EP0079273B1 - In Leuchtpartikel zerfallender Feuerwerkskörper - Google Patents

In Leuchtpartikel zerfallender Feuerwerkskörper Download PDF

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Publication number
EP0079273B1
EP0079273B1 EP82401996A EP82401996A EP0079273B1 EP 0079273 B1 EP0079273 B1 EP 0079273B1 EP 82401996 A EP82401996 A EP 82401996A EP 82401996 A EP82401996 A EP 82401996A EP 0079273 B1 EP0079273 B1 EP 0079273B1
Authority
EP
European Patent Office
Prior art keywords
pyrotechnic
composition
pyrotechnic device
binder
phenoplast
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82401996A
Other languages
English (en)
French (fr)
Other versions
EP0079273A1 (de
Inventor
Lucien Autret
Jean-Philippe Godfrin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe Nationale des Poudres et Explosifs
Original Assignee
Societe Nationale des Poudres et Explosifs
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe Nationale des Poudres et Explosifs filed Critical Societe Nationale des Poudres et Explosifs
Publication of EP0079273A1 publication Critical patent/EP0079273A1/de
Application granted granted Critical
Publication of EP0079273B1 publication Critical patent/EP0079273B1/de
Expired legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B4/00—Fireworks, i.e. pyrotechnic devices for amusement, display, illumination or signal purposes
    • F42B4/30—Manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/113—Inorganic oxygen-halogen salt

