EP1089955B1 - Method for producing pyrotechnic primer charges - Google Patents

Method for producing pyrotechnic primer charges Download PDF

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Publication number
EP1089955B1
EP1089955B1 EP99926266A EP99926266A EP1089955B1 EP 1089955 B1 EP1089955 B1 EP 1089955B1 EP 99926266 A EP99926266 A EP 99926266A EP 99926266 A EP99926266 A EP 99926266A EP 1089955 B1 EP1089955 B1 EP 1089955B1
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EP
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Prior art keywords
process according
dispersing agent
components
metal
pyrotechnic
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EP99926266A
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German (de)
French (fr)
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EP1089955A1 (en
Inventor
Uwe Krone
Dirk Cegiel
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Nico Pyrotechnik Hanns Juergen Diederichs GmbH and Co KG
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Nico Pyrotechnik Hanns Juergen Diederichs GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/06—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic oxygen-halogen salt
    • 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 invention relates to a method for manufacturing of pyrotechnic primers based on metal powders or metal hydrides, potassium perchlorate and binders.
  • Pyrotechnic igniters are mixtures of solid substances in mostly powdery state, the components of which are mainly consist of reducing agents and oxidizing agents.
  • reducing agents e.g. reducing agents
  • oxidizing agents e.g. reducing agents
  • a redox process is initiated: the pyrotechnic charge burns depending on the structure and arrangement more or less violently.
  • Pyrotechnic igniters are widely used and e.g. as match heads of matches, in luminous and Signal ammunition, in smoke and fog bodies, in gas generators, e.g. for safety air cushions (airbags) and in numerous different arrangements used in fireworks.
  • Pyrotechnic primers are usually manufactured by dry mixing the individual components. happens this by hand, so the crushed components pressed through sieves and mixed. With machine The components of the pyrotechnic primer will be mixed possibly unmixed after previous grinding filled in containers and in this by stirrers, rotary movements of the mixing container or applying shear forces Facilities mixed homogeneously. As mixing devices Tumble mixer, tetrahedron mixer, planetary mixer or from it derived and combined mixers used.
  • Pyrotechnic primers are often used as granules, because they pour and dose better in this form to let.
  • the granulation is done by adding a suitable one Solvent for dry primer and mixing in Special containers.
  • the solvent can already bind the binder dissolved or the binder component, which with the solvent is swellable or soluble in it already in powder form in the pyrotechnic sentence, so that Adhesive forces develop when the solvent is added can eventually lead to the form of granules.
  • special granule mixers are provided for training In the granulate form. Subsequent drying removes the solvent removed so that you get a meterable bulk.
  • Another difficulty with this method is dimensioning the amount of liquid.
  • the invention has for its object a method for Manufacture of pyrotechnic primers of the type in question Specify the way in which the components used are homogeneous are mixed, at the same time the risk of triggering the mixture significantly reduced and a reproduced dosage is made possible.
  • the individual components for the pyrotechnic Ignition charge with the help of suitable liquid dispersants made several homogeneous suspensions that didn't or are only slightly explosive. These suspensions are mixed in small quantities using ultrasound. The mixture is immediately in this consistency for the lighter in the desired amount e.g. dosed in lighter or on ignition elements, after which from the metered amount the dispersion medium are removed.
  • the little or not explosive Suspensions mixed in batches in small quantities and dosed immediately after this mixing e.g. in the housing of an airbag lighter.
  • the liquid mixture is preserved so that Cracks and voids are avoided and the ignition properties of the lighter are reproducible.
  • the grain sizes of the solids used i.e. metal powder or metal hydrides and the potassium perchlorate are here smaller than 50 ⁇ m, preferably smaller than 20 ⁇ m.
  • the invention can by a suitable amount of dispersant both an optimal mixing of the components as well as a suitable viscosity of the suspension for that subsequent dosing can be achieved.
  • the homogeneous distribution of the components in the suspension required energy is introduced into the mixture by cavitation.
  • the cavitation is preferred by ultrasound with frequencies generated greater than 16 kHz.
  • With the implosion of the by Cavitation gas bubbles can reach temperatures of approx. 5500 ° C and pressures up to 500 bar can be reached.
  • Rapidity of gas bubble disintegration in a period of time of less than 1 ⁇ s and due to the small size of the Gas bubbles, which are usually smaller than 150 ⁇ m, are Cooling rate at implosion so high that the warming the suspension remains negligible.
  • the chemical Effects of ultrasound have been reported by K. S. Suslick in the magazine Spektrum dermaschine, Issue 4, pages 60ff, 1989, here essentially Aspects of liquid and solid sonochemistry Surfaces as well as suspended particles were examined.
  • the components can be mixed directly in the container from which subsequently is also metered to the preparation of the dispersion. This is e.g. through the use of appropriately shaped sonotrodes, very possible.
  • the mixtures are e.g. in cartridges or cartridges, which are then placed in a dosing device be used.
  • the liquid mixtures will be then with light pressure or by vacuum, e.g. in prepared Ignition housing or dosed on ignition elements.
  • the mixing room can be with a sonotrode connection or be provided with a mechanical sonotrode contact.
  • the per se dangerous Mix made only as much as for one or a few lighters is needed.
  • the production can then be mechanically more economical in one for series production suitable high clock sequence can be controlled.
  • a composition of the ignition charge from potassium perchlorate, Zirconium powder, a binder and a solvent selected then two suspension-like premixes can be produced that are not or only slightly explosive are, as a component that in the solvent dispersed potassium perchlorate and as a second component the zirconium powder dispersed in the solvent, the Binder is already dissolved in the solvent.
  • the primers e.g. by drying the rest Dispersion medium freed and further processing fed.
  • the ratio of solid to dispersant is variable and experience has shown that it is in the range of 70% to 80% solids.
  • the metal used is preferably titanium or zirconium or their Hydride used.
  • the binder is preferably made from the Group of fluorinated polymeric aliphates selected.
  • the dispersant preferably acts as a solvent for the binder and preferably comes from the series of aliphatic Ketones. Acetone or methyl ethyl ketone have been used for this proven.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Air Bags (AREA)

