EP1173394B1 - Pyrotechnic active mass for producing an aerosol highly emissive in the infrared spectrum and impenetrable in the visible spectrum - Google Patents
Pyrotechnic active mass for producing an aerosol highly emissive in the infrared spectrum and impenetrable in the visible spectrum Download PDFInfo
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- EP1173394B1 EP1173394B1 EP00901589A EP00901589A EP1173394B1 EP 1173394 B1 EP1173394 B1 EP 1173394B1 EP 00901589 A EP00901589 A EP 00901589A EP 00901589 A EP00901589 A EP 00901589A EP 1173394 B1 EP1173394 B1 EP 1173394B1
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- impenetrable
- active mass
- red phosphorus
- aerosol
- alkali metal
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- 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)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H3/00—Camouflage, i.e. means or methods for concealment or disguise
Definitions
- the present invention relates to a human and ecotoxicological compatible pyrotechnic active material consisting of red phosphorus, one metallic fuel from the group of transition metals, preferably Titanium, zirconium or iron, a moderator from the group of metalloids boron and silicon, an oxidizing agent from the group of the alkali metal nitrates is preferred Cesium nitrate and potassium nitrate, which are used to produce an im Infrared (3-5, 8-14 ⁇ m) highly emissive and visually impenetrable Aerosols are suitable.
- Aerosols based on organic azo dyes are used (white, orange, red, violet, green, blue) which are only in the visible range of the spectrum absorb, preferably used for camouflage, deception and blinding Aerosols, which also include the infrared region of the electromagnetic spectrum especially in the area of the atmospheric transmission window at 0.3 - 1.5; 1.6-1.8; 2.0-2.5; 3.0-5.0 and 8.0-14 ⁇ m through different mechanisms interrupt. These mechanisms include scattering, absorption and Radiation emission.
- I the radiation intensity weakened by the interactions
- I 0 the initial intensity
- c corresponds to the concentration of the aerosol per unit volume
- l is the path length of the isotropic density assumed by the aerosol cloud
- the scattering process mainly depends on the particle morphology and size of the particles, the absorption is only determined by the chemical composition of the particles. Only the refractive index m of an aerosol, which is determined both by the physical and chemical properties, influences both the scattering and the absorption behavior.
- the particle diameter assuming the spherical morphology of the particles, and the wavelength of the radiation to be scattered must be identical. This means that for optimal scattering of radiation in the micrometer range there must be particles with particle diameters of 0.3 - 14 ⁇ m.
- the aerosols described under a) and b) have a chemical composition to absorb infrared radiation. Both soot and Brass dust is electrically conductive and therefore for coupling infrared radiation suitable.
- the disadvantages of the methods for generating infrared radiation described above shielding aerosol clouds consist in a) in the contamination of the produced soot particles with partly carcinogenic polyaromatic Hydrocarbons (PAH) and in the case of energetic halogenated ones Components in such pyrotechnic sentences in the contamination of the Carbon black particles with polyhalogenated oxyarenes such as e.g. Polyhalogendibenzofuranen and polyhalodibenzodioxins or also polyhalogenated Biphenyls.
- PAH polyaromatic Hydrocarbons
- EP106394 active compounds which contain red phosphorus, CsNO 3 , B, Ti or a Zr / Ni alloy and a binder.
- a disadvantage of this process is that the polyaromatics formed are also contain carcinogenic substances, and the emissive effect due to use of magnesium subsides very quickly.
- the object of the present invention was therefore to create a new camouflage fog develop, in addition to the impenetrability in the visible area also a long-lasting coverage in the IR range.
- the main components of the mist sets according to the invention include red phosphorus, an alkali metal nitrate such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate and cesium nitrate, or a mixture thereof, and, as secondary components, a metallic fuel from the group of transition metals such as titanium, zirconium or iron or one metal-rich alloy or compound of these elements such as TiH, Zr / Ni, Zr / Fe or ZrSi 2 , at least one metalloid such as boron or silicon or an electron-donating compound of these elements, and a polymeric organic binder.
- red phosphorus serves as a carrier for the transmission-damping effect in the visible range, but new is the knowledge that under certain circumstances the red phosphorus also acts as a carrier for the emissive effect in the infrared range.
- the red phosphorus is largely evaporated during the conversion of the energetic components nitrate / metal / metalloid (Eq. 3) and burns to phosphorus pentoxide in the presence of atmospheric oxygen according to equation (4).
- Phosphorus pentoxide reacts with the air humidity according to equation 5 to phosphoric acid.
- alkali metal nitrates as an oxidizing agent according to the invention provides alkali metal oxides during combustion, which in the presence of atmospheric moisture acc. GI. 6 react to the hydroxides.
- M Na, K, Rb, Cs
- the aerosol droplets formed have a size of 0.01-2 ⁇ m and thereby high absorption and scattering coefficients in the visible and short-wave Infrared range from 0.3 - 1.9 ⁇ m and low attenuation values in the middle and long-wave infrared from 2 - 14 ⁇ m.
