EP0914306A1 - Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors - Google Patents

Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors

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Publication number
EP0914306A1
EP0914306A1 EP97934480A EP97934480A EP0914306A1 EP 0914306 A1 EP0914306 A1 EP 0914306A1 EP 97934480 A EP97934480 A EP 97934480A EP 97934480 A EP97934480 A EP 97934480A EP 0914306 A1 EP0914306 A1 EP 0914306A1
Authority
EP
European Patent Office
Prior art keywords
blowing agent
nitrate
agent according
weight
propellant
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.)
Withdrawn
Application number
EP97934480A
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German (de)
French (fr)
Inventor
Ulrich Bley
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.)
Delphi Technologies Inc
Original Assignee
Dynamit Nobel AG
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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Publication date
Application filed by Dynamit Nobel AG, Dynamit Nobel GmbH Explosivstoff und Systemtechnik filed Critical Dynamit Nobel AG
Publication of EP0914306A1 publication Critical patent/EP0914306A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • Pyrotechnic mixture as a blowing agent or as a gas charge with carbon monoxide-reduced steam
  • the invention relates to a pyrotechnic mixture as a blowing agent or as a gas charge with carbon monoxide-reduced fumes
  • NC propellants based on nitrocellulose are used in a wide variety of applications, for example in civil and military ammunition or as gas-generating components in commercial cartridges, such as in bolt-setting tools.
  • NC propellants are characterized by their high degree of spreading and their favorable price and great experience in handling and use as well as a high degree of variability in the combustion properties, which can be controlled via the composition, the geometric shape and surface treatment, from NC propellants provide a high proportion of gas due to their almost slag-free combustion.
  • These gas vapors contain as main component (40-60 vol -%) the toxic carbon monoxide (CO) For this reason, good ventilation or limited use must be ensured when using NC blowing agents, especially in closed rooms
  • Propellants or pyrotechnic mixtures with a reduced CO content are widely described in the literature, for example as gas-generating mixtures which are used, for example, in airbags. These mixtures are used it is a combination of nitrogen-rich compounds such as, for example, sodium azide or 5-aminotetrazole and suitable oxidizing agents such as sodium nitrate or calcium perchlorate. These mixtures burn to form a large proportion of slag. As a result, and owing to their combustion properties, they are not suitable for use in ammunition, for example
  • CONFIRMATION COPY can be found which, in addition to the suitable burning properties, also have a low carbon content. Blowing agents that contain nitroaminoguanidine (NAGu) are suitable and meet this requirement. Nitroaminoguanidine is a nitrogen-rich molecule with explosive properties.
  • the object of the present invention was therefore to provide blowing agents which do not have the disadvantages of the blowing agents known in the prior art.
  • the blowing agents according to the invention are distinguished by the fact that they have a significantly reduced CO concentration in the gas clouds compared to NC blowing agents.
  • the blowing agents according to the invention are furthermore distinguished by an almost slag-free combustion.
  • the proportion of CO in the gas vapor is reduced by more than 50% compared to NC blowing agents.
  • the main components of the propellants according to the invention are nitrogen (approx. 40-50 vol.%) And water (approx. 20-30 vol.%).
  • the burning properties and safety-related characteristics of the mixtures according to the invention are comparable to those of typical NC propellants. Blowing agent comparable
  • the blowing agents according to the invention contain, as the main component, nitroaminoguanidine in a proportion by weight of 40-80% by weight.
  • Suitable additives are explosives such as nitroguanide, derivatives of tetrazole such as 5-aminotetrazole, 5-aminotetrazole nitrate, bistrazolamine, bitetrazole and their salts of the elements of I, II and III main group and I, II and VIII subgroup of the periodic table, as well as salts of titanium and manganese, salts of nitraminotetrazolate such as ammonium nitraminotetrazolate and aminoguanidinium nitrammotetrazolate, aminoguanidium nitrate, diaminoguamdinnitrate, triaminogyanidinitrididine, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium
  • Nitroguanide, taminoguanidine nitrate, aminotetrazole, hexogen and nitrocellulose and also mixtures of the components with one another are preferably used.
  • the proportions by weight of the explosive additive can be 0 to 40% by weight
  • binders such as polyvinyl butyral, polynitropolyphenylene, t ⁇ acetin, gelatin and glue.
  • Polyvinyl butyral is preferably used in proportions by weight of 0 to 10% by weight
  • Nitrates of the alkali and alkaline earth elements, perchlorates of the alkali and alkaline earth elements, ammonium nitrate, ammonium perchlorate or mixtures of these components can be used as the oxidizing agent.