Abstract

The invention relates to pyrotechnic primer charges produced on the basis of metal powders or metal hydride powders, potassium perchlorate and binders. In order to obtain a homogenous mixture, the powdery components are mixed with a liquid dispersing agent in a suspension with the aid of ultrasound and dosed having said consistency. Mixing for obtaining a suspension can also be carried out directly in a casing receiving the pyrotechnic primer charges.

Description

Die Erfindung bezieht sich auf ein Verfahren zum Herstellen von pyrotechnischen Anzündsätzen auf der Basis von Metallpulvern oder Metallhydriden, Kaliumperchlorat und Bindern.The invention relates to a method for manufacturing of pyrotechnic primers based on metal powders or metal hydrides, potassium perchlorate and binders.

Pyrotechnische Anzündsätze sind Gemische von festen Stoffen in zumeist pulverförmigen Zustand, deren Komponenten hauptsächlich aus Reduktionsmitteln und Oxidationsmitteln bestehen. Bei Zuführen einer der geeigneten Menge Energie, z.B. in Form einer Anzündflamme, wird ein Redoxvorgang eingeleitet: der pyrotechnische Satz brennt je nach Aufbau und Anordnung mehr oder weniger heftig ab.Pyrotechnic igniters are mixtures of solid substances in mostly powdery state, the components of which are mainly consist of reducing agents and oxidizing agents. When applying an appropriate amount of energy, e.g. in In the form of an ignition flame, a redox process is initiated: the pyrotechnic charge burns depending on the structure and arrangement more or less violently.

Pyrotechnische Anzündsätze finden vielfältige Verwendung und werden z.B. als Zündköpfe von Streichhölzern, in Leucht- und Signalmunition, in Rauch- und Nebelkörpern, in Gasgeneratoren, z.B. für Sicherheitsluftkissen (Airbags) und in zahlreichen verschiedenen Anordnungen bei Feuerwerkskörpern benutzt.Pyrotechnic igniters are widely used and e.g. as match heads of matches, in luminous and Signal ammunition, in smoke and fog bodies, in gas generators, e.g. for safety air cushions (airbags) and in numerous different arrangements used in fireworks.

