FR2471959A1 - Castable, lighting, pyrotechnic compsn. - comprising inorganic oxidant, pref. magnesium powder and aminoplast or phenoplast resin binder - Google Patents
Castable, lighting, pyrotechnic compsn. - comprising inorganic oxidant, pref. magnesium powder and aminoplast or phenoplast resin binder Download PDFInfo
- Publication number
- FR2471959A1 FR2471959A1 FR7931039A FR7931039A FR2471959A1 FR 2471959 A1 FR2471959 A1 FR 2471959A1 FR 7931039 A FR7931039 A FR 7931039A FR 7931039 A FR7931039 A FR 7931039A FR 2471959 A1 FR2471959 A1 FR 2471959A1
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- composition according
- magnesium
- pref
- composition
- powder
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- 239000011230 binding agent Substances 0.000 title claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 title claims abstract 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 23
- 229920005989 resin Polymers 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 title abstract description 6
- 229920003180 amino resin Polymers 0.000 title 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002033 PVDF binder Substances 0.000 claims abstract description 12
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract 2
- 239000005011 phenolic resin Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 70
- 239000011777 magnesium Substances 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 230000009969 flowable effect Effects 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 239000000395 magnesium oxide Substances 0.000 abstract description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001095 magnesium carbonate Substances 0.000 abstract description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000014380 magnesium carbonate Nutrition 0.000 abstract 1
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical class [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
- C06B45/32—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/02—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with an organic non-explosive or an organic non-thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
Abstract
Description
Composition pyrotechnique éclairante coulable comportant
une poudre métallique
Le secteur technique de la présente invention est celui des compositions pyrotechniques éclairantes coulables comprenant un réducteur à base de poudre métallique, un oxydant minéral et un liant du type résine macromoléculaire.Pourable illuminating pyrotechnic composition comprising
a metallic powder
The technical sector of the present invention is that of flowable lighting pyrotechnic compositions comprising a reducing agent based on metal powder, a mineral oxidant and a binder of the macromolecular resin type.
Le rendement global d'une composition éclairante est traduit par son efficacité lumineuse (E) qui est une des caractéristiques photométriques essentielles. Elle est définie commela somme en fonction du temps de l'intensité lumineuse instantanée exprimée en candelas (Cd), le tout rapporté à la masse de composition brûlée. The overall yield of an illuminating composition is expressed by its luminous efficacy (E) which is one of the essential photometric characteristics. It is defined as the sum as a function of the time of the instantaneous light intensity expressed in candelas (Cd), all relative to the mass of composition burned.
De nombreuses compositions pyrotechniques éclairantes mettant en oeuvre un métal réducteur sont connues et on distingue les compositions éclairantes comprimées et les compositions éclairantes coulables. Numerous pyrotechnic lighting compositions using a reducing metal are known and a distinction is made between compressed lighting compositions and flowable lighting compositions.
Les compositions comprimées présentent des caractéristiques photométriques très intéressantes. Ainsi, une composition comprimée contenant 56, 5% de magnésium, 35, 5% de NaNO3 et 8% de polyester chargée dans un pot de 69 mm de diamètre intérieur donne une efficacité lumineuse spécifique de 45000 cd. s/g avec une vitesse de combustion de 2, 45 mm/s ce qui donne une durée d'éclairement suffisante et une intensité lumineuse de 0,58 X 106 cd. The compressed compositions have very interesting photometric characteristics. Thus, a compressed composition containing 56.5% of magnesium, 35.5% of NaNO3 and 8% of polyester loaded in a jar with an internal diameter of 69 mm gives a specific luminous efficacy of 45,000 cd. s / g with a combustion speed of 2.45 mm / s which gives a sufficient duration of illumination and a light intensity of 0.58 X 106 cd.