Definitions

  • the invention relates to an illuminating pyrotechnic device, intended to emit a light flux from multiple mobile point sources, in particular during fireworks shows, this pyrotechnic device consisting of an envelope which contains a solid pyrotechnic composition made from at least one polymerized binder, an oxidant and a combustible metal.
  • Pyrotechnic devices comprising an incombustible or scarcely combustible external envelope are in common use, and for example the Bengal lights are very often constituted by a thick cardboard tube in which is poured and solidified the illuminating pyrotechnic composition which adheres completely to this envelope .
  • Illuminating pyrotechnic compositions with polymerized binder are known, and for example French patent 2 248 252 relates to such compositions which have a high luminous efficacy and which use a binder which can be either a polybutadiene carboxylic or a silicone, such compositions being intended to be shaped into cylinders, in order to constitute signaling torches or lighting devices which have a long operating life since these compositions burn in parallel layers, as a propellant would do, and the combustion rate is low, generally less than 2 millimeters per second.
  • compositions using a binder of the phenoplast type are also known from patent FR 2 471 959, which describes in particular a block burning in parallel layers with a diameter of 45 millimeters in which the mineral oxidant has a particle size less than 100 micrometers and which comprises a metallic fuel, the patent GB 1 202390 also describing compositions with a polymerized binder of the phenoplast type comprising an oxidant and a combustible metal.
  • the object of the present invention is to produce pyrotechnic devices, the composition of which bursts into a multitude of incandescent fragments after ignition, the different fragments continuing to burn and to emit sparks with a bright glow which marks their aerial trajectories, l 'assembly constituting an immense star or an immense scintillating sheaf, and, the invention is characterized in that on the one hand this block comprises incipient fractures within this composition, caused by rapid cooling after polymerization which creates tensions internal, and on the other hand the pyrotechnic composition only partially adheres to the envelope, so that this composition bursts after the ignition of the device.
  • the envelope is cylindrical and has an internal diameter greater than 20 millimeters for the most effective compositions, with easy comminution, and greater than 30 millimeters for the compositions with current comminution.
  • the phenoplast binder is an alkaline phenolic resin which polymerizes at a temperature above 140 ° C.
  • the resins which catalyze in an acid medium and the phenol-formaldehyde-resorcinol resins make it only difficult to obtain self-dispersible compositions, and require a much greater heat treatment which is difficult to reproduce.
  • the unpolymerized phenoplast binder has a concentration of less than 60% and constitutes from 25 to 45% of the total weight of the pyrotechnic composition.
  • concentration is the percentage of solid products relative to the solvent, this solvent possibly being in particular water, alcohol or formaldehyde, and a concentration rate of less than 60% makes it possible to obtain a polymerization shrinkage sufficient for producing detachments between the polymerized composition and the envelope which partially surrounds this composition, which facilitates the subsequent bursting of the block of polymerized composition.
  • the phenoplast binder is combined with an oxidant chosen from the group of perchlorates of alkaline character, and more particularly with potassium perchlorate, introduced in proportions of between 40% and 60% of the total weight of the composition.
  • the particle size of the oxidant is one of the essential parameters which allows the adjustment of the burst effect, and preferably the particle size is less than 100 micrometers and even less than 70 micrometers when the cooling of the composition is not fast enough or when blocks with a diameter less than 50 millimeters want to be obtained.
  • the phenoplast binder is combined with a combustible metal which constitutes from 10% to 30% of the total weight of the pyrotechnic composition, and the combustible metal can be passivated aluminum such as oxidized or surface chromated aluminum.
  • the pyrotechnic composition is polymerized in place in the outer envelope, but it is then desirable for the binder to be an alkaline phenolic resin, the polymerization temperature of which is greater than 140 ° C., and this outer envelope is conveniently constituted by a cylindrical tube. provided with a bottom.
  • cylindrical blocks of polymerized composition can be added in external envelopes, but it is then advantageous that on the one hand a clearance of at least a few tenths of a millimeter is provided, and that on the other hand, a discontinuous bonding is carried out between this block and this envelope so as to provide zones of lateral inflammation, the zones of non-adhesion having to be all the more important on the surface the smaller the dimension of the block. .
  • the device after the polymerization time of the binder, carried out in an oven, the device is immediately placed in the open air, the various devices being sufficiently distant from each other so that the thermal interactions are negligible .
  • the internal tensions and the incipient fractures constituted by microcracks which determine a three-dimensional network of cracks, can be increased either by choosing an alkaline phenolic resin which polymerizes at higher temperature, or by carrying out a more rapid cooling after polymerization, for example , by placing the fireworks in a stream of air at room temperature, or by placing the fireworks in cells formed in metal plates which are partially immersed in a coolant.
  • the advantages obtained thanks to this invention essentially lie in the distribution of the light source within a very large volume.
  • Such a distribution can be used in particular in the context of a firework show to constitute "very large flashovers which are similar to light fountains since each fragment of the initial block emits multiple stars, which remain lit for a few seconds or a few fractions of seconds, and which mark the wake of these fragments.
