EP2935160B1 - Pyrotechnic mixture for producing an aerosol - Google Patents

Pyrotechnic mixture for producing an aerosol Download PDF

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Publication number
EP2935160B1
EP2935160B1 EP13817671.4A EP13817671A EP2935160B1 EP 2935160 B1 EP2935160 B1 EP 2935160B1 EP 13817671 A EP13817671 A EP 13817671A EP 2935160 B1 EP2935160 B1 EP 2935160B1
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EP
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Prior art keywords
pyrotechnic mixture
pyrotechnic
mixture according
acid
mixtures
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EP13817671.4A
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German (de)
French (fr)
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EP2935160A2 (en
Inventor
Ernest Schulz
Dirk Cegiel
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Rheinmetall Waffe Munition GmbH
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Rheinmetall Waffe Munition GmbH
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Priority to PL13817671T priority Critical patent/PL2935160T3/en
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Classifications

    • 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)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
    • C06B29/08—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with an organic non-explosive or an organic non-thermic component

Definitions

  • the invention relates to a pyrotechnic mixture for producing an aerosol containing at least one oxidizing agent, at least one reducing agent and an evaporable, mist-forming mixture.
  • the aerosol can z. G. for daytime signaling, as a non-lethal agent in police and military deployment scenarios and as a camouflage nebula.
  • Such a pyrotechnic mixture is for example from the EP 0 329 718 B1 known.
  • pyrotechnic composition is for example from the EP 0 329 718 B1 known.
  • mist-forming substances the inorganic salts of potassium chloride and sodium chloride.
  • a pyrotechnic mixture is known in which an aliphatic dicarboxylic acid is used as a fog-forming substance.
  • the invention has for its object to provide a pyrotechnic mixture for generating an aerosol that is simple and inexpensive to produce and human and ecotoxicologically harmless as possible.
  • the invention is based on the claim of producing a humanoid and ecotoxicologically harmless aerosol which has good optical activity (high extinction, low transmission).
  • the temperature required for the evaporation of the mist-forming substance mixture should be as low as possible. This has the advantage that a special insulation of the mist container is not required.
  • the flame should be as low as possible, so that in combination with the low burning temperature, the fire load on the environment is low.
  • the pyrotechnic composition is then used in sealed containers, containers, etc., the z. B. made of metal or cardboard and have at least one opening.
  • the pyrotechnic composition is ignited by means of a corresponding ignition charge.
  • the released thermal energy is used to evaporate the aliphatic monocarboxylic acid and the emulsifier.
  • the mist set burns with a relatively low temperature and low flame.
  • the mist container itself does not have to be particularly insulated; the fire load on the environment is relatively low.
  • the pyrotechnic mixture can be added to a heat-resistant, porous filler which is chemically inert to the other constituent constituents. It may be z. B. natural, amorphous silica (diatomaceous earth) or natural clays such. B. Kaolin act.
  • Fat phases of fatty acid and emulsifier are known and provide the basis for oil in fat or fat in oil emulsions, the z. B. in the food or cosmetic industry. As intended, these fat phases are intended to store or store water, ie. H. they are supposed to bind water physically so that an emulsion is formed.
  • the particles vaporized on firing the pyrotechnic mixture behave in air like condensation nuclei, d. H. they can physically store or store water from the air and form an aerosol of solid and liquid particles that scatters and absorbs the visible light like a natural mist.
  • the pyrotechnic mixture according to the invention has the advantage that the aerosol formed from the vaporizable solids, in particular the monocarboxylic acids, already scatter the light so well that a good optical effectiveness is given even at low atmospheric humidity.
  • This pronounced property of the active ingredient components gives the pyrotechnic mixture certain climate independent properties.
  • This property is further enhanced by the fact that the pyrotechnic mixture according to the invention during firing, d. H. in the reaction of the oxidation with the reducing agent, generates a significant amount of water vapor, which allows an "insitive" (dense) formation of the mist.
  • the active ingredient components monocarboxylic acids and emulsifiers specified in the pyrotechnic mixture according to the invention are known as such and can be found in the food industry outside the industry.
  • carboxylic acids and emulsifiers are usually approved for use in foods or ingredients of natural foods. As a result, these components are easily available.
  • the active ingredient components in turn contain no cyclic hydrocarbons.
  • the active components in the aerosol, carboxylic acids and emulsifiers, are themselves human and ecotoxicologically harmless.
  • palmitic acid hexadecanoic acid
  • stearic acid octadecanoic acid
  • / or behenic acid doosanoic acid
  • the height of the melting point of the mono-carboxylic acids depends on the carbon chain length.
  • pyrotechnic mixtures especially for military applications, must withstand temperatures above 64 ° C over an extended period of time and must not lose their safety and function.
  • the chemical stability of the low-melting mono-carboxylic acids is given in the proposed pyrotechnic mixture, they have the disadvantage that they begin to melt below 60 ° C. in the mixture. As a result, the solid structure of the pyrotechnic mixture changes - usually disadvantageous.
  • the melting point of low melting waxes can be increased by admixing a high melting polymer, e.g. B. with polyethylene glycol.
  • a high melting polymer e.g. B.
  • polyethylene glycol polyethylene glycol
  • the melting point of, for example, stearic acid from 58 ° C to 88 ° C raises when both substances are mixed in a mixing ratio of 50:50.
  • mixing ratios of the polyethylene with stearic acid from 5:95 to 10:90 results in a melting point reduction by about 4 ° C, d. H.
  • These mixtures melt below the melting points of the individual components.
  • the melting point rises above the melting point of low melting stearic acid.
  • the mixed melting point is approx. 78 ° C.
  • the inventive mixture In order to compensate for the mentioned disadvantage of low-melting mono-carboxylic acids in the inventive mixture, it is provided to mix the low-melting mono-carboxylic acids a higher-melting substance, preferably polyethylene glycol or polyethylene in proportions of 10% - 20%.
  • a higher-melting substance preferably polyethylene glycol or polyethylene in proportions of 10% - 20%.
  • chlorates from the group of alkali metals can be used.
  • potassium chlorate has proven to be advantageous as an oxidizing agent.
  • the reducing agent may be a carbohydrate or a mixture of different carbohydrates from the groups of mono- or di-saccharides.
  • the reducing agent may be glucose, sucrose and lactose.
  • the pyrotechnic mixture may additionally contain a filler.
  • Hydrated aluminum silicates in particular natural kaolins such as bolus alba, have proven particularly advantageous for the composition according to the invention.
  • the components of the pyrotechnic mixture can be mixed and processed in powdered form.
  • the mixture can also be granulated without addition of a binder with water.
  • the powder mixture or the granulate can then be filled directly into a corresponding container, etc.
  • the mixture is pressed together with a primer in the / the container, etc.
  • the mist set or the mist body can be produced easily and inexpensively.
  • the burning speed depends on a. on the size of the surface (grain size, geometry) of the granules.
  • this granulate can be used in a container filled.
  • the granules may still be coated with a pyrotechnic igniter mixture in order to improve the firing of the granules.
  • the pyrotechnic mixture but also a binder can be added, preferably from the group of cellulose esters, dextrins or similar. comes.
  • precautionary neutralizing salts may be added to the mixture in order to prevent the formation of auto-ignitable chloric acid.
  • the neutralizing agents are preferably carbonates or Hydroxidcarbonate the alkaline earth group, such as. For example, calcium carbonate and magnesium hydroxide carbonate, or aluminum hydroxide.
  • these neutralizing agents 2% to the pyrotechnic mixture is sufficient.
  • these neutralizing agents can, similar to aluminum silicate, regulate the combustion of the pyrotechnic mixture and replace part of the aluminum silicate.
  • this graphite or boron nitride can be mixed.
  • the container can also be a throwing body, a grenade or a grenade carrying the container, which consist of a multiplicity of different materials.
  • the container can also be a throwing body, a grenade or a grenade carrying the container, which consist of a multiplicity of different materials.
  • certain materials such. B. special plastics but also inorganic residues from surface treatments of metallic components, at temperatures above 64 ° C and / or presence of residual moisture by formation of the dreaded chloric acid from the alkali chlorate can lead to spontaneous combustion of the pyrotechnic mixture, these are not used.
  • cellulose esters in proportions of 1-5% can be added to the mixtures and the water-moist mixture subsequently granulated.