Die Herstellung pyrotechnischer Anzündsätze erfolgt zumeist durch trockenes Vermischen der einzelnen Bestandteile. Geschieht dieses von Hand, so werden die zerkleinerten Komponenten durch Siebe gedrückt und durchgemischt. Bei maschinellem Mischen werden die Komponenten des pyrotechnischen Anzündsatzes eventuell nach vorheriger Zerkleinerung unvermischt in Behälter gefüllt und in diesem durch Rührer, Drehbewegungen des Mischbehälters oder Scherkräfte applizierende Einrichtungen homogen vermischt. Als Mischgeräte werden Taumelmischer, Tetraedermischer, Planetenmischer oder daraus abgeleitete und auch kombinierte Mischapparate verwendet.Pyrotechnic primers are usually manufactured by dry mixing the individual components. happens this by hand, so the crushed components pressed through sieves and mixed. With machine The components of the pyrotechnic primer will be mixed possibly unmixed after previous grinding filled in containers and in this by stirrers, rotary movements of the mixing container or applying shear forces Facilities mixed homogeneously. As mixing devices Tumble mixer, tetrahedron mixer, planetary mixer or from it derived and combined mixers used.

Oft werden pyrotechnische Anzündsätze als Granulat verwendet, weil sie sich in dieser Form besser schütten und dosieren lassen. Die Granulierung geschieht durch Zufügen eines geeigneten Lösemittels zum trockenen Anzündsatz und Vermischen in Spezialbehältern. Dabei kann das Lösemittel den Binder bereits gelöst enthalten oder die Binderkomponente, welche mit dem Lösemittel quellfähig oder in ihm löslich ist, befindet sich bereits in Pulverform im pyrotechnischen Satz, so dass bei Zugabe des Lösemittels sich adhäsive Kräfte ausbilden können, die schließlich zur Granulatform führen. Zur Ausbildung der Granulatform sind spezielle Granulatmischer vorgesehen. Durch anschließendes Trocknen wird das Lösemittel wieder entfernt, so dass man ein dosierfähiges Schüttgut erhält.Pyrotechnic primers are often used as granules, because they pour and dose better in this form to let. The granulation is done by adding a suitable one Solvent for dry primer and mixing in Special containers. The solvent can already bind the binder dissolved or the binder component, which with the solvent is swellable or soluble in it already in powder form in the pyrotechnic sentence, so that Adhesive forces develop when the solvent is added can eventually lead to the form of granules. For training In the granulate form, special granule mixers are provided. Subsequent drying removes the solvent removed so that you get a meterable bulk.

Wenn die Komponenten des pyrotechnischen Anzündsatzes sehr fein sind oder wenn die in ihnen gespeicherte chemische Energie groß ist, müssen Maßnahmen ergriffen werden, um die Gefahr bei der Herstellung beherrschbar zu halten. Die mechanische und thermische Empfindlichkeit dieser Anzündsätze ist oft so ausgeprägt, dass sich ein Umgang mit ihnen ohne geeignete Sicherheitsmaßnahmen verbietet.If the components of the pyrotechnic primer very are fine or if the chemical energy stored in them is large, measures must be taken to reduce the risk to keep it manageable during production. The mechanical and thermal sensitivity of these primers often so pronounced that dealing with them without suitable Security measures prohibited.

Der Gefährlichkeit bei der Herstellung tragen zahlreiche Sicherheitsvorschriften Rechnung. So werden pyrotechnische Sätze z.B. bei den berufsgenossenschaftlichen Unfallverhütungsvorschriften entsprechend ihrer Gefährlichkeit in Gruppen eingeteilt, die abgestufte Sicherheitsvorkehrungen bei der Herstellung der Sätze fordern. Die beiden gefährlichsten Gruppen dürfen nicht mehr von Hand gemischt werden. Sie werden hinter Schutzwänden oder in einem abgeteiltem Raum automatisch gemischt, der vom Bedienungsraum durch eine Widerstandswand getrennt ist. Diese Art der Herstellung nennt man gewöhnlich "Arbeiten unter Sicherheit". Dies gilt primär für trockene pulverige Komponenten.The safety during manufacture is borne by numerous safety regulations Bill. This is how pyrotechnic sentences become e.g. in the accident prevention regulations of the trade association according to their danger in groups divided, the graded security precautions at the Request the production of sentences. The two most dangerous Groups may no longer be mixed by hand. you will be automatically behind protective walls or in a compartment mixed that from the service room through a resistance wall is separated. This type of production is called usually "working under safety". This applies primarily to dry powdery components.

Werden beim Mischen Maßnahmen ergriffen, welche die Auslösbarkeit und die mechanische oder thermische Empfindlichkeit der Sätze herabsetzen, so können in der obigen Gruppeneinteilung Herabstufungen vorgenommen werden. Eine Maßnahme hierfür ist z.B., die Komponenten nicht trocken, sondern zusammen mit einer Flüssigkeit zu mischen.Are measures taken during mixing that determine the triggerability and mechanical or thermal sensitivity the rates, in the above grouping Downgrades are made. A measure for this For example, the components are not dry, but together with to mix a liquid.

