it is a mixture of the aforementioned agents.
  5. Igniter agent according to one or more of claims 1 to 4, characterised in that it is pigmented or colouring pigments are added thereto.
  6. Igniter agent according to one or more of claims 1 to 5, characterised in that as combustion moderators there are used substances or mixtures thereof that are capable, by heterogeneous or homogeneous catalysis, of influencing the combustion and its rate.
  7. Process for the production of the igniter agent according to one or more of claims 1 to 6, characterised in that the corresponding individual components are mixed and then compacted.
  8. Use of the igniter agent according to one or more of claims 1 to 6 for igniting pyrotechnical mixtures or batches as well as propellant charges.
EP97921748A 1996-04-26 1997-04-24 Firing mixtures Expired - Lifetime EP0894235B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19616627A DE19616627A1 (en) 1996-04-26 1996-04-26 Kindling mixtures
DE19616627 1996-04-26
PCT/EP1997/002104 WO1997041403A1 (en) 1996-04-26 1997-04-24 Firing mixtures

Publications (2)

Publication Number Publication Date
EP0894235A1 EP0894235A1 (en) 1999-02-03
EP0894235B1 true EP0894235B1 (en) 2005-09-07

Family

ID=7792474

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97921748A Expired - Lifetime EP0894235B1 (en) 1996-04-26 1997-04-24 Firing mixtures

Country Status (6)

Country Link
US (4) US20010054462A1 (en)
EP (1) EP0894235B1 (en)
AT (1) ATE304156T1 (en)
DE (2) DE19616627A1 (en)
ES (1) ES2249799T3 (en)
WO (1) WO1997041403A1 (en)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19805976C1 (en) * 1998-02-13 1999-04-29 Nigu Chemie Gmbh Pre-ignition powder for thermal safety device for car air-bags
WO1999048842A1 (en) * 1998-03-20 1999-09-30 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Primary explosives and primers which can be ignited by electric triggering
US6165296A (en) * 1999-02-02 2000-12-26 Autoliv Development As Gas generant igniter composition and method
US6132480A (en) * 1999-04-22 2000-10-17 Autoliv Asp, Inc. Gas forming igniter composition for a gas generant
ATA75099A (en) * 1999-04-28 2001-03-15 Hirtenberger Ag IGNITION BLOCK
DE10058705C1 (en) 2000-11-25 2002-02-28 Rheinmetall W & M Gmbh Pourable bursting charge consisting of crystalline explosive embedded in a polymer matrix, containing finely divided metal powder, e.g. vanadium, as solid lubricant to provide low viscosity at high solids content
DE10221044A1 (en) * 2001-05-10 2002-11-14 Dynamit Nobel Ag Igniter composition useful for coating metal strip, hot wire or spark gap igniters comprises soluble igniter substances e.g. cesium azotetrazolate
AT410315B (en) * 2001-11-14 2003-03-25 Josef Koehler Low signature pyrotechnic product, used as electrically-ignitable bullet-hit for special effects or in cable cutter, pelican hook, glass breaker or trunnion gun, contains atoxic metal diazinate, passivator and nitro compounds
KR100561952B1 (en) * 2002-09-13 2006-03-21 주식회사 한화 Slight-shock blasting composition
US20040089383A1 (en) * 2003-02-06 2004-05-13 Mendenhall Ivan V. Gas generant igniter coating materials and methods
DE102004001980A1 (en) * 2003-01-14 2004-07-22 Ruag Ammotec Gmbh Propellant charge useful in weapons training systems comprises a soft friction material
CA2526475A1 (en) 2003-05-21 2004-12-02 Alexza Pharmaceuticals, Inc. Optically ignited or electrically ignited self-contained heating unit and drug-supply unit employing same
US7402777B2 (en) 2004-05-20 2008-07-22 Alexza Pharmaceuticals, Inc. Stable initiator compositions and igniters
FR2897864B1 (en) * 2006-02-24 2008-04-11 Cheddite France Sa PRIMING COMPOSITION AND APPLICATIONS
US8540828B2 (en) * 2008-08-19 2013-09-24 Alliant Techsystems Inc. Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same
US8641842B2 (en) 2011-08-31 2014-02-04 Alliant Techsystems Inc. Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same
US20130333815A1 (en) * 2012-06-13 2013-12-19 Alliant Techsystems Inc. Non-lethal payloads and methods of producing same
BRPI0921212B1 (en) * 2008-11-07 2019-10-15 Ruag Ammotec Gmbh IGNITION SETS AS INITIAL EXPLOSIVE SUBSTANCES
US8465606B1 (en) * 2009-01-16 2013-06-18 The United States Of America As Represented By The Secretary Of The Army Composition of matter for an incendiary device and method of manufacture
DE102011108146B4 (en) * 2011-07-20 2014-03-20 Diehl Bgt Defence Gmbh & Co. Kg Use of a salt of bistetrazolylamine and detonator
RU2522611C2 (en) * 2012-10-18 2014-07-20 Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" Light sensitive explosive composition
KR101740620B1 (en) * 2015-02-27 2017-05-26 부산대학교 산학협력단 Nano Energetic Material Composites with Explosion via Optical Ignition and Method for fabricating the same
EP3523266A4 (en) * 2016-10-05 2020-06-10 Olin Corporation Pyrotechnic compositions
US10460941B2 (en) * 2016-11-08 2019-10-29 Varian Semiconductor Equipment Associates, Inc. Plasma doping using a solid dopant source
RU2637016C1 (en) * 2017-03-20 2017-11-29 Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") Method for manufacturing heat-resistant light-sensitive explosive compositions and light detonator on their basis
RU2729490C1 (en) * 2019-06-14 2020-08-07 Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") Initiating composition and method for production thereof

