EP2615077B1 - Aktivierung von energetischen Zusammensetzungen durch magnetische Mischung - Google Patents

Aktivierung von energetischen Zusammensetzungen durch magnetische Mischung Download PDF

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Publication number
EP2615077B1
EP2615077B1 EP13151038.0A EP13151038A EP2615077B1 EP 2615077 B1 EP2615077 B1 EP 2615077B1 EP 13151038 A EP13151038 A EP 13151038A EP 2615077 B1 EP2615077 B1 EP 2615077B1
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European Patent Office
Prior art keywords
composition
particles
energetic
magnetic field
motive
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EP13151038.0A
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English (en)
French (fr)
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EP2615077A1 (de
Inventor
Marc Comet
Denis Spitzer
Dominique Hassler
Etienne Rauscher
Jean Caillard
Vincent Rafin
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Isl - Institut Franco-Allemand De Recherches De SA
Centre National de la Recherche Scientifique CNRS
MBDA France SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Institut Franco Allemand de Recherches de Saint Louis ISL
MBDA France SAS
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/60—Mixing solids with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
    • B01F33/451—Magnetic mixers; Mixers with magnetically driven stirrers wherein the mixture is directly exposed to an electromagnetic field without use of a stirrer, e.g. for material comprising ferromagnetic particles or for molten metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71—Feed mechanisms
    • B01F35/713—Feed mechanisms comprising breaking packages or parts thereof, e.g. piercing or opening sealing elements between compartments or cartridges
    • B01F35/7137—Piercing, perforating or melting membranes or closures which seal the compartments
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase

Definitions

  • the present invention relates to the field of energy compositions, and in particular energy compositions which can be integrated into pyrotechnic systems, in particular of the military or space industry, such as igniters, detonators or devices integrating these elements.
  • the energy composition is considered to be the primary element of the chain.
  • the energy composition used at the start of the pyrotechnic chain is most often a sensitive composition (primary composition) in order to allow the pyrotechnic chain to start operating. Due to their high sensitivity, it is necessary to guard against accidental operation of the latter.
  • the normal operation of the pyrotechnic system is generally implemented by a mechanical, thermal or electrical effect, of low power.
  • the misalignment of the primary elements of a pyrotechnic chain constitutes a physical device making it possible to achieve the required level of safety by separating the active elements from the pyrotechnic chain and only bringing them together when necessary, under the conditions of shot or ignition planned.
  • the methods currently used involve the integration of sensitive energetic substances capable of giving rise to a pyrotechnic reaction in the event of accidental stresses during storage or use, in armaments or other systems which contain them. These stresses can occur during handling, aging, a fire, or by a hit, etc.
  • the consequences of an accidental pyrotechnic reaction can range from neutralization to destruction of the system and present a cost and associated material and human damage.
  • the regulations applicable in the transport and handling of explosive materials require special, cumbersome and costly conditions to set up.
  • WO 2009/008794 A1 describes a method and a system for mixing and igniting a pyrotechnic charge.
  • the object of the invention is to solve all of the technical problems mentioned above, and in particular the technical and regulatory problems linked to the use of energetic materials made up.
  • the invention aims to provide an energy composition having a very high level of safety from a pyrotechnic point of view, in particular to facilitate the muratization of the systems including it.
  • the object of the invention is in particular to provide an energy composition which does not activate following accidental stresses which may occur during the life cycle of the product.
  • the invention also aims to provide an energy composition available only when it is necessary and without affecting its energy performance.
  • the invention also aims to provide a method for activating this energy composition, and devices implementing it.
  • the invention relates to an energy composition capable of being activated by mixing its elementary constituents which are individually inert.
  • the invention relates to an energy composition
  • an energy composition comprising ferromagnetic or magnetized particles, of micrometric to centimeter size, called motor particles, and at least two types of powdery solid compounds of nanometric size initially physically separated, called inert precursors of final energy composition, said precursors.
  • a redox system comprising an oxidizing composition and a reducing composition, said energetic composition being capable of being activated from the pyrotechnic point of view by mixing inert precursors of final energetic composition by agitation of said driving particles either by means of a varying magnetic field as a function of time.
  • the energetic composition of the invention comprises at least two types of precursor compounds, which physically separated, are inactive from the pyrotechnic point of view, but become active from the pyrotechnic point of view when they are mixed.
  • the composition of the invention is therefore an inert composition from the pyrotechnic point of view which becomes active after contacting the precursors with one another.
  • the invention therefore consists of an energy composition which can be activated from the pyrotechnic point of view by mixing its elementary constituents by means of a magnetic field varying over time and applying directly to the particles.
  • the elementary constituents making it possible to activate the energy composition are the precursors of final energy composition.
  • active or “activated” from the pyrotechnic point of view means making the composition sufficiently energy for its use in a pyrotechnic device, in particular as a priming composition.
  • the size of the driving particles must be sufficient to drive the precursors in motion and ensure their mixing. However, the inertia should not be too great in order to avoid igniting the composition under the effects of shocks or friction produced by the movements of the driving particles.
  • the size of the driving particles is generally between 0.1 and 10,000 micrometers.
  • the driving particles generally have a geometric shape displacing as much of the surrounding material as possible when they move.
  • the driving particles are preferably in the form of plates or strips, possibly notched.
  • the ferromagnetic driving particles which are directly animated by the magnetic field, are chosen from iron, cobalt, nickel, a Heusler alloy, the family of lanthanides, mixed oxides of iron II and iron III, and ferrites.
  • Ferrites can be defined by the formula (MO; Fe 2 O 3 ) where M is a divalent metal.
  • MO magnetite Fe 3 O 4 (FeO; Fe 2 O 3 ).
  • the magnetized driving particles which are directly animated by the magnetic field, are chosen from permanent magnets.