Dieses Verfahren findet besonders Anwendung beim Mischen von hier interessierenden pyrotechnischen Anzündsätzen. Unter Zusatz von Lösemitteln, z.B. Wasser, können die pyrotechnischen Anzündsätze wesentlich gefahrloser als in trockenem Zustand hergestellt werden. Trotzdem ist die in Anzündsätzen gespeicherte Energie so hoch, dass die Wirkung einer unfallbedingten Auslösung deren Verarbeitung von Hand auch im feuchten Zustand verbietet. Zudem muss die Mischungsmenge in der Masse klein gehalten werden, in der Regel unter 100 Gramm, so dass eine Auslösung auch bei der Herstellung unter Sicherheit beherrschbar bleibt.This method is particularly useful when mixing pyrotechnic primers of interest here. With addition of solvents, e.g. Water, the pyrotechnic Ignition charges are much less dangerous than when dry getting produced. Nonetheless, the one stored in ignition kits Energy so high that the effect of an accident Triggering their processing by hand even in the damp Condition prohibits. In addition, the amount of mixture in the mass be kept small, usually under 100 grams, so that triggering can also be managed safely during production remains.

Eine weitere Schwierigkeit bei diesem Verfahren ist die Bemessung der Flüssigkeitsmenge. Sie muss einerseits so groß sein, dass die Gefahr einer Auslösung bei der Mischung des Satzes deutlich gesenkt wird; andererseits erhöht sich mit steigender Flüssigkeitsmenge auch die anschließende Trocknungsdauer; außerdem nimmt die Gefahr der Riss- und Lunkerbildung beim Trocknen zu: Risse und Lunker gefährden die sichere Funktion des Anzündsatzes bei dessen Anzündung. Another difficulty with this method is dimensioning the amount of liquid. On the one hand, it has to be this big be that the risk of triggering when mixing the Rate is significantly reduced; on the other hand increases with increasing amount of liquid also the subsequent drying time; furthermore, the risk of cracking and blowholes increases when drying too: cracks and cavities endanger the safe Function of the primer when it is ignited.

Da nach der Herstellung der Mischung bei der anschließenden Dosierung für den Anzünder die Flüssigkeit mitdosiert wird, am eigentlichen Umsatz der Anzündmischung jedoch nicht beteiligt ist, muss der Flüssigkeitsgehalt der Mischung genau bestimmbar sein und auch während des Dosierens konstant gehalten werden. Nur dann werden die Anzündsätze bei der anschließenden Trocknung gleichmäßige Eigenschaften aufweisen.Since after the preparation of the mixture in the subsequent Dosage for the lighter the liquid is added, not involved in the actual ignition mixture sales the liquid content of the mixture must be precisely determinable be and kept constant even during dosing become. Only then will the igniter charges be given to the subsequent one Drying have uniform properties.

Des weiteren ist es bekannt, dass sich flüssige pastöse Mischungen für pyrotechnische Anzündsätze mit Komponenten unterschiedlicher Dichte, Löslichkeit oder elektrischem Umfeld, d. h. Ausbildung von Dipolen bzw. gleichsinniger oder gegensinniger Aufladung, relativ schwer handhaben lassen. In den Mischungen haben die verschiedenen Feststoffkomponenten unterschiedliche Sedimentationsgeschwindigkeiten, so dass sich nach kurzer Standzeit Flüssigkeit und Feststoff trennen und eine reproduzierbare Dosierung der Mischung erschweren, was wiederum die Qualität des Anzünders beeinträchtigt.Furthermore, it is known that there are liquid pasty mixtures for pyrotechnic primers with components different Density, solubility or electrical environment, d. H. Formation of dipoles or in the same or opposite directions Charging, relatively difficult to handle. In the Mixtures have different solid components Sedimentation speeds so that after a short standstill, separate liquid and solid and a reproducible dosage of the mixture complicate what again the quality of the lighter is impaired.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Herstellen von pyrotechnischen Anzündsätzen der in Rede stehenden Art anzugeben, mit dem die verwendeten Komponenten homogen vermischt werden, gleichzeitig die Gefahr einer Auslösung der Mischung deutlich gesenkt und eine reproduziere Dosierung ermöglicht wird.The invention has for its object a method for Manufacture of pyrotechnic primers of the type in question Specify the way in which the components used are homogeneous are mixed, at the same time the risk of triggering the mixture significantly reduced and a reproduced dosage is made possible.