- the Reactions 4 - 6 but especially heat generated in steps 7 and 8 for strong emission of the aerosol droplets in the middle and long-wave infrared, and thus compensates for the low scatter and Absorption coefficient.
- the heat development according to the invention occurs in part through chemical processes that are only delayed by the onset of education of the aerosol droplets become possible, so that this emissive effect 50 - 200 sec., I.e. for the time necessary for camouflage.
- transition metals Through the use of transition metals according to the invention, their oxides have high levels of heat, such as zirconium and titanium, as well Metalloids such as boron and / or silicon have very high combustion temperatures reached, therefore the aerosol particles get a high thermal Energy, which increases the emission in the long-wave IR.
- transition metals and their alloys or metal-rich compounds continue to suppress the formation of Phosphansentnern.
- the incineration due to oxygen underbalancing formed metal phosphides e.g. zirconium phosphide or titanium phosphide have non-ionic character, which is why with humidity or acid Rain does not result in hydrolysis or acidolysis with the release of phosphines.
- fog sentences laboratoryized according to the invention are human and ecotoxicological compatible and considerably safer than conventional fog sets based on red phosphorus and light metal such as magnesium or aluminum. This is also typical for mist sets based on red phosphorus self-igniting of the combustion residues no longer occurs.
- Radiometric measurement of the resulting aerosol at a distance of 4 m from the source reveals the following radiation levels in the infrared range: Band V (8 - 14 ⁇ m) Band II (3 - 5 ⁇ m) > 100 W / sr> 25 s > 20 W / sr> 25 s > 60 W / sr> 75 s > 10 W / sr> 75 s.
- FIG. 1 shows the radiant intensity of the aerosol clouds which are produced by burning off a compact of the mass 120 g, which has been processed according to the invention, at a distance of 5 m from the source.
- the aerosol clouds generated according to the invention very good irradiation (> 95%) of emissive targets, the color temperature 300 ° C., is achieved.
Abstract
Description
Gegenstand der vorliegenden Erfindung ist eine human- und ökotoxikologisch verträgliche pyrotechnische Wirkmasse, bestehend aus rotem Phosphor, einem metallischen Brennstoff aus der Gruppe der Übergangsmetalle, vorzugsweise Titan, Zirconium oder Eisen, einem Moderator aus der Gruppe der Metalloide Bor und Silicium, einem Oxidationsmittel aus der Gruppe der Alkalimetallnitrate vorzugsweise Caesiumnitrat und Kaliumnitrat, welche sich zur Erzeugung eines im Infraroten (3-5, 8-14 µm) stark emissiven und im Visuellen undurchdringlichen Aerosols eignet.The present invention relates to a human and ecotoxicological compatible pyrotechnic active material consisting of red phosphorus, one metallic fuel from the group of transition metals, preferably Titanium, zirconium or iron, a moderator from the group of metalloids boron and silicon, an oxidizing agent from the group of the alkali metal nitrates is preferred Cesium nitrate and potassium nitrate, which are used to produce an im Infrared (3-5, 8-14 µm) highly emissive and visually impenetrable Aerosols are suitable.
Pyrotechnisch erzeugte Aerosole werden heute überwiegend im militärischen Bereich zum Tarnen, Täuschen, Blenden, Simulieren und Markieren eingesetzt.Today, pyrotechnically generated aerosols are mainly used in the military Area used for camouflaging, deceiving, dazzling, simulating and marking.
Während für die Anwendungsfälle Markieren und Simulieren vorzugsweise farbige Aerosole auf Basis organischer Azofarbstoffe zum Einsatz kommen (weiß, orange, rot, violett, grün, blau) die nur im sichtbaren Bereich des Spektrums absorbieren, verwendet man zum Tarnen, Täuschen und Blenden vorzugsweise Aerosole, die auch den infraroten Bereich des elektromagnetischen Spektrums speziell im Bereich der atmosphärischen Transmissionsfenster bei 0,3 - 1,5; 1,6-1,8; 2,0 - 2,5; 3,0- 5,0 und 8,0 - 14 µm durch verschiedene Mechanismen unterbrechen. Zu diesen Mechanismen zählen die Streuung, Absorption und Emission von Strahlung. While marking and simulating are preferably colored for use cases Aerosols based on organic azo dyes are used (white, orange, red, violet, green, blue) which are only in the visible range of the spectrum absorb, preferably used for camouflage, deception and blinding Aerosols, which also include the infrared region of the electromagnetic spectrum especially in the area of the atmospheric transmission window at 0.3 - 1.5; 1.6-1.8; 2.0-2.5; 3.0-5.0 and 8.0-14 µm through different mechanisms interrupt. These mechanisms include scattering, absorption and Radiation emission.
Streuung und Absorption von Strahlung werden durch das Lambert-Beersche
Gesetz beschrieben.
