EP2698360B1 - Utilisation d'un adjuvant dans une masse active pour une cible fictive à rayonnement spectral lors de la combustion de la masse active - Google Patents

Utilisation d'un adjuvant dans une masse active pour une cible fictive à rayonnement spectral lors de la combustion de la masse active Download PDF

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Publication number
EP2698360B1
EP2698360B1 EP13004007.4A EP13004007A EP2698360B1 EP 2698360 B1 EP2698360 B1 EP 2698360B1 EP 13004007 A EP13004007 A EP 13004007A EP 2698360 B1 EP2698360 B1 EP 2698360B1
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EP
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Prior art keywords
active composition
oxide
catalyst
phthalocyanine
fuel
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Active
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EP13004007.4A
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German (de)
English (en)
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EP2698360A2 (fr
EP2698360A3 (fr
Inventor
Arno Hahma
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Diehl Defence GmbH and Co KG
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Diehl Defence GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C15/00—Pyrophoric compositions; Flints

Definitions

  • the invention relates to a use of an additive in an active mass for a spectrally radiating decay when burning the active mass to a ratio of intensity of a radiation emitted during combustion of the active mass radiation in the wavelength range of 3.7 to 5.1 microns to an intensity of the burn-up to increase the effective mass emitted radiation in the wavelength range of 1.9 to 2.3 microns, wherein the additive is distributed in the active material.
  • the said ratio of the radiation intensity is also referred to as the spectral ratio.
  • US 6,123,790 A discloses a gas generant composition for a gas generator of a vehicle occupant restraint system comprising a mixture of high bulk density nitroguanidine, one or more non-azide fuels, an oxidizer containing a phase stabilized ammonium nitrate and an amount of copper phthalocyanine sufficient to cause combustion of the gas generant Maintain composition at ambient pressure of about 100 psi or less.
  • the DE 10 2010 053 783 A1 discloses a high performance pyrotechnic infrared target active composition
  • a high performance pyrotechnic infrared target active composition comprising a first fuel, at least one second fuel, an oxidizer and a binder, wherein the first fuel and the oxidizer are selected for their redox potentials such that the oxidant subjects the first fuel to ignition in an exothermic reaction Emergence of a primary flame and emission of infrared radiation can oxidize.
  • the second fuel ignites, heats and / or pyrolyzes in the reaction and is released from the high performance active mass.
  • the second fuel is selected so that its redox potential or the redox potential of at least one pyrolysis product of the second fuel is higher than the redox potential of the first fuel and that the heated or ignited second fuel or the pyrolysis product can burn in the air.
  • the amount of oxidizing agent contained in the high-performance active mass is at most so great that it is just sufficient to completely oxidize the first fuel.
  • a decoy comprising a first gable housing having an interior and an exterior, a pyrotechnic composition adapted to be received and burned in the interior of this enclosure, the pyrotechnic composition comprising about 8% to about 60% by weight % of an aromatic polycarboxylic anhydride fuel component, about 40% to about 90% by weight of an oxidizing agent, from about 1% to about 20% by weight of a binder and an ignition layer surrounding at least a portion of the pyrotechnic composition.
  • the object of the present invention is to provide a use of an additive in a fake target effective mass, by which the spectral ratio is increased over that of a known active mass, the fake target effective mass still shows a high radiant power during combustion.
  • the active mass should burn stably even at high wind speeds.
  • a use of an additive is provided in an active mass for a spectrally radiating decay target during the burnup of the active mass to a ratio of an intensity of a radiation emitted during the burnup of the active mass in the wavelength range from 3.7 to 5.1 ⁇ m to an intensity during burnup to increase the effective mass emitted radiation in the wavelength range of 1.9 to 2.3 microns.
  • the additive is distributed in the effective mass and the active material comprises a fuel containing carbon and hydrogen atoms and an oxidant for the fuel containing oxygen atoms, the amount of the oxidizing agent being such that it is insufficient for complete oxidation of the carbon.
  • the additive is a particulate redox reaction catalyzing catalyst.
  • the redox reaction is a reaction according to the reaction scheme CO + H 2 O ⁇ CO 2 + H 2 .
  • the spectral ratio increases significantly compared to a working mass without this additive.