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3519505A (en) * 1967-03-01 1970-07-07 Space Ordnance Systems Inc Ignition material containing tellurium dioxide,boron and fluoropolymeric binder
DE1771943C2 (en) * 1968-08-05 1975-03-27 Dynamit Nobel Ag, 5210 Troisdorf Ignition kit for propellants and rocket propellants
US3618521A (en) * 1969-07-07 1971-11-09 Us Navy Propellant gas generator
US3876478A (en) * 1972-12-18 1975-04-08 Us Navy Light sensitive explosive mixture
DE2543971C2 (en) * 1975-10-02 1986-05-22 Dynamit Nobel Ag, 5210 Troisdorf Ignition system for high temperature resistant propellants
DE2752166C2 (en) * 1977-11-23 1986-10-23 Dynamit Nobel Ag, 5210 Troisdorf Polynitro aromatic polymers
DE2952069C2 (en) * 1979-12-22 1983-02-17 Dynamit Nobel Ag, 5210 Troisdorf Use of zinc peroxide in explosive or pyrotechnic mixtures
US4620046A (en) * 1983-03-21 1986-10-28 Dynamit Nobel Aktiengesellschaft Nitrated aryl ethers
LU85320A1 (en) * 1984-04-17 1985-11-27 Oreal COSMETIC COMPOSITION CONTAINING ALOESIN AS A PROTECTIVE AGENT AGAINST SUNLIGHT AND ITS USE FOR PROTECTING SKIN AND HAIR
DE3707694A1 (en) * 1987-03-11 1988-09-29 Dynamit Nobel Ag ELECTRICALLY APPLICABLE SETS FOR SLEEVELESS AMMUNITION AND DRIVING CARTRIDGES
FR2615609B1 (en) * 1987-05-20 1991-12-20 Aerospatiale PHOTOPYROTECHNICAL PRIMING DEVICE AND PHOTOPYROTECHNICAL CHAIN USING THE SAME
US4861924A (en) * 1988-08-25 1989-08-29 Jet Research Center, Inc. 1,3,5-trinitro-2,4,6-tripicrylbenzene
SE462092B (en) * 1988-10-17 1990-05-07 Nitro Nobel Ab INITIATIVE ELEMENT FOR PRIMARY EXTENSION FREE EXPLOSION CAPS
US4892037A (en) * 1989-01-03 1990-01-09 The United States Of America As Represented By The Secretary Of The Army Self consumable initiator
US5212343A (en) * 1990-08-27 1993-05-18 Martin Marietta Corporation Water reactive method with delayed explosion
US5099761A (en) * 1991-01-28 1992-03-31 The United States Of America As Represented By The Secretary Of The Army Laser actuated thru-bulkhead initiator
JP2956913B2 (en) * 1991-05-15 1999-10-04 株式会社アドバンテスト IC test equipment
JPH05208885A (en) * 1991-06-26 1993-08-20 Asahi Chem Ind Co Ltd Slurry explosive composition
US5179247A (en) * 1991-07-15 1993-01-12 Ensign-Bickford Aerospace Corporation Optically initiated detonator
US5625165A (en) * 1992-02-24 1997-04-29 Wight; Charles A. Desensitized energetic materials
DE4302476C2 (en) * 1993-01-29 1995-12-07 Dynamit Nobel Ag Ignition-sensitive electrical detonators with a weak detonative output, process for their production and their use
US5406889A (en) * 1993-09-03 1995-04-18 Morton International, Inc. Direct laser ignition of ignition products
US5552257A (en) * 1994-01-21 1996-09-03 Minnesota Mining And Manufacturing Company Thermal decomposition of azide-containing materials
EP0704415B1 (en) * 1994-08-27 1999-03-03 Eley Limited Primer composition
US5747723A (en) * 1996-11-26 1998-05-05 The United States Of America As Represented By The Secretary Of The Army Modular artillery charge system
FR2774684B1 (en) * 1998-02-10 2000-03-03 Poudres & Explosifs Ste Nale NEW NON-DETONATED PYROTECHNIC MATERIALS FOR MICROSYSTEMS