Dans ces compositions, le couple réducteur oxydant le plus performant du point de vue des caractéristiques photométriques est le couple magnésium/nitrate de sodium qui est également le couple le plus fréquemment utilisé. Le taux de liant varie entre 411O et 9%. Les compositions sont préparées par malaxage puis sont comprimées sous des pressions élevées comprises entre 5 105 Pa et 106 Pa. Ce mode de fabrication présente quelques inconvénients du fait de la sensibilité à la friction de ces compositions et il arrive que des déflagrations se produisent dans les malaxeurs Ces compositions permettent difficilement, compte tenu des taux de compression, l'obtention de pains éclairants d'une taille supérieure à 155 mm.Au délà, il faut en effet des presses importantes ce qui est du domaine du possible, mais également des moules de compression de masse très élevée supérieure à 60 kg. In these compositions, the most efficient oxidizing reducing couple from the point of view of photometric characteristics is the magnesium / sodium nitrate couple which is also the most frequently used pair. The binder rate varies between 411O and 9%. The compositions are prepared by kneading and then are compressed under high pressures of between 5 105 Pa and 106 Pa. This method of manufacture has some disadvantages due to the sensitivity to friction of these compositions and it happens that deflagrations occur in the kneaders These compositions make it difficult, taking into account the compression ratios, to obtain illuminating bars of a size greater than 155 mm. Beyond that, large presses are indeed needed which is in the realm of possibility, but also molds very high mass compression greater than 60 kg.
La géométrie des charges est également limitée.The load geometry is also limited.
On a déjà proposé l'utilisation de résine du type urée-formaldéhyde dans les compositions pyr otecinîques comprimées. The use of urea-formaldehyde type resin has already been proposed in compressed pyr otecinique compositions.
Ainsi, le brevet américain 2 841 481 décrit des compositions comprenant une résine uree-formaldéhyde et un oxydant. La résine représente toutefois 65 à 75% en poids de la masse totale de la composition et joue le rôle d'un réducteur. Le brevet américain 3 474 732 décrit l'enrobage du magnésium dans des compositions éclairantes. Cependant, il s'agit de ltenrobage de magnésium se présentant sous forme de copeaux, de lamelles etc. afin d'assurer leur inflammation. On utilise pour cela un liant du type polyamide acrylique renfermant un réducteur par exemple de la poudre de magnésium et un oxydant par exemple le nitrate de sodium. Thus, American patent 2,841,481 describes compositions comprising a urea-formaldehyde resin and an oxidant. The resin however represents 65 to 75% by weight of the total mass of the composition and plays the role of a reducing agent. US Patent 3,474,732 describes the coating of magnesium in lighting compositions. However, it is the coating of magnesium in the form of chips, strips etc. to ensure their inflammation. For this, a binder of the acrylic polyamide type containing a reducing agent, for example magnesium powder and an oxidizing agent, for example sodium nitrate, is used.
Quant aux compositions éclairantes coulables, elles ne présentent pas les inconvénients des formules comprimées,
Elles sont d'une fabrication et d'une mise en oeuvre aisées, les pots étant remplis par coulée, une cuisson est nécessaire pour réaliser la polymérisation. I1 nXy a plus de limitation de formes ni de dimensions mais l'efficacité lumineuse est toujours limitée.As for the flowable lighting compositions, they do not have the drawbacks of the compressed formulas,
They are easy to manufacture and use, the pots being filled by casting, baking is necessary to carry out the polymerization. I1 nXy has no more limitation of shapes or dimensions but the luminous efficiency is always limited.
Le brevet américain 3 432 370 propose par exemple une composition éclairante coulable enfermant le couple oxydoréducteur nitrate de sodium/magnésium et un liant constitué par un copolymère résultant de la réaction d'un époxy et d'un sel d'amine comportant des terminaisons polyglycol. Ainsi, une formulation à 12% de liant donne une efficacité lumineuse d'environ 24 000 cd. s/g ce qui est très bas avec une vitesse de combustion de l'ordre de 1 mm/sec. American patent 3,432,370 proposes, for example, a flowable illuminating composition enclosing the redox sodium nitrate / magnesium couple and a binder consisting of a copolymer resulting from the reaction of an epoxy and an amine salt comprising polyglycol endings. Thus, a formulation containing 12% of binder gives a luminous efficacy of approximately 24,000 cd. s / g which is very low with a combustion speed of the order of 1 mm / sec.