  • the spectrum of the radiation is shifted from the short-wave range into the medium-wave range, and the blackbody radiation of the windrows resulting from the formation of soot is reduced.
  • the active mass can also be equipped with a large excess of oxidizing agent, ie a very negative oxygen balance and thus a very high specific energy, without the spectral ratio being reduced by the resulting soot.
  • the particles stabilize the flame and prevent it from being blown out by wind.
  • the flame-stabilizing effect is based on the fact that the particles act as reaction nuclei and at the same time as an ignition source.
  • the catalyst may in the active material in an amount of at most 5 wt .-%, in particular at most 2 wt .-%, in particular at most 1 wt .-%, in particular at most 0.5 wt .-%, in particular at most 0.1 wt. -%, be included.
  • the specific energy of the active mass is thereby only slightly or almost not affected, while the spectral ratio can even be doubled.
  • the particles distributed in the active mass may have a maximum average particle size of 50 ⁇ m, in particular 20 ⁇ m, in particular 10 ⁇ m, in particular 1 ⁇ m.
  • the catalyst present in the form of particles should functionally survive all of the flame zones formed during the combustion and its catalytic If possible, unfold the effect on the edge of the flame. This can be ensured by solid, heat-resistant catalysts that only become effective at higher temperatures.
  • Catalysts that efficiently accelerate both the reaction according to the reaction scheme CO + H 2 O ⁇ CO 2 + H 2 and the oxidation of carbon, in particular soot are the rare earth oxides, such. CeO 2 and Ce 2 O 3 , yttrium oxide, ytterbium oxide, neodymium oxide and other rare earth oxides and mixtures thereof. Very efficient is a mixture of CeO 2 or Ce 2 O 3 and yttrium oxide.
  • Catalysts that accelerate a reaction according to the reaction scheme CO + H 2 O ⁇ CO 2 + H 2 are known in the art, for example, as LTS and HTS catalysts.
  • LTS low temperature shift
  • HTS high temperature Shift
  • the LTS catalyst consists of a copper-doped mixture of aluminum and zinc oxide and the HTS catalyst of a chromium-doped magnetite (Fe 3 O 4 ).
  • catalysts which accelerate the reaction according to the reaction scheme CO + H 2 O ⁇ CO 2 + H 2 only at temperatures above 300 ° C. Furthermore, it is favorable that the catalyst itself does not catalyze the burnup of the active material itself.
  • catalysts are those that effectively accelerate a reaction only from about 500 ° C.
  • copper phthalocyanine (Vossenblau) is very suitable for increasing the spectral ratio, which is very temperature-resistant and does not decompose until about 600 ° C.
  • Phthalocyanines of iron, chromium, cobalt, nickel and molybdenum are also well suited catalysts.
  • the catalyst forming the additive comprises at least one organometallic pigment, a salt of a rare earth metal, a compound containing a rare earth metal which forms an oxide of a rare earth metal in a flame resulting from combustion of the active material, an oxide of zirconium, titanium, aluminum, zinc, magnesium, Calcium, strontium, barium, hafnium, vanadium, niobium, tantalum, chromium, nickel, iron, manganese, molybdenum, tungsten, cobalt or thorium or a compound containing one of said metals, which in an emerging during combustion of the active material flame an oxide of a of such metal, silver, a platinum metal, Rhenium or a compound containing one of said metals, which is reduced to the metal in a flame resulting from the combustion of the active material, or a mixture of at least two of the aforementioned compounds or elements or yttrium oxide, ytterbium oxide, neodymium oxide, a mixture of said oxide
  • the fuel of the active mass may contain, in addition to carbon atoms and hydrogen atoms, oxygen and / or nitrogen atoms.
  • the fuel may comprise at least one nitrate ester, in particular a liquid nitrate ester, in particular glyceryl trinitrate, ethylene glycol dinitrate, diethylene glycol dinitrate, triethylene glycol dinitrate or methriol trinitrate, or a nitrate ester present as a polymeric solid, in particular nitrocellulose, polyvinyl nitrate or polyglycidyl nitrate and / or a nitrosamine, in particular 1,3,5- trinitroso-1,3,5-hexahydrotriazine, or an amine, amide, nitrile, cyanate, isocyanate, urethane, imine, ketimine, imide, azide, nitramine, nitrosamine, hydroxylamine, hydrazine, hydrazone, oxime,
  • each of the abovementioned compounds comprises at least one CN, one CNO or one CON group and optionally at least one CO group.
  • the groups mentioned can be present in straight or annular chains and with single, double or triple bonds.
  • the gases forming the flame include predominantly carbon monoxide, hydrogen and water vapor.
  • Hydrogen does not radiate at all, water in the short-wave wavelength range and CO in the desired B-band but with low emissivity.
  • the catalyst converts water and carbon monoxide in the flame into carbon dioxide and hydrogen.
  • the radiation of carbon dioxide is emitted to about 99% in the wavelength range between 4 and 5 microns.