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  • Chemical & Material Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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Description

Die Erfindung betrifft eine pyrotechnische Mischung zur Erzeugung eines Aerosols, die mindestens ein Oxidationsmittel, mindestens ein Reduktionsmittel sowie ein verdampfbares, nebelbildendes Stoffgemisch enthält. Das Aerosol kann z. g. zur Signalgebung bei Tag, als nicht letales Wirkmittel in polizeilichen und militärischen Einsatzszenarien und als Tarnnebel eingesetzt werden.The invention relates to a pyrotechnic mixture for producing an aerosol containing at least one oxidizing agent, at least one reducing agent and an evaporable, mist-forming mixture. The aerosol can z. G. for daytime signaling, as a non-lethal agent in police and military deployment scenarios and as a camouflage nebula.

Eine derartige pyrotechnische Mischung (pyrotechnischer Satz) ist beispielsweise aus der EP 0 329 718 B1 bekannt. Dabei werden als verdampfbare, nebelbildende Stoffe, die anorganischen Salze Kaliumchlorid und Natriumchlorid verwendet.Such a pyrotechnic mixture (pyrotechnic composition) is for example from the EP 0 329 718 B1 known. Here are used as vaporizable, mist-forming substances, the inorganic salts of potassium chloride and sodium chloride.

Nachteilig ist bei dieser bekannten pyrotechnischen Mischung allerdings, dass zur Verdampfung des Kochsalzes hohe Temperaturen (>1450 °C) erforderlich sind. Als Reduktionsmittel wird daher Magnesiumpulver eingesetzt, so dass sich in Verbindung mit Kaliumnitrat und Kaliumperchlorat als Oxidationsmittel Reaktionstemperaturen von > 1450 °C ergeben. Aufgrund dieser hohen Temperaturen müssen die die pyrotechnische Mischung enthaltenden Metallbehälter (Nebelbehälter) in der Regel eine entsprechend aufwendige Wärmeisolierung aufweisen.A disadvantage of this known pyrotechnic mixture, however, that the evaporation of the common salt high temperatures (> 1450 ° C) are required. As a reducing agent therefore magnesium powder is used, so that in conjunction with potassium nitrate and potassium perchlorate as the oxidizing agent reaction temperatures of> 1450 ° C result. Due to these high temperatures, the metal container containing the pyrotechnic mixture (mist container) must generally have a correspondingly expensive thermal insulation.