  • This distribution of the light source in a very large volume can also be useful for intense short-term illumination, generally less than 5 seconds, which attenuates the shadows cast, and, applications can be envisaged either for the lighting of monuments, or sites as part of a "sound and light show using articles, or for the temporary lighting of a" battlefield ".
  • the non-polymerized composition is in the form of a more or less thick pourable liquid, or of an injectable soft paste, which offers great manufacturing safety since the fluid composition is hardly flammable and no significant evacuation of solvent is to be expected.
  • all of the compositions are pourable and, for the most part, require only cooling in the open air after polymerization in an oven, the use of forced air or refrigeration tanks. may nevertheless be necessary for compositions close to the limits of the preferential range.
  • This preferred area of the invention therefore excludes the phenoplast binders which catalyze in an acid medium, because these binders lead to a very reduced and not instantaneous dispersion, the device then tending to behave more like an illuminating fountain with irregular frontal combustion than like a self-dispersing block; more the use of an acidic catalytic system requires the use of rigorously passivated aluminum in order to avoid attack by the acid, and the evolution of hydrogen which accentuates the swelling at the time of the polymerization harms a homogeneous and reproducible polymerization.
  • the phenolic resin sold by the French company CDF-CHIMIE under the reference 1221 constitutes an example of binder with which it is very difficult to carry out the invention in a satisfactory manner.
  • the preferred field of the invention also excludes very alkaline and very condensed phenolic resins which are self-hardening at 120 D C because such resins, for example that marketed by the company HOECHST under the reference PHENODUR PW 799, cause significant swelling of the paste into during polymerization, but the device obtained fragments only partially and irregularly, in particular when rapid cooling is only carried out in the open air.
  • one of the resins allowing the best results to be obtained is the resin sold by the company HOECHST under the reference PHENODUR PW 759. It is a resin which uses water as solvent, this which is particularly advantageous in terms of safety, which is self-hardening in one hour at 170 ° C., which is slightly alkaline, which has a concentration of 50%, and which is weakly condensed. It should however be noted that the raw aluminum is slightly attacked by this resin and that it is therefore preferable to use passivated aluminum to obtain a more spectacular light effect.
  • the rate and the quality of the combustible metal to be used are essentially determined by the light effects sought by a person skilled in the art, and, for example, by choosing as a base a rate of 13% of thinly oxidized fine aluminum.
  • potassium perchlorate with a particle size of 40 ⁇ m and with HOECHST resin reference PW 759 the various examples below illustrate the possibilities of implementation:
  • compositions given as examples, into 1.5 mm thick cardboard tubes, provided with an insert also made of cardboard, the internal diameter of which is 34 millimeters and the height of 50 millimeters.
  • the composition weight being 45 grams per tube, which corresponds to an initial filling substantially equal to three quarters of the internal volume of the tubes.
  • the fireworks are extracted from the oven and suddenly pass from 170 ° C to 18 ° C in a ventilated room, these fireworks being spaced apart from each other by about 25 centimeters and being arranged on the same plane.
  • the swelling during the polymerization is very important since it can reach a quarter of the initial volume, while the contraction by cooling is much weaker, however it is the cooling phase which is essential to obtain the bursting of the block and it is these cooling conditions which must be adapted to optimize the desired effect, the initial bursting regime more or less close to an internal explosion being caused by the very large initial combustion surface offered by the internal slots and the detached areas of the carton, which ensure the initial pressurization and determine the bursting of the composition block.
  • This bursting phenomenon also depends on the particle size of the oxidant and the smallest dimension of the block, the bursting being favored by a fine particle size, less than 70 micrometers, and by the increase in the smallest dimension, if possible beyond 25 millimeters.
  • the ignition of the test devices was carried out with a simple drill bit in contact with the free surface of the cylindrical block of composition, but any other means of ignition commonly used by the fireworks can be used, in particular a relay charge , a primer, or a pyrotechnic delay.
  • the ignitions of the devices of examples n Ds 2, 3 and 4 determine real instantaneous explosions which project in a radius of 40 meters small incandescent and very bright fragments.
  • the number of fragments and the directions of projections are random, but there are compensation effects between the thousands of ejected fragments, and the overall effects are very well reproducible.
  • Each incandescent fragment is accompanied by a trail of stars which remain lit for a few seconds, and the combustion of the largest fragments can reach 5 seconds.
  • the manufacturing of the device n ° 1 leads to an excessive swelling during the polymerization which leads to poorer mechanical properties, as for the devices in Example 5, cooling in the open air is no longer suitable, because the block burns with strong projections of incandescent elements, which causes an effect appreciable aesthetics, but the artifice does not burst significantly and repetitively.
  • the pyrotechnic lighting device according to the invention can be surrounded by a resistant tube which transforms the multidirectional burst into a directed jet whose incandescent fragments and generators of lasting sparks are projected at great distance.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Air Bags (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)