  • Ammonium nitrate and ammonium perchlorate are preferably used in proportions by weight of 0 to 30% by weight Ferrocene and derivatives, acetylacetonate and derivatives, Aerosil, graphite, talc or mixtures of these components can be used as combustion moderators and processing aids.
  • the proportions by weight can be 0 to 10% by weight.
  • the production and processing takes place according to known and customary methods. For example, kneading, extrusion, extrusion, granulation or tableting
  • the pyrotechnic mixtures according to the invention are suitable for use in civil and military ammunition, as a gas-generating component in commercial cartridges such as, for example, in bolt-setting devices and as a propellant for gas generation in automotive safety systems such as belt tensioners or airbags
  • NC blowing agents can typically be characterized by their safety-related characteristics and the burning rate. This is typical data of NC blowing agents
  • Friction sensitivity 160 - 240 N Friction sensitivity 160 - 240 N
  • the burning rates are pressure-dependent and are typically around 10-20 mm / s at 100 bar and around 50-70 mm / s at 500 bar
  • the components of the pyrotechnic mixture according to the invention are well contracted with one another (gas elimination on selected mixtures at 90 ° C. and 40 hours ⁇ 3 ml).
  • Thermogravimetric tests show decomposition from 180 ° C. and with isothermal storage (90 ° C.) weight changes ⁇ 0.5% by weight at 48 hours, storage time.
  • Table 1 shows the composition of 5 different pyrotechnic mixtures according to the invention.
  • the specified components for the mixtures according to the invention are weighed out in the stated weight ratios in plastic containers and homogenized in a tumble mixer for 30 minutes
  • Table 2 shows the friction, impact sensitivities, deflagration points and heat of explosion.
  • the measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Material Research and Testing (BAM).
  • the deflagration points were determined using thermogravimetry analysis (Mettler) and the The heat of explosion was measured using a calorimeter from EKA
  • the burning rate was determined by tableting the mixtures into tablets with a height of approximately 2.5 mm and a diameter 7 mm 2 g of the tabletted samples were reacted using 0.2 g boron / potassium nitrate (25 75 wt. parts) as an ignition mixture and an electrically heatable iron wire in a 25 ml stainless steel pressure bomb.
  • the pressure development was recorded as a function of time Pressure-time curve and the shape function, the burn-up speeds (r) can be calculated depending on the pressure. For better clarity, the burn-up speeds at 100 and 500 bar are shown in Table 3
  • Characteristic values such as flame temperature and specific energy can be read from thermodynamic calculations.
  • typical values for the flame temperature are 2800-3600 K and specific energies of 1100-1200 J / g. Table 4 shows these values for the example mixtures. The flame temperatures are significantly reduced, while the specific energies are comparable to those of NC propellants

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)

Abstract

The invention pertains to propellants that have a substantially reduced CO concentration in the gas vapors compared to NC propellants. These propellants contain nitroaminoguanidines as main component, explosives as additives and oxidising agents.

Description

Pyrotechnische Mischung als Treibmittel oder als Gassatz mit Kohlenmonoxid-reduzierten Schwaden Pyrotechnic mixture as a blowing agent or as a gas charge with carbon monoxide-reduced steam
Gegenstand der Erfindung ist eine pyrotechnische Mischung als Treibmittel oder als Gassatz mit Kohlenmonoxid-reduzierten AbbrandschwadenThe invention relates to a pyrotechnic mixture as a blowing agent or as a gas charge with carbon monoxide-reduced fumes
Treibmittel auf Basis von Nitrocellulose (NC) finden in den unterschiedlichsten Anwendungen z B in Zivil- und Militarmunition oder als gaserzeugende Kompo- nente in gewerblichen Kartuschen wie z B in Bolzensetzgeraten Verwendung NC-Treibmittel zeichnen sich durch ihren hohen Verbreituπgsgrad, ihren dadurch bedingten gunstigen Preis und große Erfahrungswerte im Umgang und Einsatz sowie einer hohen Variabilität der Abbrandeigenschaften, die über die Zusammensetzung, die geometrische Form und Oberflachenbehandlung steuerbar sind, aus NC-Treibmittel liefern durch ihren nahezu schlackefreien Abbrand einen hohen Gasanteil Diese Gasschwaden enthalten als Hauptkomponente (40-60 Vol - %) das toxische Kohlenmonoxid (CO) Bei Verwendung von NC-Treibmitteln muß aus diesem Grund vor allem in geschlossenen Räumen für eine gute Belüftung oder für einen limitierten Einsatz gesorgt werdenPropellants based on