Aus der US 4,032,374 ist eine pyrotechnische Mischung bekannt, bei der als nebelbildender Stoff eine organische Verbindung (Zimtsäure) verwendet wird, zu deren Verdampfung eine relativ niedrige Temperatur in der Größenordnung von 300 °C erforderlich ist. Nachteilig ist bei dieser Mischung allerdings, dass in dem sich bildenden Nebel gesundheitsschädliche, cyclische Kohlenwasserstoffverbindungen, wie Styrol, auftreten.From the US 4,032,374 is a pyrotechnic mixture is known in which the fog-forming substance, an organic compound (cinnamic acid) is used, the evaporation of which a relatively low temperature of the order of 300 ° C is required. A disadvantage of this mixture, however, that harmful noxious, cyclic hydrocarbon compounds such as styrene occur in the forming mist.

Aus der US 5,154,782 ist eine pyrotechnische Mischung bekannt, bei der als nebelbildender Stoff eine aliphatische Dicarbonsäure verwendet wird. Der Erfindung liegt die Aufgabe zugrunde, eine pyrotechnische Mischung zur Erzeugung eines Aerosols anzugeben, die einfach und kostengünstig herstellbar und möglichst human- und ökotoxikologisch unbedenklich ist.From the US 5,154,782 is a pyrotechnic mixture is known in which an aliphatic dicarboxylic acid is used as a fog-forming substance. The invention has for its object to provide a pyrotechnic mixture for generating an aerosol that is simple and inexpensive to produce and human and ecotoxicologically harmless as possible.

Diese Aufgabe wird erfindungsgemäß durch die Merkmale des Anspruchs 1 gelöst. Weitere, besonders vorteilhafte Ausgestaltungen der Erfindung offenbaren die Unteransprüche.This object is achieved by the features of claim 1. Further, particularly advantageous embodiments of the invention disclose the dependent claims.

Die Erfindung beruht auf dem Anspruch, ein möglichst human- und ökotoxikologisch unbedenkliches Aerosol zu erzeugen, welches eine gute optische Wirksamkeit (große Extinktion, geringe Transmission) aufweist. Die zur Verdampfung des nebelbildenden Stoffgemisches erforderliche Temperatur sollte dabei möglichst niedrig sein. Das bringt den Vorteil mit sich, dass eine besondere Isolierung des Nebelbehälters nicht erforderlich ist. Außerdem sollte die Flammenbildung möglichst gering sein, sodass in Kombination mit der niedrigen Abbrandtemperatur die Brandlast auf die Umgebung gering ist.The invention is based on the claim of producing a humanoid and ecotoxicologically harmless aerosol which has good optical activity (high extinction, low transmission). The temperature required for the evaporation of the mist-forming substance mixture should be as low as possible. This has the advantage that a special insulation of the mist container is not required. In addition, the flame should be as low as possible, so that in combination with the low burning temperature, the fire load on the environment is low.

Dieser Anspruch wird im Wesentlichen dadurch realisiert, dass als nebelbildende Mischung erfindungsgemäß ein Gemisch aus mindestens einer gesättigten, aliphatischen Monocarbonsäure (Fettsäure) mit einer Kohlenstoffkettenlänge C14 bis C24 und einem Emulgator aus der Gruppe der mono- oder mono-di-Glycerid-Fettsäureester oder mit Fruchtsäure veresterte mono- oder mono-di-Glycerid-Fettsäureester verwendet wird (=Monoglyceride und Diglyceride sowie Mischung aus Monoglyceriden und Diglyceriden).This claim is essentially realized in that the fog-forming mixture according to the invention, a mixture of at least one saturated aliphatic monocarboxylic acid (fatty acid) having a carbon chain length C14 to C24 and an emulsifier from the group of mono- or mono-di-glyceride fatty acid esters or Fruit acid esterified mono- or mono-di-glyceride fatty acid ester is used (= monoglycerides and diglycerides and mixture of monoglycerides and diglycerides).

Bevorzugt wird der pyrotechnische Satz dann in verschlossenen Containern, Behältern etc. verwendet, die z. B. aus Metall oder Pappe bestehen und zumindest eine Öffnung aufweisen. Zur Erzeugung des Aerosols wird der pyrotechnische Satz mittels eines entsprechenden Anzündsatzes angezündet. Die freigesetzte Wärmeenergie wird dazu genutzt, die aliphatische Monocarbonsäure und den Emulgator zu verdampfen. Der Nebelsatz brennt mit relativ niedriger Temperatur und geringer Flamme. Der Nebelbehälter selbst muss nicht besonders isoliert sein; die Brandlast auf die Umgebung ist relativ gering.Preferably, the pyrotechnic composition is then used in sealed containers, containers, etc., the z. B. made of metal or cardboard and have at least one opening. To generate the aerosol, the pyrotechnic composition is ignited by means of a corresponding ignition charge. The released thermal energy is used to evaporate the aliphatic monocarboxylic acid and the emulsifier. The mist set burns with a relatively low temperature and low flame. The mist container itself does not have to be particularly insulated; the fire load on the environment is relatively low.

