EP0800496B1 - Lead- and barium-free igniter compounds - Google Patents

Lead- and barium-free igniter compounds Download PDF

Info

Publication number
EP0800496B1
EP0800496B1 EP96937260.6A EP96937260A EP0800496B1 EP 0800496 B1 EP0800496 B1 EP 0800496B1 EP 96937260 A EP96937260 A EP 96937260A EP 0800496 B1 EP0800496 B1 EP 0800496B1
Authority
EP
European Patent Office
Prior art keywords
compositions according
weight
igniter compositions
contained
proportion
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
EP96937260.6A
Other languages
German (de)
French (fr)
Other versions
EP0800496A1 (en
Inventor
Rainer Hagel
Klaus Redecker
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
RUAG Ammotec GmbH
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 RUAG Ammotec GmbH filed Critical RUAG Ammotec GmbH
Publication of EP0800496A1 publication Critical patent/EP0800496A1/en
Application granted granted Critical
Publication of EP0800496B1 publication Critical patent/EP0800496B1/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
    • C06C7/00—Non-electric detonators; Blasting caps; Primers

Definitions

  • the invention provides lead and barium-free ignition charges with initial explosives mixed with oxygen-supplying substances.
  • the EP-0 129 081 B1 describes lead and barium-free primer from initial explosives in a mixture with zinc peroxide as the oxidant, the initial explosives strontium salts of mono- and / or Dinitrodihydroxydiazobenzols in proportions between 5 and 70 wt .-% in admixture with passivators and additionally tetrazene in amounts up to 30 wt .-% and zinc peroxide in amounts between 10 and 70 wt .-%, each based on the total mixture.
  • primer compositions contain as initial explosives compounds, in particular of the lead, which are derived from trinitropolyphenols, such as, for example, trinitrophenol, trinitroresorcinol or hydrazoic acid. Furthermore there are also known primers containing double salts of lead, for example hypophosphite nitrate. Burning of these ignition charges leads to elevated concentrations of lead and its compounds in the ambient air, which already reach the permissible limit concentrations after a low shot number. Solutions have already been proposed which consist of heavy metal-free initial explosives. As such, in particular diazodinitrophenol has prevailed.
  • diazodinitrophenol-containing primer mixtures for example with zinc peroxide as the oxygen-providing substance, show very strong gas pressure surges, which are caused by the vigorously reacting diazodinitrophenol. This can lead to disturbances of the function in the weapon or the internal and external ballistics.
  • diazodinitrophenol shows increased thermal reactivity.
  • the present invention thus provides improved lead and barium-free ignition charges with initial explosives mixed with oxygen-supplying substances.
  • a first embodiment for solving the above problem is therefore in lead and barium-free ignitions with Initialexplosivstoffen in admixture with oxygen-supplying substances, which are characterized in that the initial explosives of alkali metal and / or alkaline earth metal salts of dinitrobenzofuroxanes and the oxygen-supplying Substances from, nitrates of ammonium, guanidine, aminoguanidine, triaminoguanidine, dicyandiamidine and the elements sodium, potassium, magnesium, calcium and / or cerium are selected.
  • the ignition compositions according to the invention exhibit improved stability with respect to the state of the art in moist / warm storage.
  • the initial explosives are preferably used in a proportion of 5 to 70 wt .-%, in particular 30 to 60 wt .-% based on the total mixture.
  • Ceria, tungsten trioxide and / or nitrates of ammonium, guanidine, aminoguanidine, triaminoguanidine, dicyandiamidine and also the elements sodium, calcium, cerium or basic cerium nitrates can be used as oxygen-supplying substances in addition to the metal peroxide zinc peroxide known from the prior art.
  • the amount of oxygen-providing substances in the igniter compositions according to the invention can vary, for example, between 5 and 70% by weight, based on the total mixture. Particularly preferred according to the invention is an amount of 8 to 60 wt .-% of the oxygen-supplying substances.
  • the substance can be used both in fine-grained state and coarse-grained.
  • Fine-grained substances with an average particle size of about 10 microns are preferably used when the primer charges are used as compressed charges, while coarse-grained substances having a particle size of about 30 microns for less highly dense charges, for example in rimfire sets are particularly suitable.
  • the primer compositions may further contain sensitizers, reducing agents, friction agents, secondary explosives and / or inert substances.
  • the sensitizer tetracene may be present in proportions up to 30% by weight, based on the total mixture.
  • Reducing agents which contribute to the reaction are suitable in the igniter compositions according to the invention for improving the ignitability and in some cases also cause an increase in the mechanical sensitivity.
  • Suitable substances are preferably selected from carbon and / or metal powders, in particular boron, cerium, titanium, zirconium and silicon, metal alloys, in particular cerium-magnesium, cerium-silicon, titanium-aluminum, aluminum-magnesium, calcium silicide and metal sulfides, in particular antimony sulfide and Molybdenum sulfide and metal hydrides, for example titanium hydride, in particular in a proportion of 0 to 20 wt .-%, based on the total mixture.
  • Some reducing agents may simultaneously perform the function of a friction agent, such as antimony sulfides or calcium silicides. While the proportion of the reducing agent in the ignition charge may be 0 to 20% by weight, friction agents which do not participate in the reaction during combustion may be present in the inventive primer in amounts of up to 45% by weight, based on the total mixture be. Such friction means are known per se; an example is glass powder.
  • Secondary explosives such as, for example, nitrocellulose or pentaerythritol tetranitrate, are particularly suitable as further components which contribute to the reaction.
  • Further examples which may be mentioned are octogen and hexogen, and also amino compounds of nitrated aromatics, for example of trinitrobenzene, such as mono-, di- or triaminotrinitrobenzene or aminohexanitrodiphenyl, furthermore the acylation products of these compounds, for example hexanitrooxanilide or hexanitrodiphenylurea.
  • these secondary explosives include hexanitrostilbene, hexanitrodiphenyloxide, hexanitrodiphenylsulfide, hexanitrodiphenylsulfone and hexanitrodiphenylamine, as well as tetranitrocarbazole, tetranitroacridone or Polyvinyl nitrate and nitrotriazolone and its compounds.
  • the proportion of these substances in the initial charge can be 0 to 30 wt .-% based on the total mixture.
  • Suitable inert substances are in the primer compositions according to the invention ansich known substances, which are often also used to vote on the properties of these sentences on the particular application.
  • binders, adhesives, dyes, passivators and / or agents for odor characterization may be mentioned, which may preferably be present in a proportion of 0 to 20 wt .-%, based on the total mixture.
  • odor characterization agents capable of withstanding thermal stress during the shot may be added to the sentence mixture or the binder and the sentence coverage.
  • vanillin meets these properties.
  • the preparation of the erfindungsgze type igniter is carried out by ansich known method by sieving the dry or kneading of the water-moist mixture.
  • the dosage of the water-moist mass can be done by brushing the perforated plates or by extrusion.
  • This example describes a primer set for an anvil primer at a set loading of 20 mg.
  • a mixture of 45 parts by weight of potassium dinitrobenzofuroxanate, 5 parts by weight of tetrazene, 30 parts by weight of zinc peroxide, 15 parts by weight of tin dioxide and 5 parts by weight of titanium was mixed with 22 parts by weight Homogenized water and dosed by brushing in perforated plates. After introduction in primer cap was dried and pressed.
  • the Zündstoffmischungen invention showed in wet / warm storage at a temperature of 71 ° C and a humidity of 90% in the course of 7 days better stability than a conventional diazole-containing primer. In the sensitivity study, no expulsion of the primer cap from the pods was observed.
  • Example 2 Analogously to Example 1, a primer for Randfeuerpatronen .221fB, sentence loading mass 16 mg was prepared. A mixture of 47 parts by weight of potassium dinitrobenzofuroxanate, 10 parts by weight of tetracene, 8 parts by weight of peroxide, 34 parts by weight of glass powder (90 to 200 microns) and 1 part by weight adhesin ® (adhesive) was analogous to Example 1 labored.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Automotive Seat Belt Assembly (AREA)
  • Catalysts (AREA)