Diese Aufgabe ist gemäß der Erfindung durch die Merkmale des Patentanspruches 1 gelöst.This object is according to the invention by the features of Claim 1 solved.

Demgemäß wird aus den einzelnen Komponenten für den pyrotechnischen Anzündsatz mit Hilfe geeigneter flüssiger Dispergiermittel mehrere homogene Suspensionen hergestellt, die nicht oder nur wenig explosionsgefährlich sind. Diese Suspensionen werden in kleinen Mengen mit Hilfe von Ultraschall gemischt. Die Mischung wird in dieser Konsistenz unmittelbar anschließend für den Anzünder in der jeweilig gewünschten Menge z.B. in Anzünder oder auf Anzündelemente dosiert, wonach aus der dosierten Menge die Dispersions mittel entfernt werden.Accordingly, the individual components for the pyrotechnic Ignition charge with the help of suitable liquid dispersants made several homogeneous suspensions that didn't or are only slightly explosive. These suspensions are mixed in small quantities using ultrasound. The mixture is immediately in this consistency for the lighter in the desired amount e.g. dosed in lighter or on ignition elements, after which from the metered amount the dispersion medium are removed.

Die Anwendung von Ultraschall auf flüssige Mischungen aus mehreren Komponenten ist an sich bekannt; so ist z.B. in der DE-A1-27 12 603 ein Verfahren und eine Vorrichtung zur Modifizierung der Charakteristiken einer Flüssigkeit beschrieben, wobei die mehreren Komponenten der Flüssigkeit beim Durchfließen eines Rohres mit Hilfe von Ultraschall homogenisiert werden. Ebenso ist es aus den sowjetischen Patentanmeldungen 2050963 bzw. 2056926 bekannt, Ultraschall-Dispergiermischer zu verwenden, um auch verschiedene Komponenten insbesondere im Lebensmittelbereich miteinander zu vermischen. Bei allen diesen Mischverfahren erfolgt die Homogenisierung bzw. Vermischung kontinuierlich, eine entsprechende Dosierung und Trocknung der dosierten Mischung ist nicht vorgesehen. Außerdem spielen bei diesen Verfahren die bei der Mischung von pyrotechnischen Anzündsätzen zu berücksichtigenden Sicherheitsmassnahmen keine Rolle.The application of ultrasound to liquid mixtures several components are known per se; for example in the DE-A1-27 12 603 a method and an apparatus for modification described the characteristics of a liquid, with the multiple components of the liquid flowing through homogenized a tube using ultrasound become. It is the same from the Soviet patent applications 2050963 or 2056926 known, ultrasonic dispersion mixer to use different components in particular to mix in the food sector. At all These mixing processes are used for homogenization or mixing continuously, an appropriate dosage and Drying of the dosed mixture is not intended. Moreover play a role in these processes when mixing pyrotechnic Safety measures to be taken into account not matter.

Gemäß der Erfindung werden die wenig oder nicht explosionsgefährlichen Suspensionen chargenweise in kleinen Mengen gemischt und unmittelbar im Anschluss an dieses Mischen dosiert, z.B. in das Gehäuse eines Airbag-Anzünders. Auf diese Weise wird eine absolut homogene Verteilung der Komponenten erreicht, die auch beim Entfernen des Dispersionsmittels aus der flüssigen Mischung erhalten bleibt, sodass Risse und Lunkerbildungen vermieden werden und die Zündeigenschaften des Anzünders reproduzierbar sind.According to the invention, the little or not explosive Suspensions mixed in batches in small quantities and dosed immediately after this mixing, e.g. in the housing of an airbag lighter. To this Wise is an absolutely homogeneous distribution of the components achieved, even when removing the dispersant the liquid mixture is preserved so that Cracks and voids are avoided and the ignition properties of the lighter are reproducible.

Die Korngrößen der verwendeten Feststoffe, also Metallpulver oder Metallhydride und das Kaliumperchlorat sind hierbei kleiner als 50 µm, vorzugsweise kleiner als 20 µm.The grain sizes of the solids used, i.e. metal powder or metal hydrides and the potassium perchlorate are here smaller than 50 µm, preferably smaller than 20 µm.