Zur Steuerung des Abbrandes kann der pyrotechnischen Mischung ein hitzebeständiger, gegenüber den übrigen Satzbestandteilen sich chemisch inert verhaltender und poröser Füllstoff zugesetzt werden. Dabei kann es sich z. B. um natürliche, amorphe Kieselsäure (Kieselgur) oder natürliche Tone, wie z. B. Kaoline handeln.To control the burn-off, the pyrotechnic mixture can be added to a heat-resistant, porous filler which is chemically inert to the other constituent constituents. It may be z. B. natural, amorphous silica (diatomaceous earth) or natural clays such. B. Kaolin act.

Beim Verdampfen der Carbonsäure und des Emulgators strömen diese aus der Öffnung des Containers und bilden mikroskopisch kleine Mischteilchen, die eine Fettphase bilden. Fettphasen aus Fettsäure und Emulgator sind bekannt und stellen die Grundlage für Öl in Fett oder Fett in Öl Emulsionen dar, die z. B. in der Nahrungsmittel- oder kosmetischen Industrie eingesetzt werden. Bestimmungsgemäß sollen diese Fettphasen Wasser an bzw. einlagern, d. h. sie sollen Wasser physikalisch binden, so dass eine Emulsion entsteht.Upon evaporation of the carboxylic acid and the emulsifier, they flow out of the container opening to form microscopically small mixing particles which form a fatty phase. Fat phases of fatty acid and emulsifier are known and provide the basis for oil in fat or fat in oil emulsions, the z. B. in the food or cosmetic industry. As intended, these fat phases are intended to store or store water, ie. H. they are supposed to bind water physically so that an emulsion is formed.

In Abhängigkeit von der Luftfeuchtigkeit, verhalten sich die beim Brennen der pyrotechnischen Mischung verdampften Teilchen an der Luft wie Kondensationskeime, d. h. sie können Wasser aus der Luft physikalisch an- bzw. einlagern und ein Aerosol aus festen und flüssige Teilchen bilden, dass das sichtbare Licht wie ein natürlicher Nebel streut und absorbiert.Depending on the humidity, the particles vaporized on firing the pyrotechnic mixture behave in air like condensation nuclei, d. H. they can physically store or store water from the air and form an aerosol of solid and liquid particles that scatters and absorbs the visible light like a natural mist.

Die erfindungsgemäße pyrotechnische Mischung hat den Vorteil, dass das aus den verdampfbaren Feststoffen gebildete Aerosol, insbesondere die Monocarbonsäuren, das Licht bereits so gut streuen, dass eine gute optische Wirksamkeit auch bei geringer Luftfeuchtigkeit gegeben ist. Diese ausgeprägte Eigenschaft der Wirkstoffkomponenten, verleiht der pyrotechnischen Mischung gewisse Klima unabhängige Eigenschaften. Diese Eigenschaft wird noch dadurch verstärkt, dass die erfindungsgemäße pyrotechnische Mischung beim Brennen, d. h. bei der Reaktion des Oxidations- mit dem Reduktionsmittel, eine nicht unerhebliche Menge Wasserdampf erzeugt, die eine "insitiv" (dichte) Bildung des Nebels ermöglicht. - Klassische pyrotechnische Signalrauchsätze, d. h. pyrotechnische Sätze die Feststoffaerosole aus organischen Farbstoffen in der Luft erzeugen und deren Teilchen hydrophob sind, weisen diese Eigenschaften nicht auf. Die Transmission durch diese Aerosole ist größer, weshalb diese nicht für Tarnzwecke oder nicht letale Wirkmittel sonder bestimmungsgemäß nur für Signalzwecke eingesetzt werden können.The pyrotechnic mixture according to the invention has the advantage that the aerosol formed from the vaporizable solids, in particular the monocarboxylic acids, already scatter the light so well that a good optical effectiveness is given even at low atmospheric humidity. This pronounced property of the active ingredient components gives the pyrotechnic mixture certain climate independent properties. This property is further enhanced by the fact that the pyrotechnic mixture according to the invention during firing, d. H. in the reaction of the oxidation with the reducing agent, generates a significant amount of water vapor, which allows an "insitive" (dense) formation of the mist. - Classical pyrotechnic signal smoke sets, d. H. Pyrotechnic sets that produce solid aerosols of organic dyes in the air and whose particles are hydrophobic, do not have these properties. The transmission through these aerosols is larger, which is why they can not be used for camouflaging or non-lethal agents specifically intended only for signaling purposes.