Description

Gegenstand der Erfindung sind Blei- und Barium-freie Anzündsätze mit Initialexplosivstoffen im Gemisch mit Sauerstoff-liefernden Substanzen.The invention provides lead and barium-free ignition charges with initial explosives mixed with oxygen-supplying substances.

Aus der EP-0 031 045 B1 ist die Verwendung von Zinkperoxid als alleiniges oder anteiliges Oxidationsmittel in sprengstoffhaltigen oder pyrotechnischen Gemischen bekannt.From the EP-0 031 045 B1 the use of zinc peroxide as the sole or proportionate oxidizing agent in explosive or pyrotechnic mixtures is known.

Die EP-0 129 081 B1 beschreibt Blei- und Barium-freie Anzündsätze aus Initialexplosivstoffen im Gemisch mit Zinkperoxid als Oxidationsmittel, die als Initialexplosivstoffe Strontiumsalze des Mono- und/oder Dinitrodihydroxydiazobenzols in Anteilen zwischen 5 und 70 Gew.-% im Gemisch mit Passivatoren sowie zusätzlich noch Tetrazen in Mengen bis zu 30 Gew.-% und Zinkperoxid in Mengen zwischen 10 und 70 Gew.-%, jeweils bezogen auf das Gesamtgemisch, enthalten.The EP-0 129 081 B1 describes lead and barium-free primer from initial explosives in a mixture with zinc peroxide as the oxidant, the initial explosives strontium salts of mono- and / or Dinitrodihydroxydiazobenzols in proportions between 5 and 70 wt .-% in admixture with passivators and additionally tetrazene in amounts up to 30 wt .-% and zinc peroxide in amounts between 10 and 70 wt .-%, each based on the total mixture.

