EP1173394A1 - 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

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Publication number
EP1173394A1
EP1173394A1 EP00901589A EP00901589A EP1173394A1 EP 1173394 A1 EP1173394 A1 EP 1173394A1 EP 00901589 A EP00901589 A EP 00901589A EP 00901589 A EP00901589 A EP 00901589A EP 1173394 A1 EP1173394 A1 EP 1173394A1
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EP
European Patent Office
Prior art keywords
impenetrable
aerosol
red phosphorus
pyrotechnic active
alkali metal
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EP00901589A
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German (de)
French (fr)
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EP1173394B9 (en
EP1173394B1 (en
Inventor
Ernst-Christian Koch
Axel Dochnahl
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Pepete GmbH
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Piepenbrock Pyrotechnik GmbH
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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)
    • 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 ecotoxicologically compatible pyrotechnic active substance consisting of red phosphorus, a 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 alkali metal nitrates, preferably cesium nitrate and potassium nitrate, which is suitable for producing a highly emissive in the infrared (3-5, 8-14 ⁇ m) and visually impenetrable aerosol.
  • a human and ecotoxicologically compatible pyrotechnic active substance consisting of red phosphorus, a 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 alkali metal nitrates, preferably cesium nitrate and potassium nitrate, which is suitable for producing a highly emiss
  • aerosols While colored aerosols based on organic azo dyes (white, orange, red, violet, green, blue) that only absorb in the visible range of the spectrum are preferably used for marking and simulating, aerosols are preferably used for camouflage, deception and masking. which also includes the infrared range of the electromagnetic spectrum, especially in the range of the atmospheric transmission window at 0.3 - 1, 5; 1, 6 - 1, 8; 2.0-2.5; Interrupt 3.0-5.0 and 8.0-14 ⁇ m using various mechanisms. These mechanisms include the scattering, absorption and emission of radiation. Scattering and absorption of radiation are described by the Lambert-Beer law.
  • I describes the radiation intensity attenuated by the interactions
  • l 0 represents the initial intensity
  • c corresponds to the concentration of the aerosol per unit volume
  • / is the path length assumed by the aerosol cloud to be the isotropic density
  • ⁇ is the wavelength-dependent mass extinction coefficient of the aerosol particles that occurs at a given Composing the substance as the sum of the scattering and absorption coefficients:
  • 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 particles' spherical morphology, 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.
  • Such particles can be generated in an established manner by the following processes:
  • the aerosols described under a) and b) contribute to the absorption of infrared radiation due to their chemical composition. Both carbon black and brass dust are electrically conductive and therefore suitable for coupling infrared radiation.
  • DE 40 30 430 describes an active composition which, when burned, produces aromatic radicals which react to polyaromatics, which form voluminous agglomerates, through a coordinated quantitative ratio of magnesium powder, a fluorinated organic polymer, chlorinated paraffin and an aromatic compound, in particular anthracene or phthalic anhydride with a fibrous structure have diameters in the range of 1 - 20 ⁇ m, which are suitable for IR radiation scattering and absorption and still float in the air due to the large specific surface.
  • a burning rate of approx. 15 g / sec. are adhered to, so that the covering effect starts relatively late. It is therefore further proposed in this patent to add a fast-burning mixture of fluorine-containing polymer, magnesium powder and an organic binder, which produces a strong IR emission in the short term when burning and thus closes the initial coverage gap.
  • a disadvantage of this process is that the polyaromatics formed also contain carcinogenic substances and the emissive effect quickly subsides due to the use of magnesium.
  • the object of the present invention was therefore to develop a new camouflage mist which, in addition to being impenetrable in the visible range, also enables long-lasting coverage in the IR range.
  • the main constituents of the mist sets according to the invention contain 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 constituents, 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.
  • 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
  • a polymeric organic binder a polymeric organic binder
  • red phosphorus serves as a carrier for the transmission-damping effect in the visible range. that under certain circumstances the red phosphorus also acts as a carrier of 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 according to the invention as an oxidizing agent provides alkali metal oxides during combustion, which in the presence of atmospheric moisture acc. Eq. 6 react to the hydroxides.
  • the aerosol droplets formed have a size of 0.01 - 2 ⁇ m and therefore high absorption and scattering coefficients in the visible and short-wave infrared range of 0.3 - 1, 9 ⁇ m and low damping values in the medium and long-wave infrared range of 2 - 14 ⁇ m. Notwithstanding this, the heat generated by reactions 4 - 6, but in particular in steps 7 and 8, ensures a strong emission of the aerosol droplets in the middle and long-wave infrared, and thus compensates for the low scattering and absorption coefficients in this spectral range.
  • the heat development according to the invention occurs in part through chemical processes which are only possible through the delayed formation of the aerosol droplets, so that they are emissive Effect 50 - 200 se ⁇ , ie for the time necessary for camouflage.
  • transition metals according to the invention whose oxides have high heat of formation, such as zirconium and titanium, and metalloids such as boron and / or silicon, very high combustion temperatures are achieved, which is why the aerosol particles receive high thermal energy, which increases the emission in the long-wave IR.
  • the use according to the invention of the transition metals and their alloys or metal-rich compounds further suppresses the formation of phosphine formers.
  • the metal phosphides eg zirconium phosphide or titanium phosphide
  • the metal phosphides formed during the combustion due to the underbalance of oxygen have a non-ionic character, which is why there is no hydrolysis or acidolysis with the release of phosphines with atmospheric humidity or acid rain. Therefore, fog sets according to the invention are compatible with human and ecotoxicology and considerably safer than conventional fog sets based on red phosphorus and light metal such as magnesium or aluminum. This also means that the self-inflammability of the burn-up residues, which typically occurs with fog sets based on red phosphorus, is no longer present.
  • a doughy batch is produced by gradually adding the components to the red phosphorus.
  • the solvent-moist mass is sieved (7 mm mesh size) and dried for 20 minutes in vacuo at 40 ° C. and 20 mbar.
  • the 42 g of granulate are pressed with a pressure of 20 tons into ring-shaped pressings with an edge height of 10 mm, an outside diameter of 57 mm and an inside diameter of 15 mm.
  • One tablet has a burning time of approx. 35 seconds and provides a visually dense white fog.
  • Radiometric measurement of the resulting aerosol at a distance of 4 m from the source reveals the following radiation levels in the infrared range:
  • FIG. 1 shows the jet strength 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.
  • very good irradiation > 95%) of emissive targets, the color temperature 300 ° C., is achieved.