nitrocellulose (NC) are used in a wide variety of applications, for example in civil and military ammunition or as gas-generating components in commercial cartridges, such as in bolt-setting tools. NC propellants are characterized by their high degree of spreading and their favorable price and great experience in handling and use as well as a high degree of variability in the combustion properties, which can be controlled via the composition, the geometric shape and surface treatment, from NC propellants provide a high proportion of gas due to their almost slag-free combustion. These gas vapors contain as main component (40-60 vol -%) the toxic carbon monoxide (CO) For this reason, good ventilation or limited use must be ensured when using NC blowing agents, especially in closed rooms
Deshalb ist das Ziel zahlreicher Entwicklungen und Erfindungen, CO-reduzierte Treibmittel oder pyrotechnische Mischungen bereitzustellen Treibmittel oder pyrotechnische Mischungen mit reduziertem CO-Anteil werden in der Literatur viel beschrieben z B als gaserzeugende Mischungen wie sie u a bei Airbags Ver- wendung finden Bei diesen Mischungen handelt es sich um Kombinationen von stickstoffreichen Verbindungen wie z B Natπumazid oder 5-Amιnotetrazol und geeigneten Oxidationsmitteln wie Natriumnitrat oder Ka umperchlorat Diese Mischungen verbrennen unter Bildung eines großen Anteils Schlacke Sie sind dadurch und aufgrund ihrer Abbrandeigenschaften beispielsweise nicht für den Em- satz in Munition geeignetThe aim of numerous developments and inventions is therefore to provide CO-reduced propellants or pyrotechnic mixtures. Propellants or pyrotechnic mixtures with a reduced CO content are widely described in the literature, for example as gas-generating mixtures which are used, for example, in airbags. These mixtures are used it is a combination of nitrogen-rich compounds such as, for example, sodium azide or 5-aminotetrazole and suitable oxidizing agents such as sodium nitrate or calcium perchlorate. These mixtures burn to form a large proportion of slag. As a result, and owing to their combustion properties, they are not suitable for use in ammunition, for example
Wegen der spezifischen Forderungen wie sie für Munition und andere verwandte Anwendungen gefordert werden, müssen deshalb Mischungen mit KomponentenBecause of the specific requirements that are required for ammunition and other related applications, mixtures with components must therefore be used
BESTATIGUNGSKOPIE gefunden werden, die neben den geeigneten Abbrandeigenschaften auch über einen niedrigen Kohlenstoffanteil verfügen. Treibmittel, die Nitroaminoguanidin (NAGu) enthalten, sind geeignet und erfüllen diese Forderung. Nitroaminoguanidin ist ein stickstoffreiches Molekül mit explosiven Eigenschaften.CONFIRMATION COPY can be found which, in addition to the suitable burning properties, also have a low carbon content. Blowing agents that contain nitroaminoguanidine (NAGu) are suitable and meet this requirement. Nitroaminoguanidine is a nitrogen-rich molecule with explosive properties.
Im US-Patent 4,373,976 wird eine Mischung mit NAGu als Hauptkomponente (50- 80 Gew.-%) beschrieben. NAGu wird dabei in Kombination mit NC (15-40 Gew - %), Oktogen (0-30 Gew.-%) und Bindern wie Triacetin (0-15 Gew.-%) verwendet. Dieses Treibmittel soll sich durch eine um 20-30% verringerte isochore Flammen- temperatur gegenüber herkömmlichen Treibmitteln auszeichnen und soll für die Verwendung in Munition geeignet sein. Aufgrund des hohen Anteils an NC, Oktogen und Bindern ist der CO-Anteil in den Gasschwaden jedoch nicht vermindert.US Patent 4,373,976 describes a mixture with NAGu as the main component (50-80% by weight). NAGu is used in combination with NC (15-40% by weight), octogen (0-30% by weight) and binders such as triacetin (0-15% by weight). This propellant is said to have a 20-30% lower isochoric flame temperature than conventional propellants and should be suitable for use in ammunition. However, due to the high proportion of NC, octogen and binders, the CO content in the gas vapor is not reduced.
Im US-Patent 3,677,841 wird neben anderen Verbindungen der Einsatz von NAGu in Kombination mit Abbrandkatalysatoren wie z.B. Vanadylacetylacetonat beschrieben. Die Mischungen sollen für den Einsatz in Gasgeneratoren als Gaserzeuger geeignet sein. Durch den Einsatz von Schwermetallkatalysatoren entsteht beim Abbrand jedoch eine schwermetallhaltige Schlacke, die toxisch ist.In U.S. Patent 3,677,841, among other compounds, the use of NAGu in combination with combustion catalysts such as e.g. Vanadylacetylacetonat described. The mixtures are said to be suitable for use in gas generators as gas generators. However, the use of heavy metal catalysts creates a slag that contains heavy metals and is toxic.