Bekannte Anzündsätze enthalten als Initialexplosivstoffe Verbindungen, insbesondere des Bleis, die sich von Trinitropolyphenolen, wie beispielsweise Trinitrophenol, Trinitroresorcin oder der Stickstoffwasserstoffsäure ableiten. Darüber hinaus sind auch Anzündsätze bekannt, die Doppelsalze des Bleis, zum Beispiel Hypophosphitnitrat, enthalten. Beim Abbrand dieser Anzündsätze treten erhöhte Konzentrationen an Blei und seinen Verbindungen in der Umgebungsluft auf, die die zulässigen Grenzkonzentrationen bereits nach geringer Schußzahl erreichen. Es wurden bereits Lösungen vorgeschlagen, die aus Schwermetallfreien Initialexplosivstoffen bestehen. Als solches hat sich insbesondere Diazodinitrophenol durchgesetzt. Die Diazodinitrophenol-haltigen Anzündsätze, beispielsweise mit zinkperoxid als Sauerstoff-liefernde Substanz, zeigen jedoch sehr starke Gasdruckstöße, die durch das heftig reagierende Diazodinitrophenol verursacht sind. Dies kann zu Störungen der Funktion in der Waffe oder der Innen- und Außenballistik führen. Daneben zeigt Diazodinitrophenol eine erhöhte thermische Reaktivität.Known primer compositions contain as initial explosives compounds, in particular of the lead, which are derived from trinitropolyphenols, such as, for example, trinitrophenol, trinitroresorcinol or hydrazoic acid. Furthermore There are also known primers containing double salts of lead, for example hypophosphite nitrate. Burning of these ignition charges leads to elevated concentrations of lead and its compounds in the ambient air, which already reach the permissible limit concentrations after a low shot number. Solutions have already been proposed which consist of heavy metal-free initial explosives. As such, in particular diazodinitrophenol has prevailed. However, the diazodinitrophenol-containing primer mixtures, for example with zinc peroxide as the oxygen-providing substance, show very strong gas pressure surges, which are caused by the vigorously reacting diazodinitrophenol. This can lead to disturbances of the function in the weapon or the internal and external ballistics. In addition, diazodinitrophenol shows increased thermal reactivity.

Gegenstand der vorliegenden Erfindung sind somit verbesserte Blei- und Barium-freie Anzündsätze mit Initialexplosivstoffen im Gemisch mit Sauerstoff-liefernden Substanzen.The present invention thus provides improved lead and barium-free ignition charges with initial explosives mixed with oxygen-supplying substances.

Eine erste Ausführungsform zur Lösung des vorgenannten Problems besteht daher in Blei- und Barium-freien Anzündsätzen mit Initialexplosivstoffen im Gemisch mit Sauerstoff-liefernden Substanzen, die dadurch gekennzeichnet sind, daß die Initialexplosivstoffe aus Alkalimetall- und/oder Erdalkalimetallsalzen von Dinitrobenzofuroxanen und die Sauerstoff-liefernden Substanzen aus, Nitraten von Ammonium, Guanidin, Aminoguanidin, Triaminoguanidin, Dicyandiamidin sowie den Elementen Natrium, Kalium, Magnesium, Calcium und/oder Cer ausgewählt sind.A first embodiment for solving the above problem is therefore in lead and barium-free ignitions with Initialexplosivstoffen in admixture with oxygen-supplying substances, which are characterized in that the initial explosives of alkali metal and / or alkaline earth metal salts of dinitrobenzofuroxanes and the oxygen-supplying Substances from, nitrates of ammonium, guanidine, aminoguanidine, triaminoguanidine, dicyandiamidine and the elements sodium, potassium, magnesium, calcium and / or cerium are selected.

Die erfindungsgemäßen Anzündsätze weisen bei Feucht-/Warmlagerung eine verbesserte Stabilität gegenüber dem Stand der Technik auf.The ignition compositions according to the invention exhibit improved stability with respect to the state of the art in moist / warm storage.

Erfindungsgemäß werden die Initialexplosivstoffe vorzugsweise in einem Anteil von 5 bis 70 Gew.-%, insbesondere 30 bis 60 Gew.-% bezogen auf die Gesamtmischung eingesetzt.According to the invention the initial explosives are preferably used in a proportion of 5 to 70 wt .-%, in particular 30 to 60 wt .-% based on the total mixture.

Als Sauerstoff-liefernde Substanzen sind neben dem aus dem Stand der Technik ansich bekannten Metallperoxid Zinkperoxid auch Cerdioxid, Wolframtrioxid und/oder Nitrate von Ammonium, Guanidin, Aminoguanidin, Triaminoguanidin, Dicyandiamidin sowie den Elementen Natrium, Calcium, Cer oder basische Cernitrate einsetzbar. Die Menge an Sauerstoff-liefernden Substanzen in den erfindungsgemäßen Anzündsätzen kann beispielsweise zwischen 5 und 70 Gew.-%, bezogen auf die Gesamtmischung, schwanken. Besonders bevorzugt im Sinne der Erfindung ist eine Menge von 8 bis 60 Gew.-% der Sauerstoff-liefernden Substanzen. Die Substanz kann sowohl in feinkörnigem Zustand als auch grobkörnig eingesetzt werden. Feinkörnige Substanzen mit einer mittleren Korngröße von ca. 10 µm werden vorzugsweise dann eingesetzt, wenn die Anzündsätze als verpreßte Ladungen verwendet werden, während grobkörnige Substanzen mit einer Korngröße von etwa 30 µm für weniger stark verdichtete Ladungen, beispielsweise in Randfeuersätzen besonders geeignet sind.Ceria, tungsten trioxide and / or nitrates of ammonium, guanidine, aminoguanidine, triaminoguanidine, dicyandiamidine and also the elements sodium, calcium, cerium or basic cerium nitrates can be used as oxygen-supplying substances in addition to the metal peroxide zinc peroxide known from the prior art. The amount of oxygen-providing substances in the igniter compositions according to the invention can vary, for example, between 5 and 70% by weight, based on the total mixture. Particularly preferred according to the invention is an amount of 8 to 60 wt .-% of the oxygen-supplying substances. The substance can be used both in fine-grained state and coarse-grained. Fine-grained substances with an average particle size of about 10 microns are preferably used when the primer charges are used as compressed charges, while coarse-grained substances having a particle size of about 30 microns for less highly dense charges, for example in rimfire sets are particularly suitable.