  • the permanent magnets mention may be made of Nd-B-Fe, coordination chemistry magnets such as the compounds [M II (Rtrz) 3 ] A 2 ⁇ xH 2 O where the metal ions M (Fe ", Zn") are linked together by triazole ligands (trz) grafted in position 4 by a group R (generally an alkyl chain), A - corresponds to the counterion used, for example Cl - or the ion paratolylsufonate; organo-metallic magnets such as [Fe (Me 5 Cp) 2 ] [TCNE], where Me 5 Cp is pentamethylcyclopentadienyl and TCNE tetracyanoethylene or V (TCNE) 2 (vanadium di-tetracyanoethylenide); and purely organic magnets.
  • the precursors of the final energy composition form a redox system comprising an oxidizing composition and a reducing composition.
  • the oxidizing composition and the reducing composition are physically separated by an intermediate layer which can include driving particles.
  • the thickness of the layer of driving particles is between 0.2 and 5 mm, and may for example be around 1 mm.
  • the oxidizing composition and the reducing composition may or may not each comprise driving particles.
  • the energetic composition is activated by agitation of the driving particles which penetrate and move through the oxidizing composition and the reducing composition. Under the effect of the agitation of the driving particles, the oxidizing and reducing compositions mix, thus activating the energetic composition.
  • the content of motor particles necessary for ensuring the mixture is between 1 and 20%, and preferably between 1 and 5%, by mass of the total mass of the energy composition. This proportion remains modest and is not high enough to significantly alter the energy performance of the final activated composition.
  • the homogenization of the energy composition is all the more effective the smaller the particles of the precursors.
  • the precursors of the final energy composition are powders of nanometric size.
  • the diameter of the elementary particles is generally between 1 and 300 nm, and preferably less than 100 nm.
  • the agitation of the driving particles allows the proliferation of the precursors, promotes their interpenetration, and consequently, promotes the efficiency and the homogeneity of the mixture.
  • the size of the driving particles is at least an order of magnitude greater than that of the larger aggregates of the precursor particles.
  • An ideal size of the driving particles is between 1 ⁇ m and one centimeter.
  • the precursors of the final energy composition are constituents of nanothermites.
  • Nanothermites (“metastable intermolecular composites” - MICs) are a very fine mixture, on a nanometric scale, of an oxidant and a reducing agent.
  • nanothermites include aluminum-molybdenum oxide (VI) compositions, such as Al-MoO 3 ; aluminum-copper (II) oxide compositions, such as Al-CuO; Aluminum-iron oxide compositions (II, III), such as Al-Fe 2 O 3 ; aluminum-tungsten oxide (VI) compositions, such as Al-WO 3 ; aluminum-bismuth (III) oxide compositions, such as Al-Bi 2 O 3 ; aluminum-manganese (IV) compositions, such as Al-MnO 2 ; mixtures of potassium permanganate with antimony; mixtures of potassium permanganate with aluminum, such as Al-KMnO 4 ; mixtures of potassium permanganate with boron, such as B-KMnO 4 ; aluminum-tungsten (VI) oxide hydrates; Titanium-boron compounds, and aluminum-fluoropolymers.
  • Nanothermites can also be formulated in mixing metal oxide powders with reducing metals such as boron, magnesium,
  • PTFE or other fluoropolymers can be used as binders for nanothermites.
  • Nanothermites are advantageous since they have an energy potential and a thermal sensitivity allowing ignition by hot wire, detonating wire, laser pulse, flame, plasma or capacitive discharge.
  • Their constituents, metals or metallic oxides have excellent stability over time, including under extreme conditions (temperature variations, etc.). This last characteristic is of capital importance for the development of systems which can be integrated into missiles.
  • the energetic composition of the invention can be complex and include organic, energetic or inert molecules, used for example as gas-generating substances, such as propellants for example.
  • the energetic composition of the invention can advantageously constitute an ignition or priming composition for a pyrotechnic system.
  • the invention also relates to a device comprising one or more inactive energy compositions as defined above, and one or more magnetic field generating means varying as a function of time to activate said energy composition from the pyrotechnic point of view.
  • the position of the field lines varies as a function of time.
  • the magnetic field is rotated. This can be done simply by rotating the magnetic field generating means or means.
  • the magnetic field generating means is chosen from one or more mechanically movable permanent magnets, one or more solenoids, one or more electromagnets supplied by an oscillating or direct current source, and any one of their combinations .
  • the magnetic field generating means are arranged around said inactive energy composition, and preferably generate a magnetic field passing substantially through all of the energy composition.
  • the device of the invention comprises a drive means, such as a motor, driving in rotation the magnetic field generator means for agitating the driving particles in order to bring the precursors into contact with each other, and thus generate the energetic composition activated.
  • a drive means such as a motor, driving in rotation the magnetic field generator means for agitating the driving particles in order to bring the precursors into contact with each other, and thus generate the energetic composition activated.