Le brevet français 2 248 252propose une composition pyrotechnique éclairante coulable comprenant un réducteur à base de poudre métallique et un oxydant classique ; le liant est choisi par les polyhitadiènes carboxiques et les résines époxy. Toutefois,. French Patent 2,248,252 proposes a flowable illuminating pyrotechnic composition comprising a reducing agent based on metallic powder and a conventional oxidant; the binder is chosen by carboxylic polyhitadienes and epoxy resins. However,.
l'efficacité lumineuse reste faible, de l'ordre de 15 000 à 25-000 cd. s/g.the light efficiency remains low, around 15,000 to 25-000 cd. s / g.
On a pensé à augmenter l'efficacité des compositions coulables en incorporant des plastifiants énergétiques tels que les di-ou triéthylène glycol dinitrates (DEGN ou TEGDN). I1 est ainsi possible d'obtenir des efficacités lumineuses de l'ordre de 46 800 Cd. s/g avec une formulation contenant 52% de Mg 40/200mesh, 28% de NaN03, 30% liant contenant 50% de DEGDN comme plastifiant. Le liant est le diacrylate de Mshydroxyéthyl-carbonate. It has been thought to increase the effectiveness of the flowable compositions by incorporating energetic plasticizers such as di- or triethylene glycol dinitrates (DEGN or TEGDN). It is thus possible to obtain luminous efficiencies of the order of 46,800 Cd. S / g with a formulation containing 52% Mg 40 / 200mesh, 28% NaNO3, 30% binder containing 50% DEGDN as plasticizer. The binder is Mshydroxyethyl-carbonate diacrylate.
Toutefois, on retrouve des difficultés de mise en oeuvre puisque si les produits nitrés sont des substances explosives assez stables, il en va autrement lors du mélange avec un couple oxydo-réducteur ; ainsi la sensibilité à l'impact est augmentée et leur emploi rend plus délicate la fabrication etla mise en oeuvre de ces compositions coulables
La présente invention a pourlrbut de fournir une composition pyrotechnique éclairante coulable douée d'une efficacité lumineuse très élevée avec une vitesse de combustion comprise entre 1 et 2 mm/s.However, there are implementation difficulties since if the nitrated products are fairly stable explosive substances, it is different when mixing with an oxidation-reduction couple; thus the sensitivity to impact is increased and their use makes it more difficult to manufacture and use these flowable compositions.
The purpose of the present invention is to provide a flowable illuminating pyrotechnic composition with very high luminous efficacy with a combustion speed of between 1 and 2 mm / s.
L'invention a donc pour objet une composition pyrotechnique éclairante coulable, caractérisée en ce quelle comporte en combinaison un système oxydo-réducteur du type connu constitué par un oxydant minéral et une poudre métallique et un liant représenté par une résine urée-formaldéhyde, formophénolique ou xylèno-phénolique. The subject of the invention is therefore a flowable illuminating pyrotechnic composition, characterized in that it comprises in combination a redox system of the known type consisting of an inorganic oxidant and a metal powder and a binder represented by a urea-formaldehyde, formophenolic or xylenophenolic.
Le liant est une résine urée-formaldéhyde ; la poudre métallique est enrobée par un polyfluorure carboné ; ce polyfluorure peut être le polyfluorure de vinylidène. The binder is a urea-formaldehyde resin; the metal powder is coated with a carbonaceous polyfluoride; this polyfluoride can be polyvinylidene fluoride.
Le réducteur peut être représenté par la poudre de magnésium, le diamètre des grains de la poudre étant de l'ordre de 0, 290 à 0, 335 mm,
Avantageusement, le pourcentage en poids de polyfluorure de vinylidène est de l'ordre de 0, 9 à 2, 5% de la masse totale du réducteur
L'oxydant est choisi dans le groupe constitué par un nitrate, un perchlorate olLun peroxyde de métal alcalin ou alcalinoterreux. The reducing agent can be represented by the magnesium powder, the diameter of the grains of the powder being of the order of 0.290 to 0.335 mm,
Advantageously, the percentage by weight of polyvinylidene fluoride is of the order of 0.9 to 2.5% of the total mass of the reducing agent
The oxidant is chosen from the group consisting of a nitrate, an olLun perchlorate, an alkali or alkaline earth metal peroxide.
Parmi ceux-ci, le nitrate de sodium est préféré. Of these, sodium nitrate is preferred.