Erfindungsgemäß können die Anzündsätze weiterhin Sensibilisatoren, Reduktionsmittel, Friktionsmittel, Sekundärsprengstoffe und/oder Inertstoffe enthalten.According to the invention, the primer compositions may further contain sensitizers, reducing agents, friction agents, secondary explosives and / or inert substances.

Der Sensibilisator Tetrazen kann in Anteilen bis 30 Gew.-%, bezogen auf die Gesamtmischung vorhanden sein.The sensitizer tetracene may be present in proportions up to 30% by weight, based on the total mixture.

Reduktionsmittel, die einen Beitrag zur Umsetzung liefern, eignen sich in den erfindungsgemäßen Anzündsätzen zur Verbesserung des Anzündvermögens und bewirken teilweise auch eine Erhöhung der mechanischen Empfindlichkeit. Geeignete Stoffe sind vorzugsweise ausgewählt aus Kohlenstoff und/oder Metallpulvern, insbesondere von Bor, Cer, Titan, Zirkon und Silizium, Metallegierungen, insbesondere Cer-Magnesium, Cer-Silizium, Titan-Aluminium, Aluminium-Magnesium, Calciumsilizid und Metallsulfiden, insbesondere Antimonsulfid und Molybdänsulfid sowie Metallhydride, beispielsweise Titanhydrid, insbesondere in einem Anteil von 0 bis 20 Gew.-%, bezogen auf die Gesamtmischung. Einige Reduktionsmittel können gleichzeitig auch die Funktion eines Friktionsmittels erfüllen, wie beispielsweise Antimonsulfide oder Calciumsilizide. Während der Anteil der Reduktionsmittel im Anzündsatz 0 bis 20 Gew.-% betragen kann, können Friktionsmittel, die nicht an der Umsetzung während des Abbrands teilnehmen in Mengen von bis zu 45 Gew.-%, bezogen auf die Gesamtmischung, in den erfindungsgemäßen Anzündsätzen vorhanden sein. Solche Friktionsmittel ansich sind bekannt; als Beispiel sei Glaspulver genannt.Reducing agents which contribute to the reaction are suitable in the igniter compositions according to the invention for improving the ignitability and in some cases also cause an increase in the mechanical sensitivity. Suitable substances are preferably selected from carbon and / or metal powders, in particular boron, cerium, titanium, zirconium and silicon, metal alloys, in particular cerium-magnesium, cerium-silicon, titanium-aluminum, aluminum-magnesium, calcium silicide and metal sulfides, in particular antimony sulfide and Molybdenum sulfide and metal hydrides, for example titanium hydride, in particular in a proportion of 0 to 20 wt .-%, based on the total mixture. Some reducing agents may simultaneously perform the function of a friction agent, such as antimony sulfides or calcium silicides. While the proportion of the reducing agent in the ignition charge may be 0 to 20% by weight, friction agents which do not participate in the reaction during combustion may be present in the inventive primer in amounts of up to 45% by weight, based on the total mixture be. Such friction means are known per se; an example is glass powder.

Als weitere Komponenten, die einen Beitrag zur Umsetzung liefern, sind insbesondere Sekundärexplosivstoffe geeignet, wie beispielsweise Nitrocellulose oder Pentaerythrittetranitrat. Als weitere Beispiele seien Oktogen und Hexogen genannt, sowie Aminoverbindungen von nitrierten Aromaten, beispielsweise des Trinitrobenzols, wie Mono-, Di- oder Triaminotrinitrobenzol oder Aminohexanitrodiphenyl, weiterhin die Acylierungsprodukte dieser Verbindungen wie beispielsweise Hexanitrooxanilid oder Hexanitrodiphenylharnstoff. Ferner zählen beispielsweise zu diesen Sekundärexplosivstoffen Hexanitrostilben,Hexanitrodiphenyloxid, Hexanitrodiphenylsulfid, Hexanitrodiphenylsulfon und Hexanitrodiphenylamin sowie Tetranitrocarbazol, Tetranitroacridon oder Polyvinylnitrat sowie Nitrotriazolon und seine Verbindungen. Der Anteil dieser Stoffe am Anzündsatz kann 0 bis 30 Gew.-% bezogen auf die Gesamtmischung ausmachen.Secondary explosives, such as, for example, nitrocellulose or pentaerythritol tetranitrate, are particularly suitable as further components which contribute to the reaction. Further examples which may be mentioned are octogen and hexogen, and also amino compounds of nitrated aromatics, for example of trinitrobenzene, such as mono-, di- or triaminotrinitrobenzene or aminohexanitrodiphenyl, furthermore the acylation products of these compounds, for example hexanitrooxanilide or hexanitrodiphenylurea. Furthermore, for example, these secondary explosives include hexanitrostilbene, hexanitrodiphenyloxide, hexanitrodiphenylsulfide, hexanitrodiphenylsulfone and hexanitrodiphenylamine, as well as tetranitrocarbazole, tetranitroacridone or Polyvinyl nitrate and nitrotriazolone and its compounds. The proportion of these substances in the initial charge can be 0 to 30 wt .-% based on the total mixture.