Aufgabe der vorliegenden Erfindung war daher die Bereitstellung von Treibmitteln, die die Nachteile der im Stand der Technik bekannten Treibmitteln nicht aufweisen.The object of the present invention was therefore to provide blowing agents which do not have the disadvantages of the blowing agents known in the prior art.
Gelöst wurde die der Erfindung zugrundeliegende Aufgabe durch ein Treibmittel mit den Kennzeichen des Hauptanspruchs. Vorzugsweise Ausgestaltungen sind in den Unteransprüchen charakterisiert.The object on which the invention is based was achieved by a propellant having the characteristics of the main claim. Embodiments are preferably characterized in the subclaims.
Die erfindungsgemäßen Treibmittel zeichnen sich dadurch aus, daß sie eine deutlich reduzierte CO-Konzentration in den Gasschwaden gegenüber NC- Treibmitteln aufweisen. Die erfindungsgemäßen Treibmitteln zeichnen sich weiterhin durch einen nahezu schlackefreien Abbrand aus. Der CO-Anteil in den Gasschwaden ist gegenüber NC-Treibmitteln um mehr als 50-% reduziert.. Im Gegensatz zu NC-Treibmitteln entstehen bei den erfindungsgemaßen Treibmitteln in den Gasschwaden als Hauptkomponenten Stickstoff (ca 40-50 Vol -%) und Wasser (ca 20-30 Vol -%) Die Abbrandeigenschaften und sicherheitstechnischen Kenndaten der erfindungsgemaßen Mischungen sind mit denen typischer NC-Treibmittel vergleichbarThe blowing agents according to the invention are distinguished by the fact that they have a significantly reduced CO concentration in the gas clouds compared to NC blowing agents. The blowing agents according to the invention are furthermore distinguished by an almost slag-free combustion. The proportion of CO in the gas vapor is reduced by more than 50% compared to NC blowing agents. Im In contrast to NC propellants, the main components of the propellants according to the invention are nitrogen (approx. 40-50 vol.%) And water (approx. 20-30 vol.%). The burning properties and safety-related characteristics of the mixtures according to the invention are comparable to those of typical NC propellants. Blowing agent comparable
Die erfindungsgemaßen Treibmittel enthalten als Hauptkomponente Nitroaminoguanidin in Gewichtsanteilen von 40-80 Gew -% Geeignete Zuschlage sind Explosivstoffe wie Nitroguanidm, Derivate des Tetrazols wie 5-Amιnotetrazol, 5-Amι- notetrazolnitrat, Bistetrazolamin, Bitetrazol und deren Salze der Elemente der I , II und III Hauptgruppe und I , II und VIII Nebengruppe des Periodensystems sowie Salze des Titans und Mangans, Salze des Nitraminotetrazolats wie Ammo- nium-Nitraminotetrazolat und Aminoguanidinium-Nitrammotetrazolat, Aminogua- nidmnitrat, Diaminoguamdinnitrat, Tπaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-azotetrazolat, Hexogen, Oktogen und Ni- trocelluloseThe blowing agents according to the invention contain, as the main component, nitroaminoguanidine in a proportion by weight of 40-80% by weight. Suitable additives are explosives such as nitroguanide, derivatives of tetrazole such as 5-aminotetrazole, 5-aminotetrazole nitrate, bistrazolamine, bitetrazole and their salts of the elements of I, II and III main group and I, II and VIII subgroup of the periodic table, as well as salts of titanium and manganese, salts of nitraminotetrazolate such as ammonium nitraminotetrazolate and aminoguanidinium nitrammotetrazolate, aminoguanidium nitrate, diaminoguamdinnitrate, triaminogyanidinitrididine, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium nitrate, guanidium nitrate, Octogen and nitrocellulose
Bevorzugt eingesetzt werden Nitroguanidm, Tπaminoguanidinnitrat, Aminotetra- zol, Hexogen und Nitrocellulose sowie auch Mischungen der Komponenten un- tereinander Die Gewichtsanteile der Zuschlage an Explosivstoffen können 0 bis 40 Gew -% betragenNitroguanide, taminoguanidine nitrate, aminotetrazole, hexogen and nitrocellulose and also mixtures of the components with one another are preferably used. The proportions by weight of the explosive additive can be 0 to 40% by weight