Die in der erfindungsgemäßen pyrotechnischen Mischung angegebenen Wirkstoffkomponenten Monocarbonsäuren und Emulgatoren sind als solche bekannt und in der branchenfremden Lebensmittelindustrie anzutreffen. Insbesondere Carbonsäuren und Emulgatoren sind üblicherweise für die Verwendung in Lebensmitteln zugelassen bzw. Bestandteile natürlicher Nahrungsmittel. Dadurch sind diese Komponenten leicht beziehbar. Die Wirkstoffkomponenten enthalten ihrerseits keine cyclischen Kohlenwasserstoffe. - Die Wirkkomponenten im Aerosol, Carbonsäuren und Emulgatoren, sind für sich human- und ökotoxikologisch unbedenklich.The active ingredient components monocarboxylic acids and emulsifiers specified in the pyrotechnic mixture according to the invention are known as such and can be found in the food industry outside the industry. In particular, carboxylic acids and emulsifiers are usually approved for use in foods or ingredients of natural foods. As a result, these components are easily available. The active ingredient components in turn contain no cyclic hydrocarbons. - The active components in the aerosol, carboxylic acids and emulsifiers, are themselves human and ecotoxicologically harmless.

Als vorteilhaft hat es sich erwiesen, wenn als Mono- Carbonsäure Palmitinsäure (Hexadecansäure), Stearinsäure (Octadecansäure) und / oder Behensäure (Docosansäure) verwendet wird. Bekanntlich hängt die Höhe des Schmelzpunktes der Mono-Carbonsäuren von der Kohlenstoffkettenlänge ab. Des Weiteren müssen pyrotechnische Mischungen, besonders für militärische Anwendungen Temperaturen über 64 °C auch über einen längeren Zeitraum, aushalten und ihre Sicherheit- und Funktion nicht verlieren. Die chemische Stabilität der niedrig schmelzenden Mono-Carbonsäuren ist zwar in der vorgeschlagenen pyrotechnischen Mischung gegeben, jedoch weisen diese den Nachteil auf, dass sie bereits unterhalb von 60 °C in der Mischung anfangen zu schmelzen. Dadurch verändert sich das feste Gefüge der pyrotechnischen Mischung - in der Regel nachteilig.It has proved to be advantageous if palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid) and / or behenic acid (docosanoic acid) is used as monocarboxylic acid. As is known, the height of the melting point of the mono-carboxylic acids depends on the carbon chain length. Furthermore, pyrotechnic mixtures, especially for military applications, must withstand temperatures above 64 ° C over an extended period of time and must not lose their safety and function. Although the chemical stability of the low-melting mono-carboxylic acids is given in the proposed pyrotechnic mixture, they have the disadvantage that they begin to melt below 60 ° C. in the mixture. As a result, the solid structure of the pyrotechnic mixture changes - usually disadvantageous.

Der Schmelzpunkt niedrig schmelzender Wachse lässt sich durch Zumischen eines hoch schmelzenden Polymers erhöhen, z. B. mit Polyethylenglycol. - In Versuchen wurde herausgefunden, dass auch Polyethylen, mit einem Schmelzpunkt von ca. 110 °C, den Schmelzpunkt von beispielsweise Stearinsäure von 58°C auf 88 °C anhebt, wenn beide Stoffe in einem Mischverhältnis von 50:50 vermischt vorliegen. Bei Mischungsverhältnissen des Polyethylens mit Stearinsäure von 5:95 bis 10:90, ergibt sich dagegen eine Schmelzpunkterniedrigung um ca. 4 °C, d. h. diese Mischungen schmelzen unterhalb der Schmelzpunkte der Einzelkomponenten. Bei Mischungen über 10% Polyethylen steigt der Schmelzpunkt über den Schmelzpunkt der niedrig schmelzenden Stearinsäure. Bei 15% Polyethylen beträgt der Mischschmelzpunkt ca. 78 °C.The melting point of low melting waxes can be increased by admixing a high melting polymer, e.g. B. with polyethylene glycol. - It has been found in experiments that also polyethylene, with a melting point of about 110 ° C, the melting point of, for example, stearic acid from 58 ° C to 88 ° C raises when both substances are mixed in a mixing ratio of 50:50. At mixing ratios of the polyethylene with stearic acid from 5:95 to 10:90, however, results in a melting point reduction by about 4 ° C, d. H. These mixtures melt below the melting points of the individual components. For blends above 10% polyethylene, the melting point rises above the melting point of low melting stearic acid. At 15% polyethylene, the mixed melting point is approx. 78 ° C.

Um den genannten Nachteil niedrig schmelzender Mono-Carbonsäuren in der erfinderischen Mischung auszugleichen, ist vorgesehen, den niedrig schmelzenden Mono-Carbonsäuren einen höher schmelzenden Stoff, vorzugsweise Polyethylenglycol oder Polyethylen in Anteilen von 10% - 20%, bei zu mischen.In order to compensate for the mentioned disadvantage of low-melting mono-carboxylic acids in the inventive mixture, it is provided to mix the low-melting mono-carboxylic acids a higher-melting substance, preferably polyethylene glycol or polyethylene in proportions of 10% - 20%.