Divers additifs peuvent être incorporés à la composition selon l'invention par exemple la magnésie MgO, le carbonate de magnésium MgC03, le sulfate de manganèseMnS040
Les pourcentages en poids des divers constituants sont choisis de préférence comme suit:
49 à 56% de magnésium enrobé ou non
. 28 à 32% de nitrate de sodium
. 12 à 20% de résine urée-formaldéhyde
. O, 5 à 3% de sulfate de magnésium.Various additives can be incorporated into the composition according to the invention, for example magnesia MgO, magnesium carbonate MgC03, manganese sulfateMnS040
The percentages by weight of the various constituents are preferably chosen as follows:
49 to 56% coated or uncoated magnesium
. 28 to 32% sodium nitrate
. 12 to 20% urea-formaldehyde resin
. 0.5 to 3% magnesium sulfate.
Outre les avantages mentionnés relativement aux compositions coulables, la composition selon l'invention ne présente pas de risques particuliers, autres que ceux inhérents à la mise en oeuvre, de tous les mélanges pyrotechniques. La tenue au vieillissement est améliorée par l'enrobage et les essais effectués ont montré que l'efficacité lumineuse n'était pas affectée par un stockage prolongé des compositions. Enfin, le prix de revient de ces compositions est nettement inférieur à celui des compositions antérieures puisqu'on utilise uniquement des produits courants du commerce. In addition to the advantages mentioned relative to flowable compositions, the composition according to the invention does not present any particular risks, other than those inherent in the use, of all pyrotechnic mixtures. The aging resistance is improved by the coating and the tests carried out have shown that the luminous efficacy was not affected by prolonged storage of the compositions. Finally, the cost price of these compositions is much lower than that of the previous compositions since only commercially available products are used.
Diverses poudres métalliques peuvent être utilisées dans les compositions selon l'invention, A titre indicatif, on peut mentionner la poudre de magnésium, d'aluminium, de zirconium, de chrome ou de silicium. Cependant, on a constaté que les meilleurs résultats sont obtenus lorsqu'on utilise le magnésium. Various metallic powders can be used in the compositions according to the invention. By way of indication, mention may be made of magnesium, aluminum, zirconium, chromium or silicon powder. However, it has been found that the best results are obtained when using magnesium.
Pour enrober, le réducteur, par exemple le magnésium, on s ty prend de la manière suivante ou de façon équivalente. On dissout dans un réacteur thermostaté à chaud le polyfluorure carboné, par exemple le polyfluorure de vinylidène dans un solvant et on ajoute la poudre métallique. On agite et on fait évaporer le solvant sous hotte en maintenant l'agitation. To coat the reducing agent, for example magnesium, it is taken in the following manner or in an equivalent manner. The carbon-containing polyfluoride, for example polyvinylidene fluoride, is dissolved in a hot thermostated reactor in a solvent and the metal powder is added. Stir and evaporate the solvent in a hood while stirring.
Lorsque la poudre métallique enrobée commence à prendre en masse, on ajoute de l'éthanol pour arrêter la réaction. Après filtration, on laisse sécher la poudre enrobée à l'air.When the coated metal powder begins to solidify, ethanol is added to stop the reaction. After filtration, the coated powder is left to air dry.
Ainsi il est possible d'utiliser une poudre métallique comme réducteur et tout particulièrement le magnésium avec un liant du type urée-formaldéhyde renfermant de l'rai en proportion notable. La poudre métallique est protégée de llattaque de l'eau contenue dans l'urée-formol, même pour des très longues périodes de stockage. De plus, lors de la mise en oeuvre de lacomposition éclairante, la viscosité du mélange est abaissée de façon importante, ce qui facilite les opérations de coulage. Thus it is possible to use a metal powder as a reducing agent and very particularly magnesium with a binder of the urea-formaldehyde type containing ore in a significant proportion. The metal powder is protected from attack by water contained in urea-formaldehyde, even for very long periods of storage. In addition, during the implementation of the illuminating composition, the viscosity of the mixture is lowered significantly, which facilitates the casting operations.
Le polyfluorure peut être quelconque et il est préférable d'utiliser un polyfluorure soluble dans un solvant classique par exemple une cétone aliphatique. Le pourcentage utilisé est généralement faible de l'ordre de 2%. The polyfluoride can be any and it is preferable to use a polyfluoride soluble in a conventional solvent, for example an aliphatic ketone. The percentage used is generally low, around 2%.