Weitere Zuschlage sind Bindemittel wie Polyvinylbutyral, Polynitropolyphenylen, Tπacetin, Gelatine und Leim Bevorzugt wird Polyvinylbutyral in Gewichtsanteilen von 0 bis 10 Gew -% eingesetztOther additives are binders such as polyvinyl butyral, polynitropolyphenylene, tπacetin, gelatin and glue. Polyvinyl butyral is preferably used in proportions by weight of 0 to 10% by weight
Als Oxidationsmittel können Nitrate der Alkali- und Erdalkalielemente, Perchlorate der Alkali- und Erdalkalielemente, Ammoniumnitrat, Ammoniumperchlorat oder Mischungen dieser Komponenten Verwendung finden Bevorzugt werden Ammo- niumnitrat und Ammoniumperchlorat in Gewichtsanteilen von 0 bis 30 Gew -% eingesetzt Als Abbrandmoderatoren und Verarbeitungshilfen können Ferrocen und Derivate Acetylacetonat und Derivate, Aerosil, Graphit, Talkum oder Mischungen dieser Komponenten eingesetzt werden Die Gewichtsanteile können 0 bis 10 Gew -%Nitrates of the alkali and alkaline earth elements, perchlorates of the alkali and alkaline earth elements, ammonium nitrate, ammonium perchlorate or mixtures of these components can be used as the oxidizing agent. Ammonium nitrate and ammonium perchlorate are preferably used in proportions by weight of 0 to 30% by weight Ferrocene and derivatives, acetylacetonate and derivatives, Aerosil, graphite, talc or mixtures of these components can be used as combustion moderators and processing aids. The proportions by weight can be 0 to 10% by weight.
Die Herstellung und Verarbeitung findet nach an sich bekannten und üblichen Verfahren statt Hierzu zahlen beispielsweise Kneten, Strangpressen, Extrudieren, Granulieren oder TablettierenThe production and processing takes place according to known and customary methods. For example, kneading, extrusion, extrusion, granulation or tableting
Die erfindungsgemaßen pyrotechnischen Mischungen sind für den Einsatz in Zivil- und Militarmunition, als gaserzeugende Komponente in gewerblichen Kartuschen wie z B in Bolzensetzgeraten und als Treibmittel zur Gaserzeugung in KFZ-Sicherheitssystemen wie z B Gurtstraffern oder Airbags geeignetThe pyrotechnic mixtures according to the invention are suitable for use in civil and military ammunition, as a gas-generating component in commercial cartridges such as, for example, in bolt-setting devices and as a propellant for gas generation in automotive safety systems such as belt tensioners or airbags
Durch geometrische Variationen und Zuschlagen können die Abbrandeigenschaften ähnlich den NC-Treibmitteln eingestellt werden NC-Treibmittel können typischerweise über ihre sicherheitstechnischen Kenndaten und die Abbrandge- schwindigkeit charakterisiert werden So sind typische Daten von NC-TreibmittelnGeometric variations and slamming allow the combustion properties to be set similarly to the NC blowing agents. NC blowing agents can typically be characterized by their safety-related characteristics and the burning rate. This is typical data of NC blowing agents
Reibempfindlichkeit 160 - 240 N,Friction sensitivity 160 - 240 N,
Schlagempfindlichkeit 2-5 J,Impact sensitivity 2-5 J,
Verpuff ungspunkt 160 - 170°CDeflagration point 160 - 170 ° C
Explosionswarmen 4000 - 5000 J/gWarm explosions 4000 - 5000 J / g
Die Abbrandgeschwindigkeiten sind druckabhangig und sind typischerweise bei 100 bar ca 10-20 mm/s und bei 500 bar ca 50-70 mm/sThe burning rates are pressure-dependent and are typically around 10-20 mm / s at 100 bar and around 50-70 mm / s at 500 bar
Die Komponenten der erfindungsgemaßen pyrotechnischen Mischung sind untereinander gut vertraglich (Gasabspaltung an ausgewählten Mischungen bei 90°C und 40h « 3 ml) Thermogravimetnsche Untersuchungen zeigen Zersetzungen ab 180°C und bei isothermen Lagerungen (90°C) Gewichtsanderungeπ < 0,5 Gew -% bei 48 Stunder, Lagerzeit Die folgenden Beispiele sollen die Erfindung naher erläutern, ohne sie einzuschränkenThe components of the pyrotechnic mixture according to the invention are well contracted with one another (gas elimination on selected mixtures at 90 ° C. and 40 hours <3 ml). Thermogravimetric tests show decomposition from 180 ° C. and with isothermal storage (90 ° C.) weight changes <0.5% by weight at 48 hours, storage time The following examples are intended to explain the invention in more detail without restricting it