Gemäß der Erfindung kann durch eine geeignete Menge an Dispergiermittel sowohl eine optimale Vermischung der Komponenten als auch eine geeignete Viskosität der Suspension für das nachfolgende Dosieren erzielt werden. Die zur homogenen Verteilung der Komponenten in der Suspension benötigte Energie wird durch Kavitation in die Mischung eingebracht. Die Kavitation wird durch Ultraschall mit Frequenzen vorzugsweise großer als 16 kHz erzeugt. Bei der Implosion der durch die Kavitation enstehenden Gasblasen können Temperaturen von ca. 5500°C und Drücke bis 500 bar erreicht werden. Durch die Schnelligkeit des Zerfalls der Gasblasen in einer Zeitspanne von kleiner als 1 µs und durch die geringe Größenordnung der Gasblasen, die in der Regel kleiner als 150 µm sind, ist die Abkühlgeschwindkeit bei der Implosion so hoch, dass die Erwärmung der Suspension vernachlässigbar bleibt. Die chemischen Wirkungen von Ultraschall wurden bereits von K.S. Suslick in der Zeitschrift Spektrum der Wissenschaft, Heft 4, Seiten 60ff, 1989 beschrieben, wobei hier im wesentlichen Aspekte der Sonochemie von Flüssigkeiten und festen Oberflächen sowie von suspendierten Teilchen untersucht wurden.According to the invention can by a suitable amount of dispersant both an optimal mixing of the components as well as a suitable viscosity of the suspension for that subsequent dosing can be achieved. The homogeneous distribution of the components in the suspension required energy is introduced into the mixture by cavitation. The cavitation is preferred by ultrasound with frequencies generated greater than 16 kHz. With the implosion of the by Cavitation gas bubbles can reach temperatures of approx. 5500 ° C and pressures up to 500 bar can be reached. Through the Rapidity of gas bubble disintegration in a period of time of less than 1 µs and due to the small size of the Gas bubbles, which are usually smaller than 150 µm, are Cooling rate at implosion so high that the warming the suspension remains negligible. The chemical Effects of ultrasound have been reported by K. S. Suslick in the magazine Spektrum der Wissenschaft, Issue 4, pages 60ff, 1989, here essentially Aspects of liquid and solid sonochemistry Surfaces as well as suspended particles were examined.

Ein weiteres Merkmal der Erfindung ist, dass die Komponenten direkt in dem Behälter gemischt werden, aus dem im Anschluss an die Herstellung der Dispersion auch dosiert wird. Dies ist z.B. durch den Einsatz von entsprechend geformten Sonotroden, sehr gut möglich. Die Mischungen werden z.B. in Kartuschen oder Patronen hergestellt, die anschließend in eine Dosierapparatur eingesetzt werden. Die flüssigen Mischungen werden dann mit leichtem Druck oder durch Vakuum, z.B. in vorbereitete Anzündgehäuse oder auf Anzündelemente dosiert.Another feature of the invention is that the components can be mixed directly in the container from which subsequently is also metered to the preparation of the dispersion. This is e.g. through the use of appropriately shaped sonotrodes, very possible. The mixtures are e.g. in cartridges or cartridges, which are then placed in a dosing device be used. The liquid mixtures will be then with light pressure or by vacuum, e.g. in prepared Ignition housing or dosed on ignition elements.

Um im Laufe des Dosierprozesses Sedimentationen oder Koagulationseffekte zu verhindern, können die Kartuschen oder Patronen, die die Anzündmischung enthalten, mechanischen Schwingungen oder Schallwellen ausgesetzt werden.To sedimentation or coagulation effects in the course of the dosing process to prevent the cartridges or cartridges, which contain the ignition mixture, mechanical vibrations or exposed to sound waves.

Durch das Mischen direkt in dem Dosierbehälter werden Abfüllund Umfüllprozesse nach dem Mischen vermieden. Durch derartige Prozesse könnten sich in den Behältern Krusten oder Antrocknungen an den Wänden ergeben, was wegen des explosionsgefährlichen Charakters der Mischung unbedingt vermieden werden muss.By mixing directly in the dosing container, filling and Transfer processes after mixing avoided. Through such Processes could become crusted or dry on the containers on the walls result in what because of the explosive Character of the mixture must be avoided got to.