Abstract

The invention relates to a pyrotechnic active mass which is impenetrable in the visible spectrum, highly emissive in the infrared spectrum and used for camouflage and decoy purposes. As principal ingredients said mass contains red phosphorus and an alkali metal nitrate or mixture of alkali metal nitrates and as secondary ingredients at least one transition metal or a metal-rich compound or alloy thereof, at least one metalloid and a binder.

Description

Pyrotechnische Wirkmasse zur Erzeugung eines im Infraroten stark emissiven und im Visuellen undurchdringlichen Aerosols Pyrotechnic active mass for the generation of a highly emissive in the infrared and in the visual impenetrable aerosol
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 ecotoxicologically compatible pyrotechnic active substance consisting of red phosphorus, a 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 alkali metal nitrates, preferably cesium nitrate and potassium nitrate, which is suitable for producing a highly emissive in the infrared (3-5, 8-14 μm) and visually impenetrable aerosol.
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 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. Streuung und Absorption von Strahlung werden durch das Lambert-Beersche Gesetz beschrieben.While colored aerosols based on organic azo dyes (white, orange, red, violet, green, blue) that only absorb in the visible range of the spectrum are preferably used for marking and simulating, aerosols are preferably used for camouflage, deception and masking. which also includes the infrared range of the electromagnetic spectrum, especially in the range of the atmospheric transmission window at 0.3 - 1, 5; 1, 6 - 1, 8; 2.0-2.5; Interrupt 3.0-5.0 and 8.0-14 μm using various mechanisms. These mechanisms include the scattering, absorption and emission of radiation. Scattering and absorption of radiation are described by the Lambert-Beer law.
I = l0 exp -adI = l 0 exp -ad
(1 )(1 )
Wobei I die durch die Wechselwirkungen abgeschwächte Strahlungsintensität beschreibt, l0 die anfängliche Intensität darstellt, c entspricht der Konzentration des Aerosols pro Volumeneinheit, / 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:Where I describes the radiation intensity attenuated by the interactions, l 0 represents the initial intensity, c corresponds to the concentration of the aerosol per unit volume, / is the path length assumed by the aerosol cloud to be the isotropic density, α is the wavelength-dependent mass extinction coefficient of the aerosol particles that occurs at a given Composing the substance as the sum of the scattering and absorption coefficients:
α(λ) = αstr(λ) + αabs(λ) (2)α (λ) = α str (λ) + α abs (λ) (2)
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. Solche Partikeln können auf etablierte Weise durch folgende Prozesse erzeugt werden:According to Rayleigh, in order for aerosols to scatter radiation, the particle diameter, assuming the particles' spherical morphology, 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. Such particles can be generated in an established manner by the following processes:
a) Verbrennung sauerstoffdefizienter, Kohlenstoff-reicher pyrotechnischer Sätze. Beim Abbrand entsteht dann aufgrund der schlechten Sauerstoffbilanz viel Ruß mit Partikeldurchmessern im relevanten Größenbereich (DD 301 646 A7, DE 3326884 C2)a) Combustion of oxygen deficient, carbon-rich pyrotechnic phrases. When burning, a lot of soot with particle diameters in the relevant size range is generated due to the poor oxygen balance (DD 301 646 A7, DE 3326884 C2)
b) Explosiv-Dissiminierung von vorkonfektionierten Partikeln vorzugsweise Messingstaub im geeigneten Größenbereich.b) Explosive dissimilation of pre-assembled particles, preferably brass dust in the appropriate size range.
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) contribute to the absorption of infrared radiation due to their chemical composition. Both carbon black and brass dust are electrically conductive and therefore suitable for coupling infrared radiation.