Wobei I die durch die Wechselwirkungen abgeschwächte Strahlungsintensität
beschreibt, I0 die anfängliche Intensität darstellt. c entspricht der Konzentration
des Aerosols pro Volumeneinheit, l ist die Pfadlänge durch die Aerosolwolke
angenommener isotroper Dichte. α ist der wellenlängenabhängige Massenextinktionskoeffizient
der Aerosolpartikeln, der sich bei einem gegebenen Stoff als
Summe der Streu- und Absorptionskoeffizienten zusammensetzt:
Während der Streuvorgang überwiegend von der Partikelmorphologie und Größe der Partikeln abhängt, wird die Absorption nur durch die chemische Zusammensetzung der Partikeln bestimmt. Lediglich der Brechungsindex m eines Aerosols welcher sowohl von den physikalischen wie chemischen Eigenschaften bestimmt wird, beeinflußt sowohl das Streu- wie auch das Absorptionsverhalten.While the scattering process mainly depends on the particle morphology and size of the particles, the absorption is only determined by the chemical composition of the particles. Only the refractive index m of an aerosol, which is determined both by the physical and chemical properties, influences both the scattering and the absorption behavior.
Damit Aerosole Strahlung streuen können, müssen nach Rayleigh der Partikeldurchmesser, bei angenommener sphärischer Morphologie der Partikeln, und die Wellenlänge der zu streuenden Strahlung identisch sein. Das bedeutet, daß für eine optimale Streuung von Strahlung im Mikrometer-Bereich Partikeln mit Teilchendurchmessern von 0,3 - 14 µm vorliegen müssen. According to Rayleigh , in order for aerosols to scatter radiation, the particle diameter, assuming the spherical morphology of the particles, and the wavelength of the radiation to be scattered must be identical. This means that for optimal scattering of radiation in the micrometer range there must be particles with particle diameters of 0.3 - 14 µm.
Solche Partikeln können auf etablierte Weise durch folgende Prozesse erzeugt
werden:
Die unter a) und b) beschriebenen Aerosole tragen durch ihre chemische Zusammensetzung zur Absorption von Infrarotstrahlung bei. Sowohl Ruß als auch Messingstaub sind elektrisch leitfähig und daher zur Einkopplung von Infrarotstrahlung geeignet.The aerosols described under a) and b) have a chemical composition to absorb infrared radiation. Both soot and Brass dust is electrically conductive and therefore for coupling infrared radiation suitable.
Die Nachteile der oben beschriebenen Methoden zur Erzeugung von Infrarotstrahlung abschirmender Aerosolwolken bestehen bei a) in der Kontamination der erzeugten Rußteilchen mit z.T. cancerogenen polyaromatischen Kohlenwasserstoffen (PAH) und im Falle energetischer halogenhaltiger Komponenten in solchen pyrotechnischen Sätzen in der Kontamination der Rußteilchen mit polyhalogenierten Oxyarenen wie z.B. Polyhalogendibenzofuranen und Polyhalogendibenzodioxinen oder auch polyhalogenierte Biphenylen.The disadvantages of the methods for generating infrared radiation described above shielding aerosol clouds consist in a) in the contamination of the produced soot particles with partly carcinogenic polyaromatic Hydrocarbons (PAH) and in the case of energetic halogenated ones Components in such pyrotechnic sentences in the contamination of the Carbon black particles with polyhalogenated oxyarenes such as e.g. Polyhalogendibenzofuranen and polyhalodibenzodioxins or also polyhalogenated Biphenyls.
Bei der Explosivdispersion von vorkonfektionierten Partikeln kommt es stets zum sogenannten Bird-nesting. Darunter versteht man das durch den Explosionsvorgang in der Aerosolwolke hervorgerufenene Loch mit sehr niedriger Teilchendichte. An dieser Stelle der Wolke wird die Line of sight (LOS) nicht blockiert. Weiterhin sinkt Messingstaub sehr schnell zu Boden, so daß nur unbefriedigende Abdeckzeiten erreicht werden. Auch sind die toxischen Effekte von Messingstaub auf Mensch und Umwelt sehr beträchtlich, so daß von einer massenhaften Anwendung im besonderen auch für Übungszwecke abgesehen werden muß.So-called bird nesting always occurs with the explosive dispersion of pre-assembled particles. This means the hole with very low particle density caused by the explosion process in the aerosol cloud. At this point in the cloud, the line of sight (LOS) is not blocked. Furthermore, brass dust sinks to the ground very quickly, so that only unsatisfactory covering times are achieved. The toxic effects of brass dust on humans and the environment are also very considerable, so that mass application, especially for exercise purposes, has to be avoided.
In der EP106394 werden Wirkmassen beschrieben, die roten Phosphor, CsNO3, B, Ti oder eine Zr/Ni-Legierung und ein Bindmittel enthalten.In EP106394 active compounds are described which contain red phosphorus, CsNO 3 , B, Ti or a Zr / Ni alloy and a binder.