  • the device of the invention is integrated into a pyrotechnic system, and for example a military pyrotechnic system.
  • the invention therefore covers in particular a military charge, a shell, a rocket, a missile in particular an interception or cruise missile, or any other armament comprising a pyrotechnic system according to the invention.
  • the invention also covers systems for very high security detonators used in civil applications.
  • the device of the invention is integrated into an igniter, a detonator or an element of a pyrotechnic system, in particular a military system.
  • a device provides a very high level of security, making it easier to obtain the MURAT label.
  • the architecture of the device used to vary the magnetic field depends on the nature of the substances to be mixed and on the specifics of the intended application.
  • the device of the invention can take any geometry suitable for mixing the precursors by stirring the driving particles under the influence of the magnetic field alone or associated with a complementary mixing means.
  • the pyrotechnic systems of the invention are centimeter-sized systems (such as igniters or detonators).
  • the invention allows the activation of the energy composition of a pyrotechnic system in the moments preceding its ignition. Before activation is triggered, the pyrotechnic system is completely inert since the primary elements of the energy composition, which are insensitive separately, are not associated.
  • the precursor compositions (for example oxidizing and reducing compositions) of the invention can be separated by a physical separation system, for example by a membrane or a diaphragm.
  • This physical separation system can be eliminated just before mixing the two precursor compositions, for example by perforation or opening.
  • the device of the invention can therefore comprise a means of perforating or opening the physical separation system.
  • the magnetic field is produced by one or more mechanically movable permanent magnets and / or by one or more solenoids and / or one or more electromagnets supplied by an oscillating or direct current source.
  • an assembly of solenoids can be used to displace the driving particles throughout the volume occupied by the activated composition.
  • the fields generated are thus controlled in order to ensure a movement allowing the effective homogenization of the constituents of the composition.
  • the method of the invention makes it possible to mix the precursors with a mixing time compatible for the use of the composition in a pyrotechnic system, for example in a missile.
  • the mixing time is of the order of a few seconds (interception missile) to a few minutes (cruise missile).
  • the mixing time is between 0.1 seconds and 5 minutes.
  • the stirring or the mixing is carried out until a homogeneous energetic composition is obtained, that is to say that the precursors are intimately mixed.
  • the driving particles are removed from the mixture, in particular by the action of a stronger magnetic field.
  • the energy composition after activation of the energy composition, it can be compressed.
  • the figure 1 shows a schematic section of a variant of the invention in which an oxidizing composition (10) is deposited at the bottom of a cup (60), said oxidizing composition (10) comprising driving particles (30).
  • a reducing composition (20) is deposited on the surface of the oxidizing composition (10).
  • the cup (60) is positioned inside a magnetic field generating means (or inductor) (50), such as a stator, for example of annular shape (not shown in the figure).
  • the inductor (50) can be connected to one or more electrical supply devices in order to activate or not the magnetic field.
  • the inductor (50) is preferably connected to a device for driving in rotation along the axis (70). This device can typically be a motor.
  • the bucket (60) is preferably kept fixed during the rotation of the inductor (50).
  • the energy composition (system (oxidizing (10) / reducing (20) ⁇ ) composition) is inactive, but may be activated by rotating the inductor (50) in operation.
  • the driving particles (30) are set in motion by the induced magnetic field so as to mix the oxidizing (10) and reducing (20) compositions.
  • inductor (50) in operation is meant the fact that it generates a magnetic field passing through the oxidizing (210) and reducing (220) compositions.
  • the stacking direction of the layers shown on the Figures 1 and 2 can be reversed (parallel to the axis of rotation (70)) if such a configuration has a better yield in terms of ability to mix. All other intermediate orientations can be retained if they are of interest, given the nature of the products to be mixed and the method of agitation.
  • the figure 2 shows a schematic section of another variant of this device in which the cup (260) contains an oxidizing composition (210) on which has been deposited a layer of driving particles (230) on which has been deposited a reducing layer (220) .
  • the layer of motor particles (230) makes it possible to isolate the oxidizing (210) and reducing (220) compositions.
  • This total composition system (oxidizing (10) / reducing (20)) composition)
  • the compositions are mixed by rotating along the axis (270) of the inductor (250) in operation which mixes the oxidizing (210) and reducing (220) compositions due to the setting in movement of the driving particles (230) by the induced magnetic field.
  • the mixing is carried out until a homogeneous composition is obtained with an intimate mixture of the oxidizing (10,210) and reducing (20,220) compositions.