Als Oxidationsmittel können Chlorate aus der Gruppe der Alkalimetalle verwendet werden. Insbesondere Kaliumchlorat hat sich als Oxidationsmittel als vorteilhaft erwiesen.As the oxidizing agent, chlorates from the group of alkali metals can be used. In particular, potassium chlorate has proven to be advantageous as an oxidizing agent.

Bei dem Reduktionsmittel kann es sich um ein Kohlehydrat oder um ein Gemisch aus verschiedenen Kohlehydraten aus den Gruppen der Mono- oder Di-Sacharide handeln. Vorzugsweise kann es sich bei dem Reduktionsmittel um Glucose, Saccharose und Milchzucker handeln.The reducing agent may be a carbohydrate or a mixture of different carbohydrates from the groups of mono- or di-saccharides. Preferably, the reducing agent may be glucose, sucrose and lactose.

Die pyrotechnische Mischung kann zusätzlich einen Füllstoff enthalten. Für die erfindungsgemäße Zusammensetzung haben sich hydratisierte Aluminiumsilikate, insbesondere natürliche Kaoline wie Bolus alba als besonders vorteilhaft erwiesen.The pyrotechnic mixture may additionally contain a filler. Hydrated aluminum silicates, in particular natural kaolins such as bolus alba, have proven particularly advantageous for the composition according to the invention.

Die Bestandteile der pyrotechnischen Mischung können in pulverisierter Form vermischt und verarbeitet werden. Die Mischung kann auch ohne Zugabe eines Bindemittels mit Wasser granuliert werden. Die Pulvermischung oder das Granulat lassen sich anschließend direkt in einen entsprechenden Container etc. abfüllen. Üblicherweise wird die Mischung zusammen mit einem Anzündsatz in den / die Container etc. gepresst. Dadurch lässt sich der Nebelsatz bzw. der Nebelkörper einfach und kostengünstig herstellen.The components of the pyrotechnic mixture can be mixed and processed in powdered form. The mixture can also be granulated without addition of a binder with water. The powder mixture or the granulate can then be filled directly into a corresponding container, etc. Usually, the mixture is pressed together with a primer in the / the container, etc. As a result, the mist set or the mist body can be produced easily and inexpensively.

Die Brenngeschwindigkeit hängt u a. von der Größe der Oberfläche (Korngröße, Geometrie) des Granulats ab. Für spezielle Anwendungen, beispielsweise wenn die pyrotechnische Mischung sehr schnell abbrennen soll (Spontannebel), kann dieses Granulat in einen Container abgefüllt verwendet werden. Zusätzlich kann das Granulat noch mit einer pyrotechnischen Anzündmischung umhüllt sein, um das Anbrennen des Granulates zu verbessern. Um die mechanische Festigkeit des Granulates zu erhöhen, kann der pyrotechnischen Mischung aber auch ein Bindemittel zugesetzt werden, das vorzugsweise aus der Gruppe der Celluloseester, Dextrine o.ä. stammt.The burning speed depends on a. on the size of the surface (grain size, geometry) of the granules. For special applications, for example, when the pyrotechnic mixture is to burn off very quickly (spontaneous mist), this granulate can be used in a container filled. In addition, the granules may still be coated with a pyrotechnic igniter mixture in order to improve the firing of the granules. In order to increase the mechanical strength of the granules, the pyrotechnic mixture but also a binder can be added, preferably from the group of cellulose esters, dextrins or similar. comes.

Um die chemische Stabilität der pyrotechnischen Mischung, die von sich aus keine sauren Bestandteile enthält und bei Zugabe von Wasser eine nahezu neutrale Reaktion zeigt, zu erhöhen, können der Mischung vorsorglich neutralisierend wirkende Salze zugemischt werden, um die Bildung selbstentzündlicher Chlorsäure zu verhindern. Bei den Neutralisationsmitteln handelt es sich vorzugsweise um Carbonate oder Hydroxidcarbonate der Erdalkaligruppe, wie z. B. Calciumcarbonat und Magnesiumhydroxidcarbonat, oder Aluminiumhydroxid. Üblicherweise ist eine Beimischung dieser Neutralisationsmittel von 2% zu der pyrotechnischen Mischung ausreichend. In Abhängigkeit von der zugegebenen Menge des Neutralisationsmittels, können diese, ähnlich wie Aluminiumsilikat, den Abbrand der pyrotechnischen Mischung regulieren und einen Teil des Aluminiumsilikates ersetzen.In order to increase the chemical stability of the pyrotechnic mixture, which by itself contains no acidic constituents and shows a nearly neutral reaction when water is added, precautionary neutralizing salts may be added to the mixture in order to prevent the formation of auto-ignitable chloric acid. The neutralizing agents are preferably carbonates or Hydroxidcarbonate the alkaline earth group, such as. For example, calcium carbonate and magnesium hydroxide carbonate, or aluminum hydroxide. Usually, an admixture of these neutralizing agents of 2% to the pyrotechnic mixture is sufficient. Depending on the added amount of the neutralizing agent, these can, similar to aluminum silicate, regulate the combustion of the pyrotechnic mixture and replace part of the aluminum silicate.