In der DE 40 30 430 wird eine Wirkmasse beschrieben, welche durch ein abgestimmtes Mengenverhältnis von Magnesiumpulver, einem fluorierten organischen Polymer, Chlorparaffin und einer aromatischen Verbindung, insbesondere Anthracen oder Phthalsäureanhydrid, beim Abbrand aromatische Radikale erzeugt, die zu Polyaromaten reagieren, welche als voluminöse Agglomerate mit faseriger Struktur Durchmesser im Bereich von 1 - 20 µm aufweisen, die für die IR-Strahlenstreuung und Absorption geeignet sind und trotzdem aufgrund der großen spezifischen Oberfläche in der Luft schweben. Um die Bildung von feinteiligem Ruß anstelle von Polyaromaten zu unterdrücken, muß eine Abbrandgeschwindigkeit von ca. 15 g/sec. eingehalten werden, so daß die deckende Wirkung erst relativ spät einsetzt. Daher wird in diesem Patent weiter vorgeschlagen, eine schnell abbrennende Mischung aus fluorhaltigem Polymer, Magnesiumpulver und einem organischen Binder zuzufügen, die kurzfristig beim Abbrennen eine starke IR-Emission erzeugt und damit die anfängliche Deckungslücke schließt.In DE 40 30 430 an active mass is described, which by a coordinated Quantity ratio of magnesium powder, a fluorinated organic Polymer, chlorinated paraffin and an aromatic compound, in particular Anthracene or phthalic anhydride, aromatic radicals on burning generated, which react to polyaromatics, which as voluminous agglomerates with fibrous structure have diameters in the range of 1 - 20 µm, which for the IR radiation scattering and absorption are suitable and nevertheless due to the large specific surface suspended in the air. To the formation of To suppress finely divided soot instead of polyaromatics, one must Burning rate of approx. 15 g / sec. be observed so that the opaque effects appear relatively late. Therefore, this patent continues proposed a rapidly burning mixture of fluorine-containing polymer, Add magnesium powder and an organic binder, the short term when Burning off produces a strong IR emission and thus the initial one Cover gap closes.
Nachteilig an diesem Verfahren ist es, daß die gebildeten Polyaromate auch noch cancerogene Substanzen enthalten, und die emissive Wirkung wegen der Verwendung von Magnesium sehr rasch abklingt.A disadvantage of this process is that the polyaromatics formed are also contain carcinogenic substances, and the emissive effect due to use of magnesium subsides very quickly.
Das Hauptproblem herkömmlicher undurchdringlicher Aerosole der oben beschriebenen Art besteht in der Unwirksamkeit, bewegliche, warme Ziele (Menschen, Fahrzeuge, gepanzerte Plattformen) gegen CLOS und SACLOS-Lenkwaffen (z.B. Milan, TOW u.s.w.) wirksam zu schützen. Diese Lenkwaffen werden vermittels Draht oder Glasfaser durch einen Bediener gesteuert, welcher über ein Wärmebildgerät (8 - 14 µm) das Ziel anvisiert. Nach erfolgter Zielauffassung kann ein Bediener aus der letzten wahrgenommenen Bewegung die ungefähre Position abschätzen und durch die typischerweise in Aerosolwolken befindlichen Transmissionslöcher das emissive Ziel weiter verfolgen und den Flugkörper ins Ziel lenken.The main problem with conventional impenetrable aerosols of the type described above is the ineffectiveness of effectively protecting moving, warm targets (people, vehicles, armored platforms) against CLOS and SACLOS guided weapons (e.g. Milan, TOW, etc.). These guided missiles are controlled by wire or glass fiber by an operator who uses a thermal imaging device (8 - 14 µm) to aim at the target. After the target has been recognized, an operator can estimate the approximate position from the last perceived movement and continue to follow the emissive target through the transmission holes typically located in aerosol clouds and guide the missile to the target.
Aufgabe der vorliegenden Erfindung war es daher, einen neuen Tarnnebel zu entwickeln, der neben der Undurchdringlichkeit im sichtbaren Bereich auch eine langanhaltende Deckung im IR-Bereich ermöglicht.The object of the present invention was therefore to create a new camouflage fog develop, in addition to the impenetrability in the visible area also a long-lasting coverage in the IR range.
Die Lösung dieser Aufgabe wird durch die Merkmale des Hauptanspruchs erreicht und durch die des Unteranspruchs gefördert.This object is achieved by the features of the main claim and promoted by that of the subclaim.