  • the oxidizing agent may contain chlorine and / or bromine atoms.
  • Ammonium perchlorate has proven to be a particularly suitable oxidizing agent, because during its reaction exclusively gaseous reaction products and no particles emitting blackbody radiation are formed.
  • an additional catalyst comprising copper or iron atoms, in particular ferrocene, iron oxide, iron acetonyl acetate or copper phthalocyanine, can be present as the oxidizing agent in the active material. This additional catalyst lowers the temperature at which ammonium perchlorate decomposes and burns off. It stabilizes the burnup of the active mass.
  • the active mass in the active mass essentially (except for the catalysts) contain no substances that contain atoms other than carbon, hydrogen, nitrogen, oxygen, sulfur, chlorine and bromine. This avoids the formation of burn-off products which shift the spectrum in the direction of the A-band. "Essentially” means that none of the selected constituents of the active material contains these substances. However, naturally, the presence of traces of substances containing such atoms can not be completely ruled out.
  • the single figure shows a schematic representation of the functional principle of an inventive use of the additive in the active mass during combustion.
  • the figure shows in the middle of the burning active mass and right of it a profile of the temperature T of the flame generated during their combustion as a function of the distance d from the burning surface 1 of the active mass.
  • hot gases exit the surface and form a diffusion zone 2.
  • oxidizing gases from an oxidant contained in the active mass and combustible gases mix from a fuel contained in the active mass and begin to react with each other in a flame.
  • these gases are mainly converted into carbon monoxide and water vapor because the amount of oxidizing agent is such that it is insufficient for complete oxidation of the carbon.
  • the temperature is still too low to activate the catalyst.
  • the line 7 shows the temperature threshold above which the catalyzed reaction proceeds according to the reaction scheme CO + H 2 O ⁇ CO 2 + H 2 and carbon monoxide and water form carbon dioxide and hydrogen.
  • This reaction produces the carbon dioxide-rich second reaction zone 4, which is hottest.
  • the hydrogen burns off in a not shown to scale thin outer reaction zone 5, whereby water vapor and carbon dioxide.
  • the outer reaction zone 5 radiates strongly into the outer zone 6.
  • the radiation emitted in the first reaction zone 3 by the water molecules in the wavelength range from 2 to 3 ⁇ m is partially shielded again by the first reaction zone 3 because water also absorbs radiation in this spectral range.
  • This shielding also occurs in the outer reaction zone 5.
  • this zone is very thin, the shielding effect in both the A and B band is low.
  • the absorption of water and carbon dioxide as a function of the wavelength is shown schematically in the diagram to the left of the flame.
  • the second reaction zone 4 radiates mainly in the range of 3 to 5 microns in the outer region 6 and is hardly shielded from the thin outer reaction zone 5. Since hardly any water is present in the second reaction zone 4, there is hardly any emission in the A band. In the outer reaction zone 5, the water is present only for a very short time, so that it emits hardly any radiation for this reason, while the residence time of the carbon dioxide in the flame and thus the emission in the B-band is relatively large.
  • BMIM-ClO 4 200 g of the ionic liquid BMIM-ClO 4 used in some of the following active compositions were synthesized as follows: 150 g of BMIM-CI were dissolved in about 600 ml of dry methanol at 25 ° C in a 2 liter one-necked flask. A stoichiometric amount of dry sodium perchlorate was also separately dissolved in 600 ml of dry methanol in a 2 liter one-necked flask. Then all the perchlorate solution was added all at once to the BMIM chloride solution. The bottle containing the perchlorate solution was washed 3 times with 50 ml of dry methanol and the methanol was added to the BMIM chloride solution. The resulting solution became cloudy and yellow after several minutes as the resulting sodium chloride began to precipitate.
  • the one-necked flask was then connected to a rotary evaporator and the methanol distilled off under about 500 mbar pressure, the water bath was heated to 90 ° C in the evaporator.
  • the warm crude BMIM-ClO 4 from the flask was again filtered through the frit into a 250 ml separatory funnel, because even more common salt had precipitated upon evaporation of the methanol.
  • the final BMIM-ClO 4 (a yellowish, viscous oil) was filled from the separating funnel into a laboratory flask and weighed. The yield was almost quantitative.
  • Active composition according to Example 4 but additionally with water gas catalyst.
  • the spectral ratio is doubled and the specific energy is slightly increased.
  • DEGDN self-synthesized 11,80 TMD 1702 BMIM-ClO 4 self-synthesized 5.9 paracyanogen powder 20.20 Akardite II 0.10 Water gas catalyst Type HTS 0.10