Claims (16)

1. Feuerwerkskörper, bestehend aus einer Hülle, die einen Block aus pyrotechnischer Zusammensetzung enthält, dessen kleinste Abmessung über 15 mm ist, der aus wenigstens einem polymerisierten Bindemittel des Phenoplasttyps, einem Oxidationsmittel mit einer Korngröße unter 150 IJ.m und einem brennbaren Metall hergestellt ist, dadurch gekennzeichnet, daß einerseits dieser Block Bruchauslösestellen im Inneren dieser Zusammensetzung aufweist, die durch eine rasche Abkühlung nach Polymerisation, die innere Spannungen erzeugt, hervorgerufen sind, und daß andererseits die pyrotechnische Zusammensetzung nur teilweise an der Hülle haftet, so daß diese Zusammensetzung nach dem Zünden des Körpers zerplatzt.
2. Feuerwerkskörper nach Anspruch 1, dadurch gekennzeichnet, daß die Hülle zylindrisch ist und einen Innendurchmesser über 20 mm aufweist.
3. Feuerwerkskörper nach Anspruch 1, dadurch gekennzeichnet, daß das Phenoplastbindemittel ein Phenolharz ist.
4. Feuerwerkskörper nach Anspruch 3, dadurch gekennzeichnet, daß das Phenolharz bei einer Temperatur über 140 °C polymerisiert.
5. Feuerwerkskörper nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß das Phenolharz ein alkalisches Harz ist.
6. Feuerwerkskörper nach einem der Ansprüche 1 oder 3, dadurch gekennzeichnet, daß das nicht polymerisierte Phenolplastbindemittel eine Konzentration unter 60 % aufweist.
7. Feuerwerkskörper nach einem der Ansprüche 1 oder 3, dadurch gekennzeichnet, daß das Phenolplastbindemittel 25 bis 45% des Gesamtgewichts der nicht polymerisierten pyrotechnischen Zusammensetzung darstellt.
8. Feuerwerkskörper nach einem der Ansprüche 1, 3 oder 7, dadurch gekennzeichnet, daß das Phenoplastbindemittel mit einem aus der Gruppe der Perchlorate alkalischer Eigenschaft gewählten Oxidationsmittel kombiniert ist.
9. Feuerwerkskörper nach einem der Ansprüche 1 oder 8, dadurch gekennzeichnet, daß das Oxidationsmittel eine Korngröße unter 100 µm hat.
10. Feuerwerkskörper nach einem der Ansprüche 8 oder 9, dadurch gekennzeichnet, daß das Perchlorat alkalischer Eigenschaft das Kaliumperchlorat ist, das in Anteilen im Bereich von 40 bis 60 % des Gesamtgewichts der Zusammensetzung eingeführt ist.
11. Feuerwerkskörper nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, daß das Kaliumperchlorat eine Korngröße unter 70 11m aufweist.
12. Feuerwerkskörper nach einem der Ansprüche 1, 3 oder 7, dadurch gekennzeichnet, daß das Phenoplastbindemittel mit einem brennbaren Metall kombiniert ist, das 10 bis 30 % des Gesamtgewichts der pyrotechnischen Zusammensetzung darstellt.
13. Feuerwerkskörper nach einem der Ansprüche 1 oder 12, dadurch gekennzeichnet, daß das brennbare Metall aus passiviertem Aluminium besteht.
14. Feuerwerkskörper nach einem der Ansprüche 1, 4 oder 5, dadurch gekennzeichnet, daß die pyrotechnische Zusammensetzung am Ort in der äußeren Hülle polymerisiert wird.
15. Feuerwerkskörper nach einem der Ansprüche 1, 2 oder 14, dadurch gekennzeichnet, daß die Hülle aus einem zylindrischen, mit einem Boden ausgestatteten Rohr besteht.
16. Feuerwerkskörper nach einem der Ansprüche 1 oder 14, dadurch gekennzeichnet, daß der Körper nach der im Heizschrank vorgenommenen Polymerisationszeitdauer des Bindemittels unverzüglich in die freie Luft gebracht wird.
EP82401996A 1981-11-10 1982-10-28 In Leuchtpartikel zerfallender Feuerwerkskörper Expired EP0079273B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8120996 1981-11-10
FR8120996A FR2516230A1 (fr) 1981-11-10 1981-11-10 Artifice pyrotechnique eclairant autodispersable

Publications (2)

Publication Number Publication Date
EP0079273A1 EP0079273A1 (de) 1983-05-18
EP0079273B1 true EP0079273B1 (de) 1986-01-22

Family

ID=9263849

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82401996A Expired EP0079273B1 (de) 1981-11-10 1982-10-28 In Leuchtpartikel zerfallender Feuerwerkskörper

Country Status (5)

Country Link
US (1) US4461213A (de)
EP (1) EP0079273B1 (de)
DE (1) DE3268707D1 (de)
ES (1) ES8308056A1 (de)
FR (1) FR2516230A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4913053A (en) * 1986-10-02 1990-04-03 Western Atlas International, Inc. Method of increasing the detonation velocity of detonating fuse
CN113402346A (zh) * 2021-07-20 2021-09-17 北京理工大学 一种安全环保的稳定型开爆药及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1202390A (en) * 1967-11-06 1970-08-19 Astra Fireworks Ltd Improvements in or relating to pyrotechnic compositions
US3736206A (en) * 1969-02-10 1973-05-29 Thiokol Chemical Corp Method for making a pyrotechnic device
US3761329A (en) * 1971-09-23 1973-09-25 Ensign Bickford Co Color flare including polyvinyl chloride color intensifier
FR2248252A1 (en) * 1973-10-23 1975-05-16 Poudres & Explosifs Ste Nale Moulded-crosslinked illuminating pyrotechnical product - from magnesium, alkali(ne earth) nitrate-nitrite, and carboxylated polybutadiene or silicone resin
US4216722A (en) * 1978-06-05 1980-08-12 Angell Howard N Exploding bullet
FR2471959A1 (fr) * 1979-12-19 1981-06-26 France Etat Composition pyrotechnique eclairante coulable comportant une poudre metallique

Also Published As

Publication number Publication date
FR2516230B1 (de) 1984-03-16
ES517221A0 (es) 1983-08-01
US4461213A (en) 1984-07-24
ES8308056A1 (es) 1983-08-01
EP0079273A1 (de) 1983-05-18
DE3268707D1 (en) 1986-03-06
FR2516230A1 (fr) 1983-05-13

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