Diese Beispiele zeigen, daß die erfindungsgemaßen Mischungen hinsichtlich ihrer Abbrandeigenschaften und sicherheitstechnischen Kenndaten mit NC-Treib- mitteln vergleichbar sind, jedoch deutlich niedrigere CO-Konzentrationen in den Abbrandschwaden aufweisenThese examples show that the mixtures according to the invention are comparable with NC propellants in terms of their burning properties and safety-related characteristic data, but have significantly lower CO concentrations in the burning clouds
In Tabelle 1 sind die Zusammensetzung von 5 verschiedenen erfindungsgemaßen pyrotechnischen Mischungen dargestellt Die spezifizierten Komponenten für die erfindungsgemaßen Mischungen werden in den angebenen Gewichtsverhalt- nissen in Plastikbehaltern eingewogen und in einem Taumelmischer 30 Minuten homogenisiertTable 1 shows the composition of 5 different pyrotechnic mixtures according to the invention. The specified components for the mixtures according to the invention are weighed out in the stated weight ratios in plastic containers and homogenized in a tumble mixer for 30 minutes
In Tabelle 2 sind die Reib-, Schlagempfindlichkeiten, Verpuffungspunkte und Ex- plosionswarmen dargestellt Die Messung der Reib- und Schlagempfindlichkeiten erfolgte nach Methoden der Bundesanstalt für Mateπalforschung und -prufung (BAM) Die Verpuffungspunkte wurden mit der Thermogravimetrie-Analyse (Mettler) bestimmt und die Messung der Explosionswarmen erfolgte mit einem Kalorimeter der Fa EKATable 2 shows the friction, impact sensitivities, deflagration points and heat of explosion. The measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Material Research and Testing (BAM). The deflagration points were determined using thermogravimetry analysis (Mettler) and the The heat of explosion was measured using a calorimeter from EKA
Zur Messung der CO-Konzentration wurden definierte Mengen (2 g) der Mischun- gen in einer 25 ml Edelstahldruckbombe zur Umsetzung mittels Zündung via Gluhdraht gebracht Anschließend wurde das entstehende Gas in einem Tedlar- Bag gefüllt und mit einem Gaschromatographen (FISON) die Zusammensetzung und CO-Konzentration des Gasgemisches bestimmt Die Ergebnisse sind in Tabelle 3 dargestelltTo measure the CO concentration, defined quantities (2 g) of the mixtures were placed in a 25 ml stainless steel pressure bomb for implementation by means of ignition using a glow wire. The resulting gas was then filled in a Tedlar bag and the composition and. Using a gas chromatograph (FISON) CO concentration of the gas mixture determined The results are shown in Table 3
Die Bestimmung der Abbrandgeschwindigkeit erfolgte durch Tablettierung der Mischungen zu Tabletten mit einer Hohe von ca 2,5 mm und einem Durchmesser von 7 mm 2 g der tablettierten Proben wurden mittels 0,2 g Bor/Ka umnitrat (25 75 Gew -Anteile) als Anzundmischung und eines elektrisch aufheizbaren Eisendrahtes in einer 25 ml Edelstahldruckbombe zur Umsetzung gebracht Aufgezeichnet wurde in Abhängigkeit der Zeit die Druckentwicklung Aus der Druck-Zeit Kurve und der Formfunktion lassen sich die Abbrandgeschwindigkeiten (r) in Abhängigkeit des Druckes berechnen Zur besseren Übersichtlichkeit sind die Abbrandgeschwindigkeiten bei 100 und 500 bar in Tabelle 3 dargestelltThe burning rate was determined by tableting the mixtures into tablets with a height of approximately 2.5 mm and a diameter 7 mm 2 g of the tabletted samples were reacted using 0.2 g boron / potassium nitrate (25 75 wt. parts) as an ignition mixture and an electrically heatable iron wire in a 25 ml stainless steel pressure bomb. The pressure development was recorded as a function of time Pressure-time curve and the shape function, the burn-up speeds (r) can be calculated depending on the pressure. For better clarity, the burn-up speeds at 100 and 500 bar are shown in Table 3