Zur Reduzierung der Reib- und Schlagempfindlichkeit der pyrotechnischen Mischung können dieser Graphit oder Bornitrid beigemischt werden.To reduce the friction and impact sensitivity of the pyrotechnic mixture, this graphite or boron nitride can be mixed.

Die Verwendung der pyrotechnischen Mischung in Containern, Behältern etc. kann sehr vielfältig sein. Beispielsweise kann es sich bei dem Container auch um einen Wurfkörper, eine Granate oder eine den Container tragende Granate handeln, die aus einer Vielzahl verschiedener Materialien bestehen. Es sollte aber darauf geachtet werden, dass, da bestimmte Materialien, wie z. B. spezielle Kunststoffe aber auch anorganische Rückstände aus Oberflächenbehandlungen von metallischen Bauteilen, bei Temperaturen über 64 °C und / oder Anwesenheit von Restfeuchte durch Bildung der gefürchteten Chlorsäure aus dem Alkalichlorat zur Selbstentzündung der pyrotechnischen Mischung führen können, diese nicht verwendet werden.The use of the pyrotechnic mixture in containers, containers, etc. can be very diverse. For example, the container can also be a throwing body, a grenade or a grenade carrying the container, which consist of a multiplicity of different materials. However, it should be ensured that, because certain materials, such. B. special plastics but also inorganic residues from surface treatments of metallic components, at temperatures above 64 ° C and / or presence of residual moisture by formation of the dreaded chloric acid from the alkali chlorate can lead to spontaneous combustion of the pyrotechnic mixture, these are not used.

Nachfolgend werden besonders bevorzugte Ausführungsbeispiele der erfindungsgemäßen pyrotechnischen Mischungen näher erläutert:
a) Beispielhafte Mischungen für schnell abbrennende Nebelsätze (Gew.-%): I II III Kaliumchlorat 40 32 28 Saccharose 40 -- 28 Glucose -- 32 -- Behensäure 15 21 19 Emulgator 5 5 5 Aluminiumsilikat -- 10 20 Calciumcarbonat +2 +2 -- Aluminiumhydroxid -- -- +2 Graphit +3 -- -- Bornitrid -- +3 --
b) Beispielhafte Mischungen für langsam abbrennende Nebelsätze (Gew.-%) IV V VI VII VIII IX Kaliumchlorat 26 28 28 28 28 35 Saccharose 26 28 -- 28 28 25 Lactose -- -- 30 -- -- -- Behensäure -- 34 30 -- 24 25 Palmitinsäure -- -- -- 26 -- -- Stearinsäure 26 -- -- -- -- -- Polyethylen 4 -- -- 4 -- -- Emulgator 10 5 5 5 5 5 Aluminiumsilikat 8 5 9 9 15 10 Calciumcarbonat -- +2 +4 -- +2 -- MgCO3 Mg(OH)2 5H20 -- -- -- +2 -- +2 Bornitrid -- +3 -- -- -- +3 In the following, particularly preferred embodiments of the pyrotechnic mixtures according to the invention are explained in more detail:
a) Exemplary Mixtures for Fast-Burning Fog Sets (% by Weight): I II III potassium chlorate 40 32 28 sucrose 40 - 28 glucose - 32 - behenic 15 21 19 emulsifier 5 5 5 aluminosilicate - 10 20 calcium carbonate +2 +2 - aluminum hydroxide - - +2 graphite +3 - - boron nitride - +3 -
b) Exemplary Mixtures for Slow-Burning Fog Sets (% by Weight) IV V VI VII VIII IX potassium chlorate 26 28 28 28 28 35 sucrose 26 28 - 28 28 25 lactose - - 30 - - - behenic - 34 30 - 24 25 palmitic - - - 26 - - stearic acid 26 - - - - - polyethylene 4 - - 4 - - emulsifier 10 5 5 5 5 5 aluminosilicate 8th 5 9 9 15 10 calcium carbonate - +2 +4 - +2 - MgCO3 Mg (OH) 2 5H20 - - - +2 - +2 boron nitride - +3 - - - +3

Zur Herstellung abriebfester Granulate, können den Mischungen vorzugsweise Zelluloseester in Anteilen von 1 - 5% zugemischt und die Wasser feuchte Mischung anschließend granuliert werden.For the production of abrasion-resistant granules, preferably cellulose esters in proportions of 1-5% can be added to the mixtures and the water-moist mixture subsequently granulated.

Claims (13)