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (8)

  1. Utilisation d'un additif dans une masse active destiné à une cible fictive rayonnant de manière spectrale lors de la combustion de la masse active, pour augmenter un rapport d'une intensité d'un rayonnement d'une longueur d'onde de 3,7 à 5,1 µm émis lors de la combustion de la masse active sur une intensité d'un rayonnement d'une longueur d'onde de 1,9 à 2,3 µm émis lors de la combustion de la masse active, l'additif étant répandu dans la masse active,
    la masse active comprenant un combustible contenant des atomes de carbone et des atomes d'hydrogène et un oxydant pour le combustible, contenant des atomes d'oxygène, la quantité d'oxydant étant dimensionnée de sorte qu'elle ne suffit pas pour une oxydation complète du carbone, l'additif étant un catalyseur catalysant une réaction rédox se présentant sous forme de particules, la réaction rédox étant une réaction correspondant au schéma de réaction CO + H2O → CO2 + H2, le catalyseur comprenant au moins un pigment organométallique, un sel d'un métal des terres rares, un composé contenant un métal des terres rares, qui forme, dans une flamme apparaissant lors de la combustion de la masse active, un oxyde d'un métal des terres rares, un oxyde de zirconium, de titane, d'aluminium, de zinc, de magnésium, de calcium, de strontium, de baryum, d'hafnium, de vanadium, de niobium, de tantale, de chrome, de nickel, de fer, de manganèse, de molybdène, de tungstène, de cobalt ou de thorium ou un composé contenant un des métaux indiqués, qui forme, dans une flamme apparaissant lors de la combustion de la masse active, un oxyde d'un de ces métaux, de l'argent, un métal du groupe du platine, du rhénium, ou un composé contenant un des métaux indiqués, qui, dans une flamme apparaissant lors de la combustion de la masse active, est réduit en métal, ou un mélange d'au moins deux des composés ou éléments indiqués ci-dessus, ou le catalyseur comprenant de l'oxyde d'yttrium, de l'oxyde d'ytterbium, de l'oxyde de néodyme, un mélange des oxydes indiqués, un mélange de CeO2 ou de Ce2O3 et d'oxyde d'yttrium, un mélange, dopé au cuivre, d'oxyde d'aluminium et d'oxyde de zinc (catalyseur LTS), une magnétite (Fe3O4) dopée au chrome (catalyseur HTS), une phtalocyanine, une phtalocyanine de cuivre (bleu Vossen), une phtalocyanine de fer, une phtalocyanine de chrome, une phtalocyanine de cobalt, une phtalocyanine de nickel ou une phtalocyanine de molybdène ou une porphyrine.
  2. Utilisation selon la revendication 1,
    le catalyseur étant contenu dans la masse active en une quantité d'au plus 5 % en poids, en particulier d'au plus 2 % en poids, en particulier d'au plus 1 % en poids, en particulier d'au plus 0,5 % en poids, en particulier d'au plus 0,1 % en poids.
  3. Utilisation selon l'une quelconque des revendications précédentes,
    les particules présentant une grosseur moyenne de particule maximale de 50 µm, en particulier de 20 µm, en particulier de 10 µm,en particulier de 1 µm.
  4. Utilisation selon l'une quelconque des revendications précédentes,
    le combustible contenant des atomes d'oxygène et/ou d'azote.
  5. Utilisation selon l'une quelconque des revendications précédentes,
    le combustible comprenant au moins un ester de nitrate, en particulier un ester de nitrate liquide, en particulier du trinitrate de glycéryle, du dinitrate d'éthylèneglycol, du dinitrate de diéthylèneglycol, du dinitrate de triéthylèneglycol ou du trinitrate de méthriol, ou un ester de nitrate présent sous forme de solide polymérique, en particilier la nitrocellulose, le poly(nitrate de vinyle) ou le poly(nitrate de glycidyle) et/ou une nitrosamine, en particulier la 1,3,5-trinitroso-1,3,5-hexahydrotiazine, ou une amine, un amide, un nitrile, un cyanate, un isocyanate, un uréthane, une imine, une cétimine, un imide, un azoture, une nitramine, une nitrosamine, une hydroxylamine, une hydrazine, une hydrazone, un oxime, un furoxane, un furazane, un sel d'ammonium tertiaire, de l'urée, de la méthylurée, de la diméthylurée, de la triméthylurée, de la tétraméthylurée, un sel de guanidine, un sel de monoaminoguanidine, un sel de diaminoguanidine, un sel de triaminoguanidine ou un composé azo, un ester de nitrite ou un hétérocycle azoté, un composé nitro, un composé nitroso ou un composé d'ammonium quaternaire, du dicyanodiamide, de l'azodicarbonamide, de la dinitrosopentaméthylènetétramine (DNPT), du glyoxime, de l'oxamide, de l'acétamide, un carbazide, un semicarbazide, un combustible pulvérulent, en particulier un composé cyano, en particulier du paracyan, ou un combustible formant, lors de la combustion de la masse active, un brouillard par pulvérisation, en particulier un liquide ionique, en particulier un liquide ionique comprenant une structure d'hétérocycle de type imidazole, pyridine, diazine ou autre, en particulier du perchlorate de 1-butyl-3-méthyimidazolium (BMIM-ClO4), chacun des composés indiqués précédemment comprenant au moins un groupe C-N, C-N-O ou C-O-N et éventuellement au moins un groupe C-O.
  6. Utilisation selon l'une quelconque des revendications précédentes, l'oxydant contenant des atomes de chlore et/ou de brome.
  7. Utilisation selon l'une quelconque des revendications précédentes, l'oxydant comprenant du perchlorate d'ammonium.
  8. Utilisation selon la revendication 7,
    un autre catalyseur contenant des atomes de cuivre ou des atomes de fer, en particulier de l'oxyde de fer, du ferrocène, de l'acétylacétonate de fer ou de la phtalocyanine de cuivre, étant contenu dans celle-ci.
EP13004007.4A 2012-08-17 2013-08-12 Utilisation d'un adjuvant dans une masse active pour une cible fictive à rayonnement spectral lors de la combustion de la masse active Active EP2698360B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102012016452.1A DE102012016452B4 (de) 2012-08-17 2012-08-17 Wirkmasse für ein beim Abbrand der Wirkmasse spektral strahlendes Scheinziel mit einem Zusatzstoff