Eine Vermeidung der Gefahren, die beim Mischen größerer Mengen auftreten können, ist das gemäß der Erfindung vorgesehene Mischen von in Suspension vorgemischten nicht oder nur wenig explosionsgefährlichen Komponenten des Anzündsatzes in einem relativ kleinen Mischraum und daraus das anschließende Einfüllen bzw. Dosieren in z.B. eine Anzünderhülse. Der Mischraum kann hierbei etwa mit einem Sonotroden-Anschluss oder einem mechanischen Sonotroden-Kontakt versehen sein.Avoiding the dangers of mixing larger amounts can occur is that provided according to the invention Mix little or no premixed in suspension Explosive components of the primer in one relatively small mixing room and the subsequent filling or dosing in e.g. an igniter sleeve. The mixing room can be with a sonotrode connection or be provided with a mechanical sonotrode contact.

Gemäß der Erfindung wird bevorzugt von der an sich gefährlichen Mischung jeweils nur soviel hergestellt wie für einen oder einige wenige Anzünder benötigt wird. Die Herstellung kann dann maschinell wirtschaftlicher in einer für eine Serienfertigung geeigneten hohen Taktfolge gesteuert werden. Wird z.B. eine Zusammensetzung des Anzündsatzes aus Kaliumperchlorat, Zirkoniumpulver, einem Binder und einem Lösemittel gewählt, dann können zwei suspensionsförmige Vormischungen hergestellt werden, die nicht oder nur wenig explosionsgefährlich sind, nämlich als eine Komponente das in dem Lösungsmittel dispergierte Kaliumperchlorat und als zweite Komponente das im Lösemittel dispergierte Zirkoniumpulver, wobei der Binder bereits im Lösemittel gelöst ist.According to the invention is preferred from the per se dangerous Mix made only as much as for one or a few lighters is needed. The production can then be mechanically more economical in one for series production suitable high clock sequence can be controlled. Becomes e.g. a composition of the ignition charge from potassium perchlorate, Zirconium powder, a binder and a solvent selected, then two suspension-like premixes can be produced that are not or only slightly explosive are, as a component that in the solvent dispersed potassium perchlorate and as a second component the zirconium powder dispersed in the solvent, the Binder is already dissolved in the solvent.

Zusammengefaßt besteht das erfindungsgemäße Verfahren zum Herstellen pyrotechnischer Anzünder mit einem Anzündsatz auf der Basis von Metallpulvern, Metallhydriden, Kaliumperchlorat und Bindern demnach aus den Verfahrensschritten:

  • 1. Wiegen und Einfüllen der Komponenten oder von nicht oder wenig explosionsgefährlichen Vormischungen in eine Mischund Dosierpatrone bzw. Dosierkartusche;
  • 2. Herstellen der Mischung in der Patrone bzw. Kartusche oder einem kleinen Mischraum durch Anwendung von Ultraschall;
  • 3. Dosieren der pyrotechnischen Anzündmischung, sofern das Mischen nicht bereits in dem für die Anwendung des pyrotechnischen Anzündsatzes verwendeten Behälter erfolgt.
    • In summary, the method according to the invention for producing pyrotechnic igniters with an ignition charge based on metal powders, metal hydrides, potassium perchlorate and binders therefore consists of the process steps:
  • 1. Weighing and filling the components or premixes that are not or not very explosively explosive into a mixing and dosing cartridge or dosing cartridge;
  • 2. Preparation of the mixture in the cartridge or cartridge or a small mixing room by using ultrasound;
  • 3. Dosing of the pyrotechnic ignition mixture, provided that the mixing is not already taking place in the container used for the application of the pyrotechnic ignition charge.

    • Danach werden die Anzündsätze z.B. durch Trocknung vom restlictien Dispersions mittel befreit und der weiteren Bearbeitung zugeführt. Then the primers e.g. by drying the rest Dispersion medium freed and further processing fed.

    Eine beispielhafte Zusammensetzung der Anzündmischung ist:

  • 55 % Zirkoniumpulver
  • 43 % Kaliumperchlorat
  • 2 % Binderkomponente;
    • alle Prozentzahlen sind jeweils Gewichtsprozente.An exemplary composition of the ignition mixture is:
  • 55% zirconium powder
  • 43% potassium perchlorate
  • 2% binder component;
    • all percentages are percentages by weight.

    Das Verhältnis von Feststoff zu Dispergiermittel ist variabel und liegt erfahrungsgemäß im Bereich von 70% bis 80% Feststoffen.The ratio of solid to dispersant is variable and experience has shown that it is in the range of 70% to 80% solids.