Als Inertstoffe eignen sich in den erfindungsgemäßen Anzündsätzen ansich bekannte Stoffe, die oft auch zur Abstimmung zur Eigenschaften dieser Sätze auf den jeweiligen Verwendungszweck miteingesetzt werden. Insbesondere seien hier Bindemittel, Klebstoffe, Farbstoffe, Passivatoren und/oder Mittel zur Geruchscharakterisierung erwähnt, die vorzugsweise in einem Anteil von 0 bis 20 Gew.-%, bezogen auf die Gesamtmischung enthalten sein können. Beispielhaft seinen hier Calciumcarbonat, Titandioxid und/oder weißes Bornitrid genannt.Suitable inert substances are in the primer compositions according to the invention ansich known substances, which are often also used to vote on the properties of these sentences on the particular application. In particular, binders, adhesives, dyes, passivators and / or agents for odor characterization may be mentioned, which may preferably be present in a proportion of 0 to 20 wt .-%, based on the total mixture. Exemplary here calcium carbonate, titanium dioxide and / or white boron nitride called.

Zur Verbesserung und Charakterisierung des Geruchs der Satzschwaden können der Satzmischung oder dem Bindemittel sowie der Satzabdeckung Mittel zur Geruchscharakterisierung beigesetzt werden, die geeignet sind, der thermischen Belastung während des Schusses zu widerstehen. Insbesondere wurde in dieser Hinsicht gefunden, daß Vanillin diese Eigenschaften erfüllt.In order to improve and characterize the odor of the sentence cloud, odor characterization agents capable of withstanding thermal stress during the shot may be added to the sentence mixture or the binder and the sentence coverage. In particular, it has been found in this regard that vanillin meets these properties.

Die Herstellung der erfindungsgmäßen Anzündsätze erfolgt nach ansich bekannten Verfahren durch Sieben der trockenen oder Kneten der wasserfeuchten Mischung. Die Dosierung der wasserfeuchten Masse kann dabei durch Einstreichen der Lochplatten oder durch Strangpressen erfolgen.The preparation of the erfindungsgmäßen igniter is carried out by ansich known method by sieving the dry or kneading of the water-moist mixture. The dosage of the water-moist mass can be done by brushing the perforated plates or by extrusion.

BeispieleExamples Beispiel 1example 1

Dieses Beispiel beschreibt einen Anzündsatz für einen Amboß-Anzündhütchen bei einer Satzlademasse von 20 mg.This example describes a primer set for an anvil primer at a set loading of 20 mg.

Eine Mischung aus 45 Gew.-Teilen Kaliumdinitrobenzofuroxanat, 5 Gew.-Teilen Tetrazen, 30 Gew.-Teilen Zinkperoxid, 15 Gew.-Teilen Zinndioxid und 5 Gew.-Teilen Titan wurde mit 22 Gew.-Teilen Wasser homogenisiert und durch Einstreichen in Lochplatten dosiert. Nach dem Einbringen in Anzündhütchen wurde getrocknet und gepreßt.A mixture of 45 parts by weight of potassium dinitrobenzofuroxanate, 5 parts by weight of tetrazene, 30 parts by weight of zinc peroxide, 15 parts by weight of tin dioxide and 5 parts by weight of titanium was mixed with 22 parts by weight Homogenized water and dosed by brushing in perforated plates. After introduction in primer cap was dried and pressed.

Die erfindungsgemäße Zündstoffmischungen zeigte bei Feucht/Warm-Lagerung bei einer Temperatur von 71°C und einer Luftfeuchtigkeit von 90 % im Verlauf von 7 Tagen eine bessere Stabilität als ein konventioneller Diazol-haltiger Anzündsatz. Bei der Untersuchung der Empfindlichkeit wurde kein Austreiben des Anzündhütchens aus den Hülsen beobachtet.The Zündstoffmischungen invention showed in wet / warm storage at a temperature of 71 ° C and a humidity of 90% in the course of 7 days better stability than a conventional diazole-containing primer. In the sensitivity study, no expulsion of the primer cap from the pods was observed.

Vergleichsbeispiel 1Comparative Example 1

Eine wasserfeuchte Mischung aus 40 Gew.-Teilen Diazodinitrophenol, 15 Gew.-Teilen Tetrazen, 8 Gew.-Teilen Zinkperoxid, 35 Gew.-Teilen Glaspulver (120 bis 170 µm) und 2 Gew.-Teilen Adhesin® (Klebstoff) wurde mit einer Lademasse von 18 mg in Randfeuerhülsen .221fB eingeschleudert.A water-moist mixture of 40 parts by weight of diazodinitrophenol, 15 parts by weight of tetracene, 8 parts by weight of zinc peroxide, 35 parts by weight of glass powder (120 to 170 microns) and 2 parts by weight Adhesin ® (adhesive) was with a load of 18 mg in Randfeuerhülsen .221fB thrown.