On choisit de préférence un oxydant micronisé dont le diamètre des grains est sensiblement inférieur à 0, 1 mm. On a constaté que le mariage des coupes granulométriques complémentaires de métal 300-800 mesh et d'oxydant 0-100 mesh a pour effet de diminuer la viscosité de la composition éclairante préparée. A micronized oxidant is preferably chosen, the grain diameter of which is substantially less than 0.1 mm. It has been found that the marriage of complementary particle size sections of metal 300-800 mesh and oxidant 0-100 mesh has the effect of reducing the viscosity of the illuminating composition prepared.
Le liant est également un produit du commerce vendu sous la marque "NOBELAMINE" renfermant environ 55% de matière sèche ; l'analyse élémentaire de ce liant donne à 1% près les résultats suivants : azote 22%, carbone 39%, oxygène 32, 5%, hydrogène 6, 5%. The binder is also a commercial product sold under the brand "NOBELAMINE" containing about 55% of dry matter; elementary analysis of this binder gives the following results to within 1%: nitrogen 22%, carbon 39%, oxygen 32.5%, hydrogen 6.5%.
I1 a été constaté que l'addition d'un sel de manganèse, le sulfate de manganèse par exemple, assure une combustion plus lente de la composition, ce qui accroc son efficacité. D'autres additifs dopants peuvent être ajoutés à la composition éclairante coulable selon l'invention pour améliorer certaines propriétés. I1 was found that the addition of a manganese salt, manganese sulfate for example, ensures a slower combustion of the composition, which increases its effectiveness. Other doping additives can be added to the flowable lighting composition according to the invention to improve certain properties.
On peut citer les anti-agglomérants, par exemple la magnésie (MgO) ou un carbonate tel le carbonate de magnésium.Mention may be made of anti-caking agents, for example magnesia (MgO) or a carbonate such as magnesium carbonate.
Pour réaliser une composition éclairante selon l'invention on s'y prend de la manière suivante : on agite dans un mélangeur-disperseur d'abord le magnésium enrobé avec le liant liquide. On agite ensuite le nitrate de sodium dans lequel on a dispersé préalablement le dopant. Au bout de quelques minutes de brassage, on obtient un mélange thixotrope qui peut être versé rapidement dans un moule de forme quelconque, Par vibration, on élimine les bulles et on tasse la composition. On peut améliorer le résultat en soumettant à un vide poussé les pots éclairants préparés. To produce an illuminating composition according to the invention, this is done in the following manner: the magnesium coated with the liquid binder is first stirred in a mixer-disperser. Then stirred the sodium nitrate in which the dopant was previously dispersed. After a few minutes of stirring, a thixotropic mixture is obtained which can be quickly poured into a mold of any shape. By vibration, the bubbles are removed and the composition is packed. The result can be improved by subjecting the prepared light pots to a high vacuum.
On réalise ensuite la polymérisation sans catalyseur dans une étuve à 80 c pendant 6 jours. On obtient finalement une masse f erme et rigide.The polymerization is then carried out without catalyst in an oven at 80 c for 6 days. We finally obtain a firm and rigid mass.
On a remarqué que l'utilisation du magnésium enrobé confère un avantage tout à fait inattendu puisque l'addition de celui-ci dans la résine urée-formaldéhyde liquide diminue sa viscosité, ce qui améliore la coulabilité. It has been noted that the use of coated magnesium confers an entirely unexpected advantage since the addition of this in the liquid urea-formaldehyde resin decreases its viscosity, which improves the flowability.
Ainsi, il est possible d'abaisser le taux de résine utilisée tout en conservant une bonne coulabilité. Thus, it is possible to lower the rate of resin used while retaining good flowability.
Une polymérisation à température élevée, 60 à 800 c environ, permet d'obtenir une meilleure cohésion de la composition et une durée de conservation pratiquement illimitée à température ambiante. Polymerization at high temperature, approximately 60 to 800 c, makes it possible to obtain better cohesion of the composition and a practically unlimited shelf life at room temperature.
