EP0079273A1 - In Leuchtpartikel zerfallender Feuerwerkskörper - Google Patents

In Leuchtpartikel zerfallender Feuerwerkskörper Download PDF

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Publication number
EP0079273A1
EP0079273A1 EP82401996A EP82401996A EP0079273A1 EP 0079273 A1 EP0079273 A1 EP 0079273A1 EP 82401996 A EP82401996 A EP 82401996A EP 82401996 A EP82401996 A EP 82401996A EP 0079273 A1 EP0079273 A1 EP 0079273A1
Authority
EP
European Patent Office
Prior art keywords
pyrotechnic
composition
pyrotechnic device
binder
block
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.)
Granted
Application number
EP82401996A
Other languages
English (en)
French (fr)
Other versions
EP0079273B1 (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

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B4/00Fireworks, i.e. pyrotechnic devices for amusement, display, illumination or signal purposes
    • F42B4/30Manufacture
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00Explosive and thermic compositions or charges
    • Y10S149/11Particle size of a component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00Explosive and thermic compositions or charges
    • Y10S149/11Particle size of a component
    • Y10S149/113Inorganic 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 being constituted by 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 hardly 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.
  • 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 the pyrotechnic composition is carried out starting from a binder of the phenoplast type and an oxidizing agent whose particle size is lower at 150 micrometers, and on the other hand the smallest dimension of the block is greater than 15 millimeters, this block having undergone rapid cooling after polymerization, which creates internal tensions and incipient fractures within this composition.
  • this composition only partially adheres to the envelope, so that the ignition takes place not only on the free surface of the composition, but also in areas of non-adhesion to the envelope, which has the effect of creating local areas of lateral overpressure which favor the bursting of the initial block of composition into a multitude of fragments.
  • 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-Formol-Resorcin resins do not allow it is difficult to obtain self-dispersing 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.
  • the 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 bursting effect, and preferably the particle size is less than 100 micrometers and even less than 70 micrometers when the composition is not cooled enough. fast or when blocks with a diameter less than 50 millimeters want to be obtained.
  • the phenoplast binder is combined with a metal fuel which constitutes from 10 % to 30% of the total weight of the pyrotechnic composition, and the combustible metal can be passive 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 greater 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. , by placing the fireworks in a stream of air at room temperature, or by placing the fireworks in cells provided in metal plates which are partially immersed in a coolant.
  • the advantages obtained thanks to this invention lie essentially in the distribution of the light source within a very large volume.
  • a distribution can be used in particular in as part of a fireworks show to constitute very large "conflagrations" 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 thus 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 fireworks, 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 field of the invention therefore excludes the phenoplast binders which catalyze in an acid medium, since 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; in addition, the use of an acidic catalytic system requires the use of strictly passive aluminum in order to avoid attack by the acid, and the evolution of hydrogen which accentuates the swelling at the time of 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 a binder with which it is very difficult to carry out the invention satisfactorily.
  • the preferred field of the invention also excludes very alkaline and highly condensed phenolic resins which are self-hardening at 120 ° 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 enabling the best results to be obtained is the commercial resin.
  • the commercial resin read by the company HOECHST under the reference PHENODUR PW 759.
  • It is a resin which uses water as solvent, 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.
  • the raw aluminum is slightly attacked by this resin and that it is therefore preferable to use passive 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. , combined with potassium perchlorate with a particle size of 40 ⁇ "m and with HOECHST resin reference PW 759, the different 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 on 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 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 fragments ejected, and the overall effects are very well reproduc tibles.
  • 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 manufacture of the device No. 1 leads to excessive swelling during the polymerization, which leads to poorer mechanical properties, as for the devices of Example No. 5, cooling in the open air is no longer suitable. , because the block burns with strong projections of incandescent elements, which results in an appreciable aesthetic effect, but the device 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.

Landscapes

  • 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)
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 true EP0079273A1 (de) 1983-05-18
EP0079273B1 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

Citations (5)

* 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
FR2154213A5 (de) * 1971-09-23 1973-05-04 Ensign Bickford Co
US3736206A (en) * 1969-02-10 1973-05-29 Thiokol Chemical Corp Method for making a pyrotechnic device
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
FR2471959A1 (fr) * 1979-12-19 1981-06-26 France Etat Composition pyrotechnique eclairante coulable comportant une poudre metallique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216722A (en) * 1978-06-05 1980-08-12 Angell Howard N Exploding bullet

Patent Citations (5)

* 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
FR2154213A5 (de) * 1971-09-23 1973-05-04 Ensign Bickford Co
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
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
EP0079273B1 (de) 1986-01-22
ES517221A0 (es) 1983-08-01
US4461213A (en) 1984-07-24
ES8308056A1 (es) 1983-08-01
DE3268707D1 (en) 1986-03-06
FR2516230A1 (fr) 1983-05-13

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