Der Anzündsatz benötigte zur sicheren Durchzündung als Verdämmung eine Lackschicht aus 3 bis 4 mg Vinnapas®A50, die zur Geruchscharakterisierung 0,2 mg Vanillin enthielt.The ignition charge required to safely cross-ignition as damming a varnish layer of 3 to 4 mg Vinnapas ® A50 containing 0.2 mg of vanillin odor characterization.

Beispiel 2 (nicht erfindungsgemäß) Example 2 (not according to the invention)

Analog Beispiel 1 wurde ein Anzündsatz für Randfeuerpatronen .221fB, Satzlademasse 16 mg, hergestellt. Eine Mischung aus 47 Gew.-Teilen Kaliumdinitrobenzofuroxanat, 10 Gew.-Teilen Tetrazen, 8 Gew.-Teilen Zinkperoxid, 34 Gew.-Teilen Glaspulver (90 bis 200 µm) und 1 Gew.-Teil Adhesin® (Klebstoff) wurde analog Beispiel 1 laboriert.Analogously to Example 1, a primer for Randfeuerpatronen .221fB, sentence loading mass 16 mg was prepared. A mixture of 47 parts by weight of potassium dinitrobenzofuroxanate, 10 parts by weight of tetracene, 8 parts by weight of peroxide, 34 parts by weight of glass powder (90 to 200 microns) and 1 part by weight adhesin ® (adhesive) was analogous to Example 1 labored.

Der Anzündsatz zündete ohne Abdecklack als Verdämmung durch und erzielte eine der handelsüblichen Munition vergleichbare Innen- und Außenballistik.The primer ignited without Abdecklack as damming and scored comparable to the commercial ammunition indoor and outdoor ballistics.

Claims (12)

  1. Lead- and barium-free igniter compositions that contain initial explosives in a mixture with oxygen-delivering substances and reducing agents, characterised in that alkali-metal and/or alkaline-earth-metal salts of dinitrobenzofuroxans are selected as the sole initial explosives, and tetrazene is contained as a sensitizer, and the oxygen-delivering substances are selected from zinc peroxide, cerium dioxide, tungsten trioxide, nitrates of ammonium, guanidine, aminoguanidine, triaminoguanidine, dicyandiamidine, the elements sodium, magnesium, calcium and/or cerium, and the reducing agents are selected from carbon, the metal powders boron, cerium, titanium, zirconium and/or silicon, metal alloys, metal sulphides or metal hydrides.
  2. Igniter compositions according to claim 1 with a proportion of initial explosives of 5 to 70 % by weight, in particular 30 to 60 % by weight, relative to the total mixture.
  3. Igniter compositions according to claim 1 or 2 with a proportion of oxygen-delivering substances of 5 to 70 % by weight, in particular 8 to 60 % by weight, relative to the total mixture.
  4. Igniter compositions according to one or more of claims 1 to 3, characterised in that the reducing agents are selected from cerium magnesium, cerium silicon, titanium aluminum, aluminium magnesium, antimony sulphide and/or molybdenum sulphide or titanium hydride.
  5. Igniter compositions according to one or more of claims 1 to 4, characterised in that friction agents, further sensitizers, secondary explosives and/or inert substances are contained, furthermore.
  6. Igniter compositions according to claim 5, characterised in that glass powder is contained as a friction agent.
  7. Igniter compositions according to one or more of claims 5 or 6, characterised in that the friction agents are contained in a proportion of 0 to 45 % by weight, relative to the total mixture.
  8. Igniter compositions according to one or more of claims 5 to 7, characterised in that the secondary explosives are selected from hexogen, octogen and amino compounds of nitrated aromatics.
  9. Igniter compositions according to one or more of claims 5 to 8, characterised in that the secondary explosives are contained in a proportion of 0 to 30 % by weight, relative to the total mixture.
  10. Igniter compositions according to one or more of claims 5 to 9, characterised in that the inert substances are selected from binding agents, adhesives, dyes, passivators and/or odour-characterising agent.
  11. Igniter compositions according to claim 10, characterised in that the odour-characterising agent is vanillin.
  12. Igniter compositions according to one or more of claims 5 to 11, characterised in that the inert substances are contained in a proportion of 0 to 20 % by weight, relative to the total mixture.
EP96937260.6A 1995-10-28 1996-10-26 Lead- and barium-free igniter compounds Expired - Lifetime EP0800496B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19540278 1995-10-28
DE19540278A DE19540278A1 (en) 1995-10-28 1995-10-28 Lead- and barium-free igniters
PCT/EP1996/004674 WO1997016397A1 (en) 1995-10-28 1996-10-26 Lead- and barium-free igniter compounds

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP02017761 Division-Into 2002-08-09

Publications (2)

Publication Number Publication Date
EP0800496A1 EP0800496A1 (en) 1997-10-15
EP0800496B1 true EP0800496B1 (en) 2016-05-25