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. Poly- halogendibenzofuranen und Polyhalogendibenzodioxiπen oder auch polyhalo- genierte Biphenylen.The disadvantages of the above-described methods for producing infrared radiation-shielding aerosol clouds exist in a) in the contamination of the soot particles produced with some. carcinogenic polyaromatic hydrocarbons (PAH) and in the case of energetic halogen-containing components in such pyrotechnic sentences in the contamination of the soot particles with polyhalogenated oxyarenes such as e.g. Polyhalodibenzofurans and Polyhalogendibenzodioxiπen or 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 Teilchen- dichte. An dieser Stelle der Wolke wird die Line ofsight (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 in the explosive dispersion of pre-assembled particles. This means the hole with very low particle size caused by the explosion process in the aerosol cloud. density. 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 people and the environment are also very considerable, so that mass application in particular also for exercise purposes must be avoided.
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 fiuorhaltigem Polymer, Magnesiumpulver und einem organischen Binder zuzufügen, die kurzfristig beim Abbrennen eine starke IR-Emission erzeugt und damit die anfängliche Deckungslücke schließt.DE 40 30 430 describes an active composition which, when burned, produces aromatic radicals which react to polyaromatics, which form voluminous agglomerates, through a coordinated quantitative ratio of magnesium powder, a fluorinated organic polymer, chlorinated paraffin and an aromatic compound, in particular anthracene or phthalic anhydride with a fibrous structure have diameters in the range of 1 - 20 μm, which are suitable for IR radiation scattering and absorption and still float in the air due to the large specific surface. To suppress the formation of fine soot instead of polyaromatics, a burning rate of approx. 15 g / sec. are adhered to, so that the covering effect starts relatively late. It is therefore further proposed in this patent to add a fast-burning mixture of fluorine-containing polymer, magnesium powder and an organic binder, which produces a strong IR emission in the short term when burning and thus closes the initial coverage gap.
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 also contain carcinogenic substances and the emissive effect quickly subsides due to the use of magnesium.
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 moving, warm targets (People, vehicles, armored platforms) against CLOS and SACLOS missiles (eg Milan, TOW, etc.) to protect effectively. 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 acquired, 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 develop a new camouflage mist which, in addition to being impenetrable in the visible range, also enables long-lasting coverage in the IR range.
Die Lösung dieser Aufgabe wird durch die Merkmale des Hauptanspruchs erreicht und durch die der Unteransprüche gefördert.This object is achieved by the features of the main claim and promoted by those of the subclaims.
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 poly- meren organischen Binder.The main constituents of the mist sets according to the invention contain 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 constituents, 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 (Gl. 3) und verbrennt in Gegenwart des Luftsauerstoffs gemäß Gleichung (4) zu Phosphorpentoxid.It was previously known that the red phosphorus serves as a carrier for the transmission-damping effect in the visible range. that under certain circumstances the red phosphorus also acts as a carrier of 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).
P(rot) + Verbrennungswärme P4(g) (3)P ( ro t) + heat of combustion P 4 (g) (3)
P4(g) + 5 02 > 2 P205 + Wärme (4)P 4 (g) + 5 0 2 > 2 P 2 0 5 + heat (4)
Phosphorpentoxid reagiert mit der Luftfeuchtigkeit gemäß Gleichung 5 zu Phosphorsäure. P205 + 3 H20 > 2 H3PO4 + Wärme (5)Phosphorus pentoxide reacts with the air humidity according to equation 5 to phosphoric acid. P 2 0 5 + 3 H 2 0> 2 H 3 PO 4 + heat (5)
Die erfindungsgemäße Verwendung von Alkalimetallnitraten als Oxidationsmittel liefert beim Abbrand Alkalimetalloxide, welche in Gegenwart der Luftfeuchtigkeit gem. Gl. 6 zu den Hydroxiden abreagieren.The use of alkali metal nitrates according to the invention as an oxidizing agent provides alkali metal oxides during combustion, which in the presence of atmospheric moisture acc. Eq. 6 react to the hydroxides.
M20(s) + H20 > 2 MOH(aq) + Wärme (6)M 2 0 (s) + H 2 0> 2 MOH (aq) + heat (6)
M = Na, K, Rb, CsM = Na, K, Rb, Cs