Die erfindungsgemäßen Nebelsätze enthalten als Hauptbestandteile roten Phosphor, ein Alkalimetallnitrat wie beispielsweise Lithiumnitrat, Natriumnitrat, Kaliumnitrat, Rubidiumnitat und Caesiumnitrat, bzw. eine Mischung derselben, sowie als Nebenbestandteile einen metallischen Brennstoff aus der Gruppe der Übergangsmetalle wie beispielsweise Titan, Zirconium oder Eisen bzw. eine metallreiche Legierung oder Verbindung dieser Elemente wie beispielsweise TiH, Zr/Ni, Zr/Fe oder ZrSi2, mindestens ein Metalloid wie beispielsweise Bor oder Silicium bzw. eine elektronenspendende Verbindung dieser Elemente, sowie einen polymeren organischen Binder.The main components of the mist sets according to the invention include red phosphorus, an alkali metal nitrate such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate and cesium nitrate, or a mixture thereof, and, as secondary components, a metallic fuel from the group of transition metals such as titanium, zirconium or iron or one metal-rich alloy or compound of these elements such as TiH, Zr / Ni, Zr / Fe or ZrSi 2 , at least one metalloid such as boron or silicon or an electron-donating compound of these elements, and a polymeric organic binder.
Daß der rote Phosphor als Träger der transmissionsdämpfenden Wirkung im
sichtbaren Bereich dient war bislang bekannt, neu hingegen ist die Erkenntnis,
daß der rote Phosphor unter bestimmten Umständen auch als Träger der emissiven
Wirkung im infraroten Bereich wirkt. Der rote Phosphor wird bei der Umsetzung
der energetischen Komponenten Nitrat/Metall/Metalloid, weitgehend verdampft
(GI. 3) und verbrennt in Gegenwart des Luftsauerstoffs gemäß Gleichung
(4) zu Phosphorpentoxid.
Phosphorpentoxid reagiert mit der Luftfeuchtigkeit gemäß Gleichung 5 zu Phosphorsäure.
Die erfindungsgemäße Verwendung von Alkalimetallnitraten als Oxidationsmittel
liefert beim Abbrand Alkalimetalloxide, welche in Gegenwart der Luftfeuchtigkeit
gem. GI. 6 zu den Hydroxiden abreagieren.
Diese Aerosoltröpfchen liefern mit den Phosphorsäuretröpfchen in einer stark
exothermen Reaktion die entsprechenden Dihydrogenphosphate.
Die Hydratisierung der Dihydrogenphosphate ist ebenfalls eine exotherme Reaktion
und liefert nochmals Wärme.
Die gebildeten Aerosoltröpfchen besitzen eine Größe von 0,01 - 2 µm und dadurch hohe Absorptions- und Streukoeffizienten im sichtbaren und kurzwelligen Infrarotbereich von 0,3 - 1,9 µm und niedrige Dämpfungswerte im mittleren und langwelligen Infrarot von 2 - 14 µm. Unbeschadet dessen sorgt die durch die Reaktionen 4 - 6 aber insbesondere in den Schritten 7 und 8 gebildete Wärme für eine starke Emission der Aerosoltröpfchen im mittleren und langwelligen Infrarot, und kompensiert so die in diesem Spektralbereich niedrigen Streu- und Absorptionskoeffizienten. Im Gegensatz zu der bekannten starken Emission von Magnesium-haltigen Wirkmassen, die direkt bei der Verbrennung auftritt und danach schnell abklingt, tritt die erfindungsgemäße Wärmeentwicklung teilweise durch chemische Prozesse auf, die erst durch die verzögert einsetzende Bildung der Aerosoltröpfchen möglich werden, so daß diese emissive Wirkung 50 - 200 sec., d.h. für die für eine Tarnung notwendige Zeit anhält.The aerosol droplets formed have a size of 0.01-2 µm and thereby high absorption and scattering coefficients in the visible and short-wave Infrared range from 0.3 - 1.9 µm and low attenuation values in the middle and long-wave infrared from 2 - 14 µm. Without prejudice to that, the Reactions 4 - 6 but especially heat generated in steps 7 and 8 for strong emission of the aerosol droplets in the middle and long-wave infrared, and thus compensates for the low scatter and Absorption coefficient. Contrary to the well known strong emission of Magnesium-containing active masses that occur directly during combustion and then quickly subsides, the heat development according to the invention occurs in part through chemical processes that are only delayed by the onset of education of the aerosol droplets become possible, so that this emissive effect 50 - 200 sec., I.e. for the time necessary for camouflage.
Durch die erfindungsgemäße Verwendung von Übergangsmetallen deren Oxide hohe Bildungswärmen aufweisen, wie beispielsweise Zirconium und Titan, sowie von Metalloiden wie Bor und/oder Silicium werden sehr hohe Verbrennungstemperaturen erreicht, daher erhalten die Aerosolpartikeln eine hohe thermische Energie, was die Emission im langwelligen IR steigert.Through the use of transition metals according to the invention, their oxides have high levels of heat, such as zirconium and titanium, as well Metalloids such as boron and / or silicon have very high combustion temperatures reached, therefore the aerosol particles get a high thermal Energy, which increases the emission in the long-wave IR.