Family

ID=7776091

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96937260.6A Expired - Lifetime EP0800496B1 (en) 1995-10-28 1996-10-26 Lead- and barium-free igniter compounds

Country Status (10)

Country Link
US (2) US20020179209A1 (en)
EP (1) EP0800496B1 (en)
JP (1) JPH11502864A (en)
KR (1) KR100537348B1 (en)
CA (1) CA2209203C (en)
CZ (1) CZ293600B6 (en)
DE (1) DE19540278A1 (en)
IL (1) IL121183A (en)
RU (1) RU2233825C2 (en)
WO (1) WO1997016397A1 (en)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19540278A1 (en) 1995-10-28 1997-04-30 Dynamit Nobel Ag Lead- and barium-free igniters
WO1999003800A1 (en) * 1997-07-18 1999-01-28 Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik Projectile cartridge
GB2329380B (en) * 1997-09-13 1999-08-18 Royal Ordnance Plc Priming composition
DE19807598A1 (en) * 1998-02-11 1999-10-21 Lell Peter Explosive or energy-containing material ignition process for pyrotechnic assemblies, e.g. gas generators, actuators, ejectors and smoke, flash and detonation generators
DE19805539A1 (en) * 1998-02-11 1999-08-12 Lell Peter Dipl Ing Dr Process for igniting explosive or combustible materials
DE19901988A1 (en) * 1999-01-20 2000-08-03 Dynamit Nobel Ag Cartridges and cartridges
ATA75099A (en) * 1999-04-28 2001-03-15 Hirtenberger Ag IGNITION BLOCK
DK1230198T3 (en) * 1999-09-15 2008-03-03 Ruag Ammotec Gmbh Ammunition
CZ288858B6 (en) * 1999-09-17 2001-09-12 Sellier & Bellot, A. S. Non-toxic and non-corroding igniting mixture
CN100465097C (en) * 1999-09-27 2009-03-04 大赛璐化学工业株式会社 Basic metal nitrate, method for producing the same and gas-generating agent composition
US6478903B1 (en) * 2000-10-06 2002-11-12 Ra Brands, Llc Non-toxic primer mix
JP4791645B2 (en) * 2001-04-05 2011-10-12 カヤク・ジャパン株式会社 Detonator delay device
WO2003105696A1 (en) 2001-06-06 2003-12-24 Closure Medical Corporation Single-use applicators, dispensers and methods for polymerizable monomer compound
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
US6964716B2 (en) 2002-09-12 2005-11-15 Daicel Chemical Industries, Ltd. Gas generating composition
DE102004001980A1 (en) * 2003-01-14 2004-07-22 Ruag Ammotec Gmbh Propellant charge useful in weapons training systems comprises a soft friction material
US20040154713A1 (en) * 2003-01-23 2004-08-12 Olin Corporation Lead-free nontoxic priming mix
CA2457248C (en) 2003-02-07 2012-07-17 Closure Medical Corporation Applicators, dispensers and methods for dispensing and applying adhesive material
US20040190975A1 (en) 2003-02-07 2004-09-30 Closure Medical Corporation Applicators, dispensers and methods for dispensing and applying adhesive material
US8784583B2 (en) 2004-01-23 2014-07-22 Ra Brands, L.L.C. Priming mixtures for small arms
DE102006024511A1 (en) * 2006-05-23 2007-11-29 Ruag Ammotec Gmbh ignition
RU2318789C1 (en) * 2006-10-16 2008-03-10 Общество с ограниченной ответственностью "ИФОХИМ" Explosive modifier
US8750826B2 (en) * 2007-01-18 2014-06-10 At&T Intellectual Property I, L.P. Methods and apparatus for alternative billing of voice over internet protocol (VoIP) services
CA2713666A1 (en) * 2007-12-24 2009-07-02 General Dynamics Ordnance And Tactical Systems - Canada Inc. Low toxicity primer compositions for reduced energy ammunition
BRPI0921212B1 (en) * 2008-11-07 2019-10-15 Ruag Ammotec Gmbh IGNITION SETS AS INITIAL EXPLOSIVE SUBSTANCES
RU2542297C2 (en) * 2012-10-01 2015-02-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Самарский государственный технический университет Percussion charge
DE102014016469B4 (en) 2014-11-06 2016-05-25 Diehl Bgt Defence Gmbh & Co. Kg Ignition device for igniting a propellant charge
DE102015014428A1 (en) * 2014-11-10 2016-05-12 Ruag Ammotec Gmbh Thermal pre-ignition agents
US20180258007A1 (en) * 2014-12-23 2018-09-13 General Dynamics OTS - Canada, Inc. Tungsten oxide primer compositions