Diese Aerosoltröpfchen liefern mit den Phosphorsäuretröpfchen in einer stark exothermen Reaktion die entsprechenden Dihydrogenphosphate.These aerosol droplets deliver the corresponding dihydrogen phosphates in a strongly exothermic reaction with the phosphoric acid droplets.
MOH + H3P04(aq) 2 MH2PO4 + H2O + Wärme (7)MOH + H 3 P0 4 (aq) 2 MH 2 PO 4 + H 2 O + heat (7)
Die Hydratisierung der Dihydrogenphosphate ist ebenfalls eine exotherme Reaktion und liefert nochmals Wärme. MH2P04 + n H20 > MH2P04 • (H20)n + Wärme (8)The hydration of the dihydrogen phosphates is also an exothermic reaction and provides heat again. MH 2 P0 4 + n H 2 0> MH 2 P0 4 • (H 2 0) n + heat (8)
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 seα, d.h. für die für eine Tarnung notwendige Zeit anhält.The aerosol droplets formed have a size of 0.01 - 2 μm and therefore high absorption and scattering coefficients in the visible and short-wave infrared range of 0.3 - 1, 9 μm and low damping values in the medium and long-wave infrared range of 2 - 14 μm. Notwithstanding this, the heat generated by reactions 4 - 6, but in particular in steps 7 and 8, ensures a strong emission of the aerosol droplets in the middle and long-wave infrared, and thus compensates for the low scattering and absorption coefficients in this spectral range. In contrast to the known strong emission of magnesium-containing active substances, which occurs directly during combustion and then quickly subsides, the heat development according to the invention occurs in part through chemical processes which are only possible through the delayed formation of the aerosol droplets, so that they are emissive Effect 50 - 200 seα, ie 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.By using transition metals according to the invention whose oxides have high heat of formation, such as zirconium and titanium, and metalloids such as boron and / or silicon, very high combustion temperatures are achieved, which is why the aerosol particles receive 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 Phosphanbildnem. Die bei der Verbrennung aufgrund der Sauerstoffunterbilan- zierung 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. 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.The use according to the invention of the transition metals and their alloys or metal-rich compounds further suppresses the formation of phosphine formers. The metal phosphides (eg zirconium phosphide or titanium phosphide) formed during the combustion due to the underbalance of oxygen have a non-ionic character, which is why there is no hydrolysis or acidolysis with the release of phosphines with atmospheric humidity or acid rain. Therefore, fog sets according to the invention are compatible with human and ecotoxicology and considerably safer than conventional fog sets based on red phosphorus and light metal such as magnesium or aluminum. This also means that the self-inflammability of the burn-up residues, which typically occurs with fog sets based on red phosphorus, is no longer present.
Das folgende Beispiel soll die Erfindung verdeutlichen ohne sie jedoch zu beschränken:The following example is intended to illustrate the invention without, however, restricting it:
Beispielexample
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 Pressungen 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.From 2750 g of red phosphorus, 990 g of potassium nitrate, 220 g of silicon, 220 g of boron, 220 g of zirconium and 990 g of Macroplast binder (30% solids), a doughy batch is produced by gradually adding the components to the red phosphorus. The solvent-moist mass is sieved (7 mm mesh size) and dried for 20 minutes in vacuo at 40 ° C. and 20 mbar. The 42 g of granulate are pressed with a pressure of 20 tons into ring-shaped pressings with an edge height of 10 mm, an outside diameter of 57 mm and an inside diameter of 15 mm. One tablet has a burning time of approx. 35 seconds and provides a visually dense white fog.
Die radiometrische Vermessung des entstehenden Aerosols in 4 m Entfernung der Quelle offenbart folgende Strahlstärken im infraroten Bereich: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 μm) Band II (3 - 5 μm)Band V (8 - 14 μm) Band II (3 - 5 μm)
> 100 W/sr > 25 s > 20 W/sr > 25 s> 100 W / sr> 25 s> 20 W / sr> 25 s
> 60 W/sr > 75 s > 10 W/sr > 75 s. 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. > 60 W / sr> 75 s> 10 W / sr> 75 s. FIG. 1 shows the jet strength 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