Also Published As

Publication number Publication date
DE19616627A1 (en) 1997-11-06
DE59712416D1 (en) 2005-10-13
EP0894235A1 (en) 1999-02-03
ES2249799T3 (en) 2006-04-01
ATE304156T1 (en) 2005-09-15
US20010054462A1 (en) 2001-12-27
WO1997041403A1 (en) 1997-11-06
US20070017612A1 (en) 2007-01-25
US20100180787A1 (en) 2010-07-22
US20110162547A1 (en) 2011-07-07

Similar Documents

Publication Publication Date Title
EP0894235B1 (en) Firing mixtures
DE69434003T2 (en) LEAD-FREE FUEL COMPOSITION FOR PERCUSSION IGNITIONS
DE69224081T2 (en) NON-TOXIC PRE-TREATMENT BLEND
DE69010180T2 (en) Improved composition for initial charge.
DE60116453T2 (en) Non-toxic primer mixture
US5388519A (en) Low toxicity primer composition
EP0800496B1 (en) Lead- and barium-free igniter compounds
EP1973863B1 (en) Primer composition
DE2543971A1 (en) LIGHTING SYSTEM FOR HIGH-TEMPERATURE-RESISTANT FUEL
DE19730872A1 (en) Propellant useful in munitions and gas generator
DE19606237A1 (en) Non-toxic detonator compsn. for light weapon munitions free of lead@ and barium@
EP1966120B1 (en) Salts of styphnic acid
DE19616628A1 (en) Ignition mixture used for igniting pyrotechnical mixtures
EP2352710B1 (en) Ignition sets with improved ignition performance
WO2000064840A1 (en) Granulated gas charges
EP0323828B1 (en) Explosive for war heads and solid propellants
Berger et al. Alkali‐Dinitramide Salts Part 2: Oxidizers for Special Pyrotechnic Applications
WO2004063128A1 (en) Propelling charge
CA2253196C (en) Firing mixtures
DE102006060145A1 (en) New styphnic acid salt of alkali- or alkaline earth metal, useful as an ignition material for ignition assembly for vehicle safety systems, ammunition and/or driving cartridge for explosive actuated tool
RU2157357C1 (en) Pellet causing no corrosion
DE1805358C3 (en) Ignition mixture for solid propellant charges
AT255287B (en) Process for the preparation of a new double salt of lead nitroaminotetrazole and lead typhnate
JPH10330183A (en) Initiator
EP3523266A2 (en) Pyrotechnic compositions

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

17P Request for examination filed

Effective date: 19981125

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE ES FI FR GB IT LI SE

17Q First examination report despatched

Effective date: 19990427

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 CH DE ES FI FR GB IT LI SE

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

REF Corresponds to:

Ref document number: 59712416

Country of ref document: DE

Date of ref document: 20051013

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: RUAG AMMOTEC GMBH

Free format text: DYNAMIT NOBEL GMBH EXPLOSIVSTOFF- UND SYSTEMTECHNIK#KAISERSTRASSE 1#53839 TROISDORF (DE) -TRANSFER TO- RUAG AMMOTEC GMBH#KRONACHER STRASSE 63#90765 FUERTH (DE)

Ref country code: CH

Ref legal event code: NV

Representative=s name: ISLER & PEDRAZZINI AG

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: RUAG AMMOTEC GMBH

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20060201

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2249799

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
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

26N No opposition filed

Effective date: 20060608

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: ISLER & PEDRAZZINI AG;POSTFACH 1772;8027 ZUERICH (CH)

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

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

Ref country code: CH

Payment date: 20160420

Year of fee payment: 20

Ref country code: GB

Payment date: 20160421

Year of fee payment: 20

Ref country code: ES

Payment date: 20160413

Year of fee payment: 20

Ref country code: FI

Payment date: 20160413

Year of fee payment: 20

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

Ref country code: AT

Payment date: 20160421

Year of fee payment: 20

Ref country code: FR

Payment date: 20160421

Year of fee payment: 20

Ref country code: IT

Payment date: 20160427

Year of fee payment: 20

Ref country code: SE

Payment date: 20160420

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20160627

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59712416

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20170423

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 304156

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170424

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 EXPIRATION OF PROTECTION

Effective date: 20170423

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20170731

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 EXPIRATION OF PROTECTION

Effective date: 20170425