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321342A (en) * 1965-03-15 1967-05-23 Tigrett Re-ignitable match
NL7403593A (en) 1973-03-23 1974-09-25
DE2543971C2 (en) 1975-10-02 1986-05-22 Dynamit Nobel Ag, 5210 Troisdorf Ignition system for high temperature resistant propellants
DE2952069C2 (en) 1979-12-22 1983-02-17 Dynamit Nobel Ag, 5210 Troisdorf Use of zinc peroxide in explosive or pyrotechnic mixtures
US4464989A (en) 1983-05-13 1984-08-14 The United States Of America As Represented By The United States Department Of Energy Integral low-energy thermite igniter
DE3321943A1 (en) * 1983-06-18 1984-12-20 Dynamit Nobel Ag, 5210 Troisdorf LEAD- AND BARIUM-FREE APPLICATION SETS
US4575379A (en) 1984-06-11 1986-03-11 Browning John M Fuel composition and method of preparation therefor
US4858534A (en) 1986-04-23 1989-08-22 Amoco Corporation Ballistic lubricating and process
DE3707694A1 (en) 1987-03-11 1988-09-29 Dynamit Nobel Ag ELECTRICALLY APPLICABLE SETS FOR SLEEVELESS AMMUNITION AND DRIVING CARTRIDGES
US4963201A (en) * 1990-01-10 1990-10-16 Blount, Inc. Primer composition
US5059261A (en) 1990-05-22 1991-10-22 Mach I Inc. Processing of materials using rupturable microcapsulates containing detection materials
US5216199A (en) 1991-07-08 1993-06-01 Blount, Inc. Lead-free primed rimfire cartridge
US5167736A (en) 1991-11-04 1992-12-01 Olin Corporation Nontoxic priming mix
US5567252A (en) 1992-01-09 1996-10-22 Olin Corporation Nontoxic priming mix
FR2693721B1 (en) * 1992-07-20 1994-10-21 Ncs Pyrotechnie Technologies Priming charge with annular percussion and its manufacturing process.
EP0705418A4 (en) 1993-06-01 1996-09-18 Steven Craig Buzick Precision shooting aerodynamic non-spherical safety-oriented projectile
US5388519A (en) * 1993-07-26 1995-02-14 Snc Industrial Technologies Inc. Low toxicity primer composition
IT1266171B1 (en) 1994-07-15 1996-12-23 Europa Metalli Sezione Difesa PRIMING MIX WITHOUT TOXIC MATERIALS AND PERCUSSION PRIMING FOR CARTRIDGES USING THIS MIX.
EP0704415B1 (en) * 1994-08-27 1999-03-03 Eley Limited Primer composition
BR9500890A (en) * 1995-02-24 1997-04-29 Companhia Brasileira De Cartuc Non-toxic starter mixtures free of lead and barium and with tin oxide as the main oxidant
DE19540278A1 (en) 1995-10-28 1997-04-30 Dynamit Nobel Ag Lead- and barium-free igniters

Also Published As

Publication number Publication date
IL121183A (en) 2000-08-31
IL121183A0 (en) 1997-11-20
CZ293600B6 (en) 2004-06-16
CA2209203C (en) 2007-10-02
US20050067073A1 (en) 2005-03-31
RU2233825C2 (en) 2004-08-10
WO1997016397A1 (en) 1997-05-09
CZ205897A3 (en) 1997-11-12
US20020179209A1 (en) 2002-12-05
KR980700942A (en) 1998-04-30
JPH11502864A (en) 1999-03-09
US6997998B2 (en) 2006-02-14
CA2209203A1 (en) 1997-05-09
KR100537348B1 (en) 2006-05-25
EP0800496A1 (en) 1997-10-15
DE19540278A1 (en) 1997-04-30

Similar Documents

Publication Publication Date Title
EP0800496B1 (en) Lead- and barium-free igniter compounds
EP0031045B1 (en) Use of zinc peroxide as oxidising agent in explosives and pyrotechnic compositions
EP0129081B1 (en) Primers free of lead and barium
DE60116453T2 (en) Non-toxic primer mixture
DE3616004C2 (en) Ignition agent composition
DE69629492T2 (en) LEAD-FREE IGNITION COMPOSITION
EP2027080A1 (en) Ignition charge
DE19616627A1 (en) Kindling mixtures
DE3707694C2 (en)
DE2543971C2 (en) Ignition system for high temperature resistant propellants
DE69513251T2 (en) Impact-sensitive primer composition containing non-toxic materials and their use for percussion primer cartridges
DE60011109T2 (en) NON-TOXIC AND NON-CORROSIVE INITIAL MIXTURE
EP1973863B1 (en) Primer composition
WO1998003449A1 (en) Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors
EP2352710B1 (en) Ignition sets with improved ignition performance
WO2012072198A2 (en) Perchlorate-free pyrotechnic mixture
EP1064241B1 (en) Primary explosives and primers which can be ignited by electric triggering
EP1966120B1 (en) Salts of styphnic acid
DE10164381B4 (en) Low-signature and low-emission, pyrotechnic presentation body
WO2001040144A2 (en) Ignition means for propellant powders
CH440173A (en) Method for driving in anchoring means and propellant for carrying out this method

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: 19970712

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19980819

APAB Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPE

APAB Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPE

APAD Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOS REFNE

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20151105

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Owner name: RUAG AMMOTEC GMBH

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 802173

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 59611541

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59611541

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: SE

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

Effective date: 20160525

Ref country code: PT

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

Effective date: 20160926

Ref country code: ES

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

Effective date: 20160525

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 802173

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161026

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20161025

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: 20161025

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 59611541

Country of ref document: DE

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: 20170228