Die erfindungsgemäße Verwendung der Übergangsmetalle und deren Legierungen bzw. metallreichen Verbindungen unterdrückt weiterhin die Entstehung von Phosphanbildnern. Die bei der Verbrennung aufgrund der Sauerstoffunterbilanzierung gebildeten Metallphosphide (z.B. Zirconiumphosphid oder Titanphosphid besitzen nichtionischen Charakter, weshalb mit Luftfeuchtigkeit oder Saurem Regen keine Hydrolyse oder Acidolyse mit Freisetzung von Phosphanen eintritt. The use according to the invention of the transition metals and their alloys or metal-rich compounds continue to suppress the formation of Phosphanbildnern. The incineration due to oxygen underbalancing formed metal phosphides (e.g. zirconium phosphide or titanium phosphide have non-ionic character, which is why with humidity or acid Rain does not result in hydrolysis or acidolysis with the release of phosphines.
Daher sind erfindungsgemäß laborierte Nebelsätze human- und ökotoxikologisch verträglich und erheblich sicherer als konventionelle Nebelsätze auf der Basis von rotem Phosphor und Leichtmetall wie beispielsweise Magnesium oder Aluminium. Auch ist damit die bei Nebelsätzen auf Basis von rotem Phosphor typischerweise auftretende Selbstentzündlichkeit der Abbrandrückstände nicht mehr gegeben.Therefore, fog sentences laboratoryized according to the invention are human and ecotoxicological compatible and considerably safer than conventional fog sets based on red phosphorus and light metal such as magnesium or aluminum. This is also typical for mist sets based on red phosphorus self-igniting of the combustion residues no longer occurs.
Das folgende Beispiel soll die Erfindung verdeutlichen ohne sie jedoch zu beschränken:The following example is intended to illustrate the invention without, however, to restrict:
Aus 2750 g Rotem Phosphor, 990 g Kaliumnitrat, 220 g Silicium, 220 g Bor, 220 g Zirconium und 990 g Macroplast-Binder (30 % Festkörper) wird durch schrittweise Zugabe der Komponenten zum roten Phosphor ein teigiger Satz erzeugt. Die lösemittelfeuchte Masse wird (7 mm Maschenweite) gesiebt und 20 Minuten im Vakuum bei 40°C und 20 mbar getrocknet. Das 42 g Granulat werden mit einem Pressdruck von 20 Tonnen zu ringförmigen Presslingen von 10 mm Kantenhöhe 57 mm Außendurchmesser und 15 mm Innendurchmesser verpresst. Eine Tablette besitzt eine Brennzeit von ca. 35 Sekunden und liefert einen im visuellen dichten weißen Nebel.Made from 2750 g red phosphorus, 990 g potassium nitrate, 220 g silicon, 220 g boron, 220 g Zirconium and 990 g Macroplast binder (30% solids) is gradually removed Adding the components to the red phosphorus produces a doughy set. The solvent moist mass is sieved (7 mm mesh size) and 20 minutes in Vacuum dried at 40 ° C and 20 mbar. The 42 g of granules are mixed with a Pressing pressure of 20 tons into ring-shaped compacts with an edge height of 10 mm 57 mm outer diameter and 15 mm inner diameter pressed. A Tablet has a burning time of approx. 35 seconds and delivers one visually thick white fog.
Die radiometrische Vermessung des entstehenden Aerosols in 4 m Entfernung
der Quelle offenbart folgende Strahlstärken im infraroten Bereich:
Figur 1 zeigt die Strahlstärke der Aerosolwolken die durch Abbrand eines erfindungsgemäß laborierten Presslings der Masse 120g in 5 m Entfernung von der Quelle erzeugt werden. Mit den erfindungsgemäß erzeugten Aerosolwolken wird eine sehr gute Überstrahlung (> 95 %) emissiver Ziele, der Farbtemperatur 300 °C erreicht. FIG. 1 shows the radiant intensity of the aerosol clouds which are produced by burning off a compact of the mass 120 g, which has been processed according to the invention, at a distance of 5 m from the source. With the aerosol clouds generated according to the invention, very good irradiation (> 95%) of emissive targets, the color temperature 300 ° C., is achieved.
Claims (2)
- Pyrotechnic active mass for camouflaging and decoy purposes impenetrable in visual.light and strongly emissive in infrared light which, as main components, there are contained red phosphorus, an alkali metal nitrate or a mixture of alkali metal nitrates and, as subsidiary components, at least one transition metal or a metal-rich compound or alloy thereof, at least one metalloid, as well as a binder, characterised in that there are contained 55% to 62% red phosphorus, 18% to 23% alkali metal nitrates, 10 to 18% subsidiary components of transition metals and metalloids and 5 to 7% of binders.