    Als Metall werden vorzugsweise Titan oder Zirkonium bzw. deren Hydride verwendet. Der Binder wird vorzugsweise aus der Gruppe der fluorierten polymeren Aliphate ausgewählt.The metal used is preferably titanium or zirconium or their Hydride used. The binder is preferably made from the Group of fluorinated polymeric aliphates selected.

    Das Dispergiermittel fungiert vorzugsweise als Lösemittel für den Binder und stammt bevorzugt aus der Reihe der aliphatischen Ketone. Aceton oder Methylethylketon haben sich hierfür bewährt.The dispersant preferably acts as a solvent for the binder and preferably comes from the series of aliphatic Ketones. Acetone or methyl ethyl ketone have been used for this proven.

    Claims (10)

    1. Process for preparing pyrotechnic igniter charges on the basis of metal powders or metal hydride powders, potassium perchlorate and binders, characterised in that suspensions presenting little or no explosion hazard are prepared from the components of the igniter charge with the help of liquid dispersing agents, that these suspensions are blended using ultrasound, that immediately following the blending operation a desired quantity of the mix with this consistency is metered out, and that thereafter the dispersing agent is removed from the metered quantity.
    2. Process according to claim 1, characterised in that using ultrasound the desired quantity of the suspensions is blended directly in a casing which receives the pyrotechnic igniter charge.
    3. Process according to claim 1 or 2, characterised in that the employed metal, metal hydride and potassium perchlorate components in powder form have a particle size of < 50 µm, preferably < 20 µm.
    4. Process according to any of the preceding claims, characterised by the use of titanium or zirconium or hydrides thereof as the metal.
    5. Process according to any of the preceding claims, characterised in that the binder is selected from the group comprising fluorinated polymeric aliphates.
    6. Process according to any of the preceding claims, characterised in that the dispersing agent acts as a solvent for the binder.
    7. Process according to any of the preceding claims, characterised in that the dispersing agent is selected from the aliphatic ketone series.
    8. Process according to any of the preceding claims, characterised in that acetone or methyl ethyl ketone is used as the dispersing agent.
    9. Process according to any of the preceding claims, characterised in that during metering the mix is set oscillating.
    10. Process according to claim 9, characterised in that sound waves are passed into the mix.
    EP99926266A 1998-05-28 1999-04-16 Method for producing pyrotechnic primer charges Expired - Lifetime EP1089955B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19823999A DE19823999C2 (en) 1998-05-28 1998-05-28 Process for the manufacture of pyrotechnic igniters
    DE19823999 1998-05-28
    PCT/DE1999/001160 WO1999061394A1 (en) 1998-05-28 1999-04-16 Method for producing pyrotechnic primer charges

    Publications (2)

    Publication Number Publication Date
    EP1089955A1 EP1089955A1 (en) 2001-04-11
    EP1089955B1 true EP1089955B1 (en) 2002-08-21

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    EP99926266A Expired - Lifetime EP1089955B1 (en) 1998-05-28 1999-04-16 Method for producing pyrotechnic primer charges

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    US (1) US6783616B1 (en)
    EP (1) EP1089955B1 (en)
    JP (1) JP2002516250A (en)
    KR (1) KR100570574B1 (en)
    AT (1) ATE222580T1 (en)
    AU (1) AU752432B2 (en)
    CA (1) CA2332903A1 (en)
    DE (2) DE19823999C2 (en)
    WO (1) WO1999061394A1 (en)

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    CN111393238B (en) * 2020-04-03 2022-01-18 朱炳强 Fireworks capable of realizing safety production, storage and transportation and setting off

    Also Published As

    Publication number Publication date
    ATE222580T1 (en) 2002-09-15
    US6783616B1 (en) 2004-08-31
    KR100570574B1 (en) 2006-04-12
    EP1089955A1 (en) 2001-04-11
    JP2002516250A (en) 2002-06-04
    WO1999061394A1 (en) 1999-12-02
    AU4358499A (en) 1999-12-13
    KR20010052391A (en) 2001-06-25
    DE19823999C2 (en) 2002-07-18
    AU752432B2 (en) 2002-09-19
    DE19823999A1 (en) 1999-12-09
    DE59902415D1 (en) 2002-09-26
    CA2332903A1 (en) 1999-12-02

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