  1. Pyrotechnic mixture for generating a smokescreen, comprising at least one oxidizer, at least one reducer and at least one vaporizable, smoke-forming composition, characterized in that the smoke-forming composition comprises a mixture of at least one saturated, long-chain aliphatic monocarboxylic acid and at least one emulsifier.
  2. Pyrotechnic mixture according to Claim 1, characterized in that the aliphatic monocarboxylic acid comprises monocarboxylic acids having a carbon chain length of C14 to C24 and the at least one emulsifier comprises an emulsifier from the group of mono- or diglyceride fatty acid esters or mixtures thereof or of fruit-acid-esterified mono- or diglyceride fatty acid esters or mixtures thereof.
  3. Pyrotechnic mixture according to Claim 1 or 2, characterized in that the monocarboxylic acid comprises palmitic acid, stearic acid or behenic acid or mixtures of these, and the fraction of the monocarboxylic acids in the pyrotechnic mixture is preferably 10% - 40%.
  4. Pyrotechnic mixture according to Claim 1 to 3, characterized in that the pyrotechnic mixture comprises a substance raising the melting point relative to the monocarboxylic acid, and the fraction of the substance raising the melting point relative to the carboxylic acid is preferably 10% - 40%.
  5. Pyrotechnic mixture according to Claim 4, characterized in that the melting-point-raising substance comprises polyethylene glycol or polyethylene or mixtures of these.
  6. Pyrotechnic mixture according to any of Claims 1 to 5, characterized in that the oxidizer comprises chlorates from the group of the alkali metals, and the fraction of the oxidizer is preferably 20% - 45%.
  7. Pyrotechnic mixture according to Claim 6, characterized in that the oxidizer comprises potassium chlorate.
  8. Pyrotechnic mixture according to any of Claims 1 to 7, characterized in that the reducer comprises a carbohydrate or comprises a mixture of different carbohydrates from the groups of the mono- or disaccharides, and the fraction of the reducer is preferably 20% - 45%.
  9. Pyrotechnic mixture according to Claim 8, characterized in that the reducer comprises glucose, sucrose, lactose or mixtures of these.
  10. Pyrotechnic mixture according to any of Claims 1 to 9, characterized in that the pyrotechnic mixture comprises a filler, preferably natural, hydrated aluminium silicate, and the fraction is preferably 0% - 20%.
  11. Pyrotechnic mixture according to any of Claims 1 to 10, characterized in that graphite or boron nitride has been admixed.
  12. Pyrotechnic mixture according to any of Claims 1 to 11, characterized in that the mixture comprises granules, preferably enveloped with a pyrotechnic ignition mixture.
  13. Use of the pyrotechnic mixture according to any of Claims 1 to 12 in encasements, containers, etc., such as, for example, in a hand grenade, a shell or a shell bearing the encasement.
EP13817671.4A 2012-12-19 2013-12-11 Pyrotechnic mixture for producing an aerosol Active EP2935160B1 (en)

Priority Applications (1)

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PL13817671T PL2935160T3 (en) 2012-12-19 2013-12-11 Pyrotechnic mixture for producing an aerosol

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DE102012024809.1A DE102012024809B4 (en) 2012-12-19 2012-12-19 Pyrotechnic mixture for generating an aerosol and its use
PCT/EP2013/076270 WO2014095532A2 (en) 2012-12-19 2013-12-11 Pyrotechnic mixture for producing an aerosol

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EP2935160A2 EP2935160A2 (en) 2015-10-28
EP2935160B1 true EP2935160B1 (en) 2018-06-20

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DE (1) DE102012024809B4 (en)
DK (1) DK2935160T3 (en)
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PL (1) PL2935160T3 (en)
WO (1) WO2014095532A2 (en)

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TWI726626B (en) 2020-02-19 2021-05-01 大陸商廣州市創韋照明燈具有限公司 Sugar-containing aqueous solution formula suitable for producing smoke and method of using sugar-containing aqueous solution to produce smoke

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US2489549A (en) * 1947-05-20 1949-11-29 Vinton John Signal smoke compositions
US4032374A (en) 1976-09-22 1977-06-28 The United States Of America As Represented By The Secretary Of The Navy Cinnamic acid containing pyrotechnic smoke composition
LU85676A1 (en) * 1984-12-10 1986-07-17 Radermecker Interchimie S A ALKALINE SMOKE AND APPLICATION FOR CONTROLLING ATMOSPHERIC POLLUTION, PARTICULARLY ACID RAIN
USH233H (en) * 1986-08-29 1987-03-03 The United States Of America As Represented By The Secretary Of The Army Smoke producing composition
DE3728380C1 (en) 1987-08-26 1988-11-24 Nico Pyrotechnik Pyrotechnic mixture for the production of a camouflage mist and ignition mixture therefor
US5154782A (en) * 1991-08-15 1992-10-13 Thiokol Corporation Obscuring and nontoxic smoke compositions
US5522320A (en) * 1993-07-12 1996-06-04 Thiokol Corporation Low-toxicity obscuring smoke formulation
US6558487B1 (en) * 2001-07-24 2003-05-06 The United States Of America As Represented By The Secretary Of The Army Smoke generating compositions and methods of making the same
EP1688049A1 (en) * 2005-02-03 2006-08-09 findusFit Sportdiätetika GmbH Dietary foodstuff
DE112006001782T5 (en) * 2005-06-30 2008-05-29 Automotive Systems Laboratory, Inc., Armada Ignition compositions

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Publication number Publication date
DE102012024809A1 (en) 2014-06-26
EP2935160A2 (en) 2015-10-28
DK2935160T3 (en) 2018-09-24
WO2014095532A3 (en) 2014-11-13
ES2687849T3 (en) 2018-10-29
PL2935160T3 (en) 2019-01-31
WO2014095532A2 (en) 2014-06-26
DE102012024809B4 (en) 2014-09-11

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