Aus thermodynamischen Berechnungen lassen sich charakteristische Großen wie Flammentemperatur und spezifische Energie ablesen Für NC-Pulver sind typische Großen für die Flammentemperatur 2800-3600 K und spezifische Energien von 1100-1200 J/g In Tabelle 4 sind diese Großen für die Beispielmischungen angeben Die Flammentemperaturen sind deutlich erniedrigt, wahrend die spezifischen Energien mit denen von NC-Treibmifteln vergleichbar sind Characteristic values such as flame temperature and specific energy can be read from thermodynamic calculations. For NC powder, typical values for the flame temperature are 2800-3600 K and specific energies of 1100-1200 J / g. Table 4 shows these values for the example mixtures. The flame temperatures are significantly reduced, while the specific energies are comparable to those of NC propellants
Tabelle 1Table 1
Beispiele für erfindungsgemaße TreibmittelExamples of blowing agents according to the invention
Beispiel Nitramino- Nitroguanidm Hexogen Amino- TπaminoguaniNr guanidm tetrazol dinnitrat [Gew -%] [Gew -%]Example Nitramino-Nitroguanidm Hexogen Amino-TπaminoguaniNr guanidm tetrazole dinnitrat [Gew -%] [Gew -%]
[Gew -%] [Gew -%] [Gew -%][% By weight] [% by weight] [% by weight]
1 60 25 5 101 60 25 5 10
50 25 5 5 1550 25 5 5 15
70 20 1070 20 10
60 30 1060 30 10
70 30 70 30
Tabelle 2Table 2
Zusammenstellung der sicherheitstechnischen DatenCompilation of the safety-related data
Beispiel- Reibempfind- Schlagempfmd- Verpuffungs- Explosionswarme Nr chkeit chkeit punktExample- Friction Sensitivity- Impact Deflagration- Explosion Warmth Point
[J/g][Y / g]
[N] [J] [°C][N] [J] [° C]
1 240 3 185 36901 240 3 185 3690
2 160 3 185 36192 160 3 185 3619
3 160 3 185 37203 160 3 185 3720
4 240 4 185 36524 240 4 185 3652
5 240 3 185 3582 5 240 3 185 3582
Tabelle 3Table 3
Zusammenfassung der CO-Konzentrationen und Abbrandgeschwindigkeiten (r)Summary of CO concentrations and burning rates (r)
Tabelle 4:Table 4:
Zusammenstellung von thermodynamisch berechneten GrößenCompilation of thermodynamically calculated quantities
Mischungs- Flammenspezifische Energie Nr. temperatur [J]Mixture-specific energy no. Temperature [J]
[K][K]
1 2751 11351 2751 1135
2 2605 10882 2605 1088
3 2700 11283 2700 1128
4 2666 11084 2666 1108
5 2680 1106 5 2680 1106

Claims

Patentansprüche claims
1. Treibmittel mit Kohlenmonoxid-reduzierten Schwaden, dadurch gekennzeichnet, daß es als Hauptkomponente Nitroaminoguanidin, Explosivstoffe als Zuschläge und Oxidationsmittel enthält.1. blowing agent with carbon monoxide-reduced steam, characterized in that it contains nitroaminoguanidine as the main component, explosives as additives and oxidizing agents.
2. Treibmittel gemäß Anspruch 1 , dadurch gekennzeichnet, daß es als Zuschläge mindestens einen Explosivstoff ausgewählt aus den Explosivstoffen Nitroguanidin, Derivaten des Tetrazols, vorzugsweise 5-Aminotetrazol, 5- Aminotetrazolnitrat, Bistetrazolamin, Bitetrazol oder deren Salze mit Elementen der I., II. und III. Hauptgruppe oder I., II. und VIII. Nebengruppe des Periodensystems oder deren Titan- oder Mangan-Salze, den Salzen des Nitrami- notetrazolats, vorzugsweise Ammonium-Nitraminotetrazolat oder Aminogua- nidinium-Nitraminotetrazolat, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-azotetrazolat, Hexogen, Oktogen oder Nitrocellulose enthält.2. Propellant according to claim 1, characterized in that it contains at least one explosive selected from the explosives nitroguanidine, derivatives of tetrazole, preferably 5-aminotetrazole, 5-aminotetrazole nitrate, bistrazolamine, bitetrazole or their salts with elements of I., II. and III. Main group or I., II. And VIII. Subgroup of the periodic table or their titanium or manganese salts, the salts of nitramino tetrazolate, preferably ammonium nitraminotetrazolate or aminoguanidinium nitraminotetrazolate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, guanidine nitrate, Contains diaminoguanidine azotetrazolate, hexogen, octogen or nitrocellulose.
3. Treibmittel gemäß Anspruch 1 , dadurch gekennzeichnet, daß es als Zuschläge mindestens einen Explosivstoff ausgewählt aus den Explosivstoffen Nitroguanidin, Triaminoguanidinnitrat, Aminotetrazol, Hexogen und Nitrocellulose enthält.3. blowing agent according to claim 1, characterized in that it contains at least one explosive selected from the explosives nitroguanidine, triaminoguanidine nitrate, aminotetrazole, hexogen and nitrocellulose as additives.