- Pyrotechnic active mass according to claim 1, characterised in that there are contained 58.5% red phosphorus, 21.1% potassium nitrate, in each case 4.7% boron, silicon and zirconium, as well as 6.3% of a polychloroprene binder.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19914097 | 1999-03-27 | ||
DE19914097A DE19914097A1 (en) | 1999-03-27 | 1999-03-27 | Pyrotechnic active mass for generating an aerosol that is highly emissive in the infrared and impenetrable in the visual |
PCT/EP2000/000498 WO2000058237A1 (en) | 1999-03-27 | 2000-01-24 | Pyrotechnic active mass for producing an aerosol highly emissive in the infrared spectrum and impenetrable in the visible spectrum |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1173394A1 EP1173394A1 (en) | 2002-01-23 |
EP1173394B1 true EP1173394B1 (en) | 2004-03-17 |
EP1173394B9 EP1173394B9 (en) | 2004-10-13 |
Family
ID=7902742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00901589A Expired - Lifetime EP1173394B9 (en) | 1999-03-27 | 2000-01-24 | Pyrotechnic active mass for producing an aerosol highly emissive in the infrared spectrum and impenetrable in the visible spectrum |
Country Status (11)
Country | Link |
---|---|
US (1) | US6581520B1 (en) |
EP (1) | EP1173394B9 (en) |
JP (1) | JP2002540058A (en) |
AT (1) | ATE261921T1 (en) |
DE (2) | DE19914097A1 (en) |
DK (1) | DK1173394T3 (en) |
ES (1) | ES2218106T3 (en) |
IL (1) | IL145133A0 (en) |
PT (1) | PT1173394E (en) |
TR (1) | TR200102777T2 (en) |
WO (1) | WO2000058237A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004024857B4 (en) * | 2004-05-19 | 2008-07-10 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic set |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10226507A1 (en) | 2002-06-14 | 2003-12-24 | Diehl Munitionssysteme Gmbh | A smoke |
FR2849690B1 (en) * | 2003-01-08 | 2006-08-18 | Lacroix Soc E | PROTECTION DEVICE IN PARTICULAR FOR TERRESTRIAL VEHICLES |
US8414718B2 (en) * | 2004-01-14 | 2013-04-09 | Lockheed Martin Corporation | Energetic material composition |
DE102004018862A1 (en) * | 2004-04-19 | 2005-11-03 | Diehl Bgt Defence Gmbh & Co. Kg | Method and device for producing an infrared panel radiator |
DE102004047231B4 (en) * | 2004-09-28 | 2008-08-21 | Rheinmetall Waffe Munition Gmbh | submunitions |
US20060219341A1 (en) | 2005-03-30 | 2006-10-05 | Johnston Harold E | Heavy metal free, environmentally green percussion primer and ordnance and systems incorporating same |
DE102005020159B4 (en) * | 2005-04-29 | 2007-10-04 | Rheinmetall Waffe Munition Gmbh | Camouflage and deception ammunition for the protection of objects against missiles |
US7343861B1 (en) | 2005-05-31 | 2008-03-18 | The United States Of America As Represented By The Secretary Of The Navy | Device and method for producing an infrared emission at a given wavelength |
US7857921B2 (en) * | 2006-03-02 | 2010-12-28 | Alliant Techsystems Inc. | Nontoxic, noncorrosive phosphorus-based primer compositions |
US8540828B2 (en) | 2008-08-19 | 2013-09-24 | Alliant Techsystems Inc. | Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same |
US8641842B2 (en) | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
US8192568B2 (en) | 2007-02-09 | 2012-06-05 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
CA2942312C (en) | 2007-02-09 | 2019-05-28 | Vista Outdoor Operations Llc | Non-toxic percussion primers and methods of preparing the same |
WO2009048599A1 (en) | 2007-10-09 | 2009-04-16 | The Trustees Of Columbia University In The City Of New York | Friend or foe detection |
US7946228B2 (en) * | 2008-05-09 | 2011-05-24 | Wendy Gainsborough, legal representative | Self contained non toxic obscurant grenade and self-contained aerosol dispersing grenade |
DE102008033494A1 (en) | 2008-07-16 | 2010-01-21 | Diehl Bgt Defence Gmbh & Co. Kg | smoke pot |
DE102008036649A1 (en) | 2008-08-06 | 2010-02-18 | Diehl Bgt Defence Gmbh & Co. Kg | Active agent for selectively causing detonation or deflagration |
DE102008060573B4 (en) * | 2008-12-04 | 2016-08-11 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic active mass for the production of a camouflage nebula |
EP2396221A4 (en) * | 2009-02-11 | 2014-03-12 | Saab Ab | Decoy material package, a dispenser and a method for dispensing decoy material |