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EP2698360A2 EP2698360A2 (fr) 2014-02-19
EP2698360A3 EP2698360A3 (fr) 2017-08-16
EP2698360B1 true EP2698360B1 (fr) 2019-12-04

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US (1) US9139487B2 (fr)
EP (1) EP2698360B1 (fr)
AU (1) AU2013213696B2 (fr)
DE (1) DE102012016452B4 (fr)
IL (1) IL227587B (fr)
ZA (1) ZA201306135B (fr)

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US10173944B2 (en) 2014-10-16 2019-01-08 Northrop Grumman Innovations Systems, Inc. Compositions usable as flare compositions, countermeasure devices containing the flare compositions, and related methods
US11014859B2 (en) 2014-10-16 2021-05-25 Northrop Grumman Systems Corporation Compositions usable as flare compositions, countermeasure devices containing the flare compositions, and related methods
GB201908786D0 (en) * 2019-06-19 2019-07-31 Spex Oil & Gas Ltd Downhole tool with fuel system
CN113831259B (zh) * 2021-11-05 2023-07-25 内蒙古工业大学 一种芳香族偶氮化合物的合成方法

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US3946555A (en) * 1973-08-22 1976-03-30 Atlantic Research Corporation Process for simulating turbojet engine plumes
JPH08151288A (ja) * 1994-11-25 1996-06-11 Otsuka Chem Co Ltd エアバッグ用ガス発生剤
US6427599B1 (en) * 1997-08-29 2002-08-06 Bae Systems Integrated Defense Solutions Inc. Pyrotechnic compositions and uses therefore
US6017404A (en) * 1998-12-23 2000-01-25 Atlantic Research Corporation Nonazide ammonium nitrate based gas generant compositions that burn at ambient pressure
US6599379B2 (en) * 2001-04-12 2003-07-29 Dmd Systems, Llc Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions
JP4847143B2 (ja) * 2006-01-26 2011-12-28 株式会社ダイセル ガス発生剤組成物
US20100212221A1 (en) * 2009-02-26 2010-08-26 Aradi Allen A Modulation of combustion rates in fuels
DE102010053783A1 (de) * 2010-12-08 2012-06-14 Diehl Bgt Defence Gmbh & Co. Kg Hochleistungswirkmasse für pyrotechnische Infrarotscheinziele

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Publication number Publication date
IL227587B (en) 2019-10-31
DE102012016452B4 (de) 2014-07-24
EP2698360A2 (fr) 2014-02-19
AU2013213696A1 (en) 2014-03-06
US9139487B2 (en) 2015-09-22
AU2013213696B2 (en) 2017-08-10
DE102012016452A1 (de) 2014-02-20
US20150047760A1 (en) 2015-02-19
IL227587A0 (en) 2014-03-31
EP2698360A3 (fr) 2017-08-16
ZA201306135B (en) 2014-04-30

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