4. Treibmittel gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es Nitroaminoguanidin in Gewichtsanteilen von 40-80 Gew.-% und die Zuschläge in Gewichtsanteilen von 0 bis 40 Gew.-% enthält.4. blowing agent according to one of claims 1 to 3, characterized in that it contains nitroaminoguanidine in parts by weight of 40-80 wt .-% and the additions in parts by weight of 0 to 40 wt .-%.
5. Treibmittel gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es außerdem Bindemittel wie Polyvinylbutyral, Polynitropolyphenylen, Triacetin, Gelatine oder Leim, vorzugsweise Polyvinylbutyral enthält.5. blowing agent according to one of claims 1 to 4, characterized in that it also contains binders such as polyvinyl butyral, polynitropolyphenylene, triacetin, gelatin or glue, preferably polyvinyl butyral.
Treibmittel gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es das Bindemittel in Gewichtsanteilen von 0 bis 10 Gew.-% enthält. Blowing agent according to one of claims 1 to 5, characterized in that it contains the binder in parts by weight of 0 to 10 wt .-%.
7. Treibmittel gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als Oxidationsmittel Nitrate der Alkali- oder Erdalkalielemente, Perchlorate der Alkali- oder Erdalkalielemente, Ammoniumnitrat, Ammonium- perchlorat, vorzugsweise Ammoniumnitrat oder Ammoniumperchlorat oder7. blowing agent according to any one of claims 1 to 5, characterized in that it is an oxidizing agent nitrates of the alkali or alkaline earth elements, perchlorates of the alkali or alkaline earth elements, ammonium nitrate, ammonium perchlorate, preferably ammonium nitrate or ammonium perchlorate or
Mischungen dieser Komponenten enthält.Contains mixtures of these components.
8. Treibmittel gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es das Oxidationsmittel in Gewichtsanteilen von 0 bis 30 Gew.-% enthält.8. blowing agent according to one of claims 1 to 7, characterized in that it contains the oxidizing agent in parts by weight of 0 to 30 wt .-%.
9. Treibmittel gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es zusätzlich Abbrandmoderatoren und/oder Verarbeitungshilfen enthält.9. blowing agent according to one of claims 1 to 8, characterized in that it additionally contains combustion moderators and / or processing aids.
10. Treibmittel gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es als Abbrandmoderatoren und/oder Verarbeitungshilfen Ferrocen oder dessen Derivate, Acetylacetonat oder dessen Derivate, Aerosil, Graphit, Talkum oder Mischungen dieser Komponenten enthält.10. A blowing agent according to one of claims 1 to 9, characterized in that it contains ferrocene or its derivatives, acetylacetonate or its derivatives, aerosil, graphite, talc or mixtures of these components as combustion moderators and / or processing aids.
11. Treibmittel gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es Abbrandmoderatoren und/oder Verarbeitungshilfen in Gewichtsanteilen von 0 bis 10 Gew.-% enthält.11. Blowing agent according to one of claims 1 to 10, characterized in that it contains combustion moderators and / or processing aids in parts by weight of 0 to 10 wt .-%.
12. Verfahren zur Herstellung der Treibmittel nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, daß die Komponenten gemischt und durch Kneten, Strangpressen, Extrudieren, Granulieren oder Tablettieren geformt werden.12. A method for producing the blowing agent according to one of claims 1 to 11, characterized in that the components are mixed and shaped by kneading, extrusion, extrusion, granulation or tableting.
13. Verwendung der Treibmittel nach einem der Ansprüche 1 bis 11 in Zivil- und Militärmunition, als gaserzeugende Komponente in gewerblichen Kartuschen, beispielsweise in Bolzensetzgeräten oder als Treibmittel zur Gaserzeugung in KFZ-Sicherheitssystemen, beispielsweise in Gurtstraffem oder Airbags. 13. Use of the propellant according to one of claims 1 to 11 in civil and military ammunition, as a gas-generating component in commercial cartridges, for example in bolt-actuating devices or as a propellant for gas generation in automotive safety systems, for example in belt tensioners or airbags.
EP97934480A 1996-07-20 1997-07-17 Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors Withdrawn EP0914306A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19629226 1996-07-20
DE19629226 1996-07-20
PCT/EP1997/003835 WO1998003449A1 (en) 1996-07-20 1997-07-17 Pyrotechnic mixture as propellant or a gas charge with carbon monoxide-reduced vapors

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EP0914306A1 true EP0914306A1 (en) 1999-05-12

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EP (1) EP0914306A1 (en)
CA (1) CA2264910A1 (en)
DE (1) DE19730872A1 (en)
WO (1) WO1998003449A1 (en)

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WO1998003449A1 (en) 1998-01-29
US6024812A (en) 2000-02-15
CA2264910A1 (en) 1998-01-29

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