US8206522B2 (en) | 2010-03-31 | 2012-06-26 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same |
DE102013002119A1 (en) * | 2013-02-08 | 2014-08-28 | Rheinmetall Waffe Munition Gmbh | Explosive-free projectile for generating a thermal signature |
KR101478643B1 (en) * | 2014-08-14 | 2015-01-02 | 국방과학연구소 | Pyrotechnic smoke material for obscruing multi-spectrum using expanded graphite and red phosphorus |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE301646C (en) | ||||
US3730093A (en) * | 1966-12-27 | 1973-05-01 | North American Rockwell | Explosive apparatus |
DE2412346A1 (en) * | 1974-03-14 | 1975-09-25 | Buck Kg | HAND FIRE DEVICE WITH FIRE CHARGE |
DE2819850C2 (en) * | 1978-05-05 | 1980-03-20 | Buck Chemisch-Technische Werke Gmbh & Co, 8230 Bad Reichenhall | Pyrotechnic smoke kit |
DE3028933C1 (en) | 1980-07-30 | 1989-11-23 | Buck Chem Tech Werke | Heavy-duty molded fog body with broadband camouflage |
DE3031369C2 (en) * | 1980-08-20 | 1987-01-02 | Pyrotechnische Fabrik F. Feistel GmbH + Co KG, 6719 Göllheim | Pyrotechnic charge consisting of a smoke composition and an ignition charge and a method for producing the mist mixture and the ignition charge |
FR2560371B1 (en) | 1982-07-27 | 1989-03-31 | France Etat Armement | PROCESS OF OCCULTATION OF VISIBLE AND INFRARED RADIATION AND SMOKE AMMUNITION IMPLEMENTING THIS PROCESS |
DE3238444C2 (en) | 1982-10-16 | 1986-10-30 | Pyrotechnische Fabrik F. Feistel GmbH + Co KG, 6719 Göllheim | Pyrotechnic smoke packs |
US4534810A (en) | 1984-01-30 | 1985-08-13 | The United States Of America As Represented By The Secretary Of The Army | Red phosphorous smoke producing composition |
GB2206343B (en) | 1987-06-17 | 1990-03-07 | Secr Defence Brit | Smoke producing composition for pyrotechnic markers, method for the production thereof and pyrotechnic markers containing same. |
DE4030430C1 (en) * | 1990-09-26 | 1993-12-02 | Buck Chem Tech Werke | Compsn. for generating IR-opaque smoke, esp. for camouflage - contains magnesium@ powder, fluoro:polymer, chloro:paraffin and aromatic cpd., esp. anthracene, phthalic anhydride, 2-benzoyl-pyridine etc. |
US5522320A (en) | 1993-07-12 | 1996-06-04 | Thiokol Corporation | Low-toxicity obscuring smoke formulation |
DE4327976C1 (en) * | 1993-08-19 | 1995-01-05 | Buck Chem Tech Werke | Flare charge for producing decoys |
US5834680A (en) * | 1995-09-22 | 1998-11-10 | Cordant Technologies Inc. | Black body decoy flare compositions for thrusted applications and methods of use |
US6427599B1 (en) * | 1997-08-29 | 2002-08-06 | Bae Systems Integrated Defense Solutions Inc. | Pyrotechnic compositions and uses therefore |
-
1999
- 1999-03-27 DE DE19914097A patent/DE19914097A1/en not_active Withdrawn
-
2000
- 2000-01-24 JP JP2000607944A patent/JP2002540058A/en active Pending
- 2000-01-24 EP EP00901589A patent/EP1173394B9/en not_active Expired - Lifetime
- 2000-01-24 DK DK00901589T patent/DK1173394T3/en active
- 2000-01-24 ES ES00901589T patent/ES2218106T3/en not_active Expired - Lifetime
- 2000-01-24 WO PCT/EP2000/000498 patent/WO2000058237A1/en active IP Right Grant
- 2000-01-24 IL IL14513300A patent/IL145133A0/en unknown
- 2000-01-24 TR TR2001/02777T patent/TR200102777T2/en unknown
- 2000-01-24 PT PT00901589T patent/PT1173394E/en unknown
- 2000-01-24 AT AT00901589T patent/ATE261921T1/en not_active IP Right Cessation
- 2000-01-24 US US09/937,619 patent/US6581520B1/en not_active Expired - Fee Related
- 2000-01-24 DE DE50005691T patent/DE50005691D1/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004024857B4 (en) * | 2004-05-19 | 2008-07-10 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic set |
Also Published As
Publication number | Publication date |
---|---|
DE19914097A1 (en) | 2000-09-28 |
JP2002540058A (en) | 2002-11-26 |
IL145133A0 (en) | 2002-06-30 |
WO2000058237A1 (en) | 2000-10-05 |
TR200102777T2 (en) | 2002-01-21 |
ES2218106T3 (en) | 2004-11-16 |
DE50005691D1 (en) | 2004-04-29 |
PT1173394E (en) | 2004-07-30 |
DK1173394T3 (en) | 2004-07-19 |
EP1173394A1 (en) | 2002-01-23 |
EP1173394B9 (en) | 2004-10-13 |
ATE261921T1 (en) | 2004-04-15 |
US6581520B1 (en) | 2003-06-24 |
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