Patentansprüche claims
1. Im Visuellen undurchdringliche und im Infraroten stark emissive pyrotechnische Wirkmasse für Tarn- und Täuschzwecke, dadurch gekennzeichnet, daß als Hauptbestandteile roter Phosphor, ein Alkalimetallnitrat oder eine Mischung von Alkalimetallnitraten, und als Nebenbestandteile mindestens ein Ubergangsmetall, bzw. eine metallreiche Verbindung oder Legierung desselben, mindestens ein Metalloid sowie ein Binder enthalten sind.1. In the visual impenetrable and in the infrared strongly emissive pyrotechnic active substance for camouflage and deception purposes, characterized in that the main components are red phosphorus, an alkali metal nitrate or a mixture of alkali metal nitrates, and as secondary components at least one transition metal, or a metal-rich compound or alloy thereof , at least one metalloid and a binder are included.
2. Pyrotechnische Wirkmasse nach Anspruch 1 , dadurch gekennzeichnet, daß 45 % bis 75 % Roter Phosphor, 15 % bis 35 % Alkalimetallnitrate, 2 bis 20 % Metalloide und 0,5 bis 8 % Binder enthalten sind.2. Pyrotechnic active composition according to claim 1, characterized in that 45% to 75% red phosphorus, 15% to 35% alkali metal nitrates, 2 to 20% metalloids and 0.5 to 8% binder are included.
3. Pyrotechnische Wirkmasse nach den vorhergehenden Ansprüchen, dadurch gekennzeichnet, daß 55% bis 62 % Roter Phosphor, 18 % bis 23 % Alkalimetallnitrate, 10 bis 18 % Metalloide und 5 bis 7 % Binder enthalten sind.3. Pyrotechnic active composition according to the preceding claims, characterized in that 55% to 62% red phosphorus, 18% to 23% alkali metal nitrates, 10 to 18% metalloids and 5 to 7% binder are included.
4. Pyrotechnische Wirkmasse nach den vorhergehenden Ansprüchen, dadurch gekennzeichnet daß 58,5 % roter Phosphor, 21 ,1 % Kaliumnitrat, jeweils 4,7 % Bor, Silicium und Zirconium sowie 6,3 % eines Polychloropren-Binders enthalten sind. 4. Pyrotechnic active composition according to the preceding claims, characterized in that 58.5% red phosphorus, 21, 1% potassium nitrate, each 4.7% boron, silicon and zirconium and 6.3% of a polychloroprene binder are included.
EP00901589A 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 Expired - Lifetime EP1173394B9 (en)

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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

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ATE261921T1 (en) 2004-04-15
TR200102777T2 (en) 2002-01-21
DK1173394T3 (en) 2004-07-19
DE50005691D1 (en) 2004-04-29
WO2000058237A1 (en) 2000-10-05
ES2218106T3 (en) 2004-11-16
IL145133A0 (en) 2002-06-30
DE19914097A1 (en) 2000-09-28
PT1173394E (en) 2004-07-30

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