L'invention sera mieux comprise à la lumière des exemples qui vont suivre de modes de réalisation particuliers sans caractère limitatif. The invention will be better understood in the light of the examples which follow of particular embodiments without limiting nature.
Exemple 1
On réalise une composition éclairante à l'aide des composés indiqués dans laquelle le magnésium n'est pas enrobé et selon les pourcentages suivants
Mg (non enrobé) 49,8%
PVDF (polyfluorure de 0,0%
vinylidène)
NaN03 30,0%
Mg0+MgC03 0,2%
Nobélamine 20,0%
On verse cette composition dans une enveloppe en carton présentant un diamètre interne de 45mm. La masse de la composition est de 137,4 g.On teste la composition après polymérisation et on obtient les résultats suivants
Temps de combustion 33, 9 s
Vitesse de combustion 1, 98 mm/s
Efficacité lumineuse 41. 000 Cd s/g
On voit qu'une telle composition présente une bonne efficacité lumineuse qui peut être mise en oeuvre chaque fois que la durée de conservation n'est pas le facteur recherché en priorité. Example 1
An illuminating composition is produced using the indicated compounds in which the magnesium is not coated and according to the following percentages
Mg (uncoated) 49.8%
PVDF (0.0% polyfluoride
vinylidene)
NaN03 30.0%
0.2% Mg0 + MgC03
Nobelamine 20.0%
This composition is poured into a cardboard envelope having an internal diameter of 45mm. The mass of the composition is 137.4 g. The composition is tested after polymerization and the following results are obtained
Burning time 33.9 s
Burning speed 1.98 mm / s
Luminous efficacy 41. 000 Cd s / g
It can be seen that such a composition has good luminous efficacy which can be implemented each time that the shelf life is not the factor sought as a priority.
Exemple 2
a) Préparation du magnésium enrobé.Example 2
a) Preparation of the coated magnesium.
On introduit dans un réacteur thermostaté à 80 0 c 200 cm3 de méthyléthylcétone et 2g de polyfluorure de vinylidène et on ajoute sous agitation 200g de poudre de magnésium. On prolonge l'agitation et on évapore le solvant Dès quele-magnésium commence à prendre en masse, on verse 50g d'éthanol. On filtre et on sèche le magnésium enrobé à l'air. 200 g of methyl ethyl ketone and 2 g of polyvinylidene fluoride are introduced into a reactor thermostatically controlled at 80 ° C. and 200 g of magnesium powder are added with stirring. The stirring is continued and the solvent is evaporated. As soon as the magnesium begins to solidify, 50 g of ethanol are poured. The coated magnesium is filtered and dried in air.
b) Préparation de la composition éclairante. b) Preparation of the illuminating composition.
On mélange de la manière indiquée les divers constituants de la composition éclairante selon les pourcentages suivants
Mg enrobé 49%
PVDF 1%
NaN03 32%
MgO 1%
Nobélamine 17%
On verse cette composition dans une enveloppe encarton dont le diamètre interne est de 45 mme La masse de la composition est de 147, 6g. Après polymérisation, on teste la composition et on obtient les résultats suivants
Temps de combustion 53,3 s
Vitesse de combustion 1,24 mm/s
Efficacité lumineuse 42, 800 Cd s/g
Une composition de ce type présente une bonne efficacité lumineuse et ses performances ne sont pas affectées parun stockage même prolongé. The various constituents of the lighting composition are mixed as indicated in the following percentages
Mg coated 49%
PVDF 1%
NaN03 32%
MgO 1%
Nobelamine 17%
This composition is poured into a cardboard envelope whose internal diameter is 45 ms. The mass of the composition is 147.6 g. After polymerization, the composition is tested and the following results are obtained
Burning time 53.3 s
Burning speed 1.24 mm / s
Luminous efficacy 42, 800 Cd s / g
A composition of this type has good luminous efficacy and its performance is not affected by even prolonged storage.
Exemple 3
On prépare la composition éclairante suivante de la manière enseignée à l'exemple 2
Mg enrobé 49%
PVDF 1%
NaN03 31%
MnS04, 1 H20 2,5%
Nobélamine 16,5%
Diamètre intérieur de l'enveloppe 65mm
Masse de composition 386,4g
Temps de combustion 68,4s
Vitesse de combustion 1,27mm/s
Efficacité lumineuse 50.400 Cd s/g
En comparant ces résultats avec ceux de 11 exemple 2, on voit que l'addition de MnS04 améliore considérablement l'effica- cité lumineuse.Example 3
The following illuminating composition is prepared in the manner taught in Example 2
Mg coated 49%
PVDF 1%
NaN03 31%
MnS04, 1 H20 2.5%
Nobelamine 16.5%
Inner diameter of the envelope 65mm
Composition mass 386.4 g
Burning time 68.4s
Burning speed 1.27mm / s
Luminous efficacy 50,400 Cd s / g
Comparing these results with those of Example 2, it can be seen that the addition of MnSO 4 considerably improves the light efficiency.
Exemple 4
On prépare comme enseigné à l'exemple 2 la composition suivante
Mg enrobé 51,4%
PVDF 1,0%
NaN03 29, 1%
MnS04, 1 H20 2,0%
Nobélamine 16,5%
Diamètre intérieur de l'enveloppe 45mm
Masse de composition 149,9 g
Temps de combustion 41, 1 s
Vitesse de combustion 1,63 mm/s
Efficacité lumineuse 52.Example 4
The following composition is prepared as taught in Example 2
Mg coated 51.4%
PVDF 1.0%
NaN03 29.1%
MnS04, 1 H20 2.0%
Nobelamine 16.5%
Inner diameter of the envelope 45mm
Composition mass 149.9 g
Burning time 41.1 s
Burning speed 1.63 mm / s
Luminous efficacy 52.
100 Cd s/g
Exemple 5
On prépare comme enseigné à l'exemple 2, la composition suivante
Mg enrobé 52,9%
PVDF 1,1%
NaN03 30,0%
MnS04, 1 H20 2,0%
Nobélamine 14,0%
Diamètre intérieur de l'enveloppe 65mm
Masse de composition 397, 7g
Temps de combustion 48, 3s
Vitesse de combustion 1, 81 mm/s
Efficacité lumineuse 54.100 Cd s / g
Example 5
The following composition is prepared as taught in Example 2
Mg coated 52.9%
PVDF 1.1%
NaN03 30.0%
MnS04, 1 H20 2.0%
Nobelamine 14.0%
Inner diameter of the envelope 65mm
Composition mass 397, 7g
Burning time 48.3 s
Burning rate 1.81 mm / s
Luminous efficacy 54.
000 Cd s/g
La comparaison des résultats exemples 3,4 et 5 permet de voir que la diminution du taux de liant permet dtaccroître l'efficacité lumineuse. 000 Cd s / g
The comparison of the results of examples 3, 4 and 5 makes it possible to see that the reduction in the level of binder makes it possible to increase the luminous efficiency.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7931039A FR2471959A1 (en) | 1979-12-19 | 1979-12-19 | Castable, lighting, pyrotechnic compsn. - comprising inorganic oxidant, pref. magnesium powder and aminoplast or phenoplast resin binder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7931039A FR2471959A1 (en) | 1979-12-19 | 1979-12-19 | Castable, lighting, pyrotechnic compsn. - comprising inorganic oxidant, pref. magnesium powder and aminoplast or phenoplast resin binder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2471959A1 true FR2471959A1 (en) | 1981-06-26 |
| FR2471959B1 FR2471959B1 (en) | 1983-01-14 |
Family
ID=9232914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR7931039A Granted FR2471959A1 (en) | 1979-12-19 | 1979-12-19 | Castable, lighting, pyrotechnic compsn. - comprising inorganic oxidant, pref. magnesium powder and aminoplast or phenoplast resin binder |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2471959A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2508896A1 (en) * | 1981-07-02 | 1983-01-07 | France Etat | Cellular pyrotechnic material with controlled porosity - comprising binder, oxidn.-redn. couple and micro-cavities, useful smoke producing, incendiary, heat vaporising or fuel compsns. |
| FR2516230A1 (en) * | 1981-11-10 | 1983-05-13 | Poudres & Explosifs Ste Nale | PYROTECHNIC ARTIFICE LIGHTENING AUTODISPERSABLE |
| WO1988007985A2 (en) * | 1987-04-10 | 1988-10-20 | Martin Marietta Corporation | Combustible delay barriers |
| RU2611872C2 (en) * | 2015-07-27 | 2017-03-01 | Акционерное общество "Чебоксарское производственное объединение имени В.И. Чапаева" | Illuminating pyrotechnic composition |
| RU2618075C1 (en) * | 2016-03-31 | 2017-05-02 | Акционерное общество "Чебоксарское производственное объединение имени В.И. Чапаева" | Illuminating pyrotechnic composition |
| EP2592060A3 (en) * | 2011-10-21 | 2017-07-26 | Diehl Defence GmbH & Co. KG | Use of zirconium or a mixture containing zirconium |
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|---|---|---|---|---|
| US2841481A (en) * | 1954-03-11 | 1958-07-01 | Brock S Crystal Palace Firewor | Pyrotechnic masses |
| DE1446913A1 (en) * | 1965-09-08 | 1969-03-06 | Bock Geb | Pyrotechnic masses and methods of making fireworks |
| GB1202390A (en) * | 1967-11-06 | 1970-08-19 | Astra Fireworks Ltd | Improvements in or relating to pyrotechnic compositions |
| FR2070262A5 (en) * | 1969-11-05 | 1971-09-10 | France Etat | |
| US3690972A (en) * | 1971-07-16 | 1972-09-12 | Us Army | Green flare composition |
| US4094711A (en) * | 1977-09-01 | 1978-06-13 | Ford Aerospace & Communications Corporation | Tracer and composition |
| FR2389867A1 (en) * | 1977-05-06 | 1978-12-01 | Oerlikon Buehrle Ag |
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1979
- 1979-12-19 FR FR7931039A patent/FR2471959A1/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2841481A (en) * | 1954-03-11 | 1958-07-01 | Brock S Crystal Palace Firewor | Pyrotechnic masses |
| DE1446913A1 (en) * | 1965-09-08 | 1969-03-06 | Bock Geb | Pyrotechnic masses and methods of making fireworks |
| GB1202390A (en) * | 1967-11-06 | 1970-08-19 | Astra Fireworks Ltd | Improvements in or relating to pyrotechnic compositions |
| FR2070262A5 (en) * | 1969-11-05 | 1971-09-10 | France Etat | |
| US3690972A (en) * | 1971-07-16 | 1972-09-12 | Us Army | Green flare composition |
| FR2389867A1 (en) * | 1977-05-06 | 1978-12-01 | Oerlikon Buehrle Ag | |
| US4094711A (en) * | 1977-09-01 | 1978-06-13 | Ford Aerospace & Communications Corporation | Tracer and composition |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2508896A1 (en) * | 1981-07-02 | 1983-01-07 | France Etat | Cellular pyrotechnic material with controlled porosity - comprising binder, oxidn.-redn. couple and micro-cavities, useful smoke producing, incendiary, heat vaporising or fuel compsns. |
| FR2516230A1 (en) * | 1981-11-10 | 1983-05-13 | Poudres & Explosifs Ste Nale | PYROTECHNIC ARTIFICE LIGHTENING AUTODISPERSABLE |
| EP0079273A1 (en) * | 1981-11-10 | 1983-05-18 | Societe Nationale Des Poudres Et Explosifs | Self-fragmenting fireworks |
| WO1988007985A2 (en) * | 1987-04-10 | 1988-10-20 | Martin Marietta Corporation | Combustible delay barriers |
| WO1988007985A3 (en) * | 1987-04-10 | 1988-11-03 | Martin Marietta Corp | Combustible delay barriers |
| EP2592060A3 (en) * | 2011-10-21 | 2017-07-26 | Diehl Defence GmbH & Co. KG | Use of zirconium or a mixture containing zirconium |
| RU2611872C2 (en) * | 2015-07-27 | 2017-03-01 | Акционерное общество "Чебоксарское производственное объединение имени В.И. Чапаева" | Illuminating pyrotechnic composition |
| RU2618075C1 (en) * | 2016-03-31 | 2017-05-02 | Акционерное общество "Чебоксарское производственное объединение имени В.И. Чапаева" | Illuminating pyrotechnic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2471959B1 (en) | 1983-01-14 |
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