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Claims (15)

  1. Inaktive energetische Zusammensetzung, umfassend ferromagnetische oder magnetisierte Partikel mit mikrometrischer bis zentimetrischer Abmessung, bezeichnet als treibende Partikel, und mindestens zwei Arten von pulverförmigen festen Verbindungen mit nanometrischer Abmessung in physischer Trennung, bezeichnet als inerte Vorläufer der endgültigen energetischen Zusammensetzung, wobei die Vorläufer ein Redoxsystem bilden, umfassend eine oxidierende Zusammensetzung und eine reduzierende Zusammensetzung, wobei die energetische Zusammensetzung vom pyrotechnischen Gesichtspunkt durch Mischung der inerten Vorläufer der endgültigen energetischen Zusammensetzung durch Rühren der treibenden Partikel mit Hilfe eines variierenden magnetischen Felds in Funktion der Zeit aktiviert werden kann.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die ferromagnetischen treibenden Partikel ausgewählt sind aus Eisen, Kobalt, Nickel, einer Heusler'schen Legierung, der Familie der Lanthanide, gemischten Eisen II- und Eisen III-Oxyden und Ferriten.
  3. Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die magnetisierten treibenden Partikel ausgewählt sind aus den Dauermagneten.
  4. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die oxidierende Zusammensetzung und die reduzierende Zusammensetzung physisch durch eine Zwischenschicht getrennt sind, die treibende Partikel einschließen kann.
  5. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die oxidierende Zusammensetzung und die reduzierende Zusammensetzung physisch getrennt z. B. durch eine Membran, ein Diaphragma oder einen Deckel, jeweils treibende Partikel umfassen oder nicht.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Vorläufer der endgültigen energetischen Zusammensetzung Bestandteile der Nanothermiten sind.
  7. Vorrichtung, umfassend eine oder mehrere energetisch aktive Zusammensetzungen, wie in den vorhergehenden Ansprüchen definiert, und ein oder mehrere Generatormittel eines magnetischen Felds, das in Funktion der Zeit variiert, um die energetische Zusammensetzung vom pyrotechnischen Gesichtspunkt zu aktivieren.
  8. Vorrichtung nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das Generatormittel des magnetischen Felds ausgewählt ist aus einem oder mehreren mechanisch beweglichen Dauermagneten, einem oder mehreren Solenoiden, einem oder mehreren Elektromagneten, versorgt von einer oszillierenden oder kontinuierlichen Stromquellen und einer ihrer Kombinationen.
  9. Vorrichtung nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass die Generatormittel eines magnetischen Felds um die inaktive energetische Zusammensetzung angeordnet sind.
  10. Vorrichtung nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass sie ein Mittel zur Fernaktivierung des magnetischen Felds umfasst.
  11. Pyrotechnisches System oder Element eines pyrotechnischen Systems, in das eine Vorrichtung integriert ist, nach einem der Ansprüche 7 bis 10.
  12. Verfahren zur Aktivierung einer inaktiven energetischen Zusammensetzung, wobei die inaktive energetische Zusammensetzung ferromagnetische oder magnetisierte Partikel mit mikrometrischer bis zentimetrischer Abmessung, bezeichnet als treibende Partikel und mindestens zwei Arten von pulverförmigen festen Verbindungen mit nanometrischer Abmessung, anfänglich physisch getrennt, bezeichnet als inerte Vorläufer der endgültigen energetischen Zusammensetzung, umfasst, wobei die inaktive Zusammensetzung wie nach einem der Ansprüche 1 bis 6 definiert ist, wobei das Verfahren Folgendes umfasst;
    (i) Rühren der treibenden Partikel mit Hilfe eines magnetischen Felds, das in Funktion der Zeit variiert, um die inerten Vorläufer der inaktiven energetischen Zusammensetzung zu mischen, und
    (ii) Aktivieren der inaktiven energetischen Zusammensetzung durch In-Kontakt-Bringen der inerten Vorläufer miteinander.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass das magnetische Feld durch einen oder mehrere mechanisch bewegliche Dauermagneten und/oder durch einen oder mehrere Solenoiden und/oder durch einen oder mehrere Elektromagneten, versorgt von einer oszillierenden oder kontinuierlichen Stromquelle, erzeugt wird.
  14. Verfahren nach einem der Ansprüche 12 bis 13, dadurch gekennzeichnet, dass nach der Aktivierung der energetischen Zusammensetzung die treibenden Partikel aus der Mischung entfernt werden, insbesondere durch Betätigung des stärksten magnetischen Felds.
  15. Verfahren nach einem der Ansprüche 12 bis 14, dadurch gekennzeichnet, dass nach der Aktivierung der energetischen Zusammensetzung die Zusammensetzung komprimiert wird.
EP13151038.0A 2012-01-13 2013-01-11 Aktivierung von energetischen Zusammensetzungen durch magnetische Mischung Active EP2615077B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1250348A FR2985726B1 (fr) 2012-01-13 2012-01-13 Activation de compositions energetiques par melange magnetique

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EP2615077A1 EP2615077A1 (de) 2013-07-17
EP2615077B1 true EP2615077B1 (de) 2020-05-06

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EP (1) EP2615077B1 (de)
ES (1) ES2817786T3 (de)
FR (1) FR2985726B1 (de)

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US78317A (en) 1868-05-26 Improved explosive compound
US325538A (en) * 1885-09-01 Shell
FR499506A (fr) 1917-07-01 1920-02-13 Chimiques Pour L Ind Soc Et Procédé pour la suppression du danger d'explosion lors de la préparation et de la manipulation de substances explosives très dangereuses
US3219318A (en) * 1961-08-22 1965-11-23 Hershler Abe Fluid treating method and apparatus
DE2341818A1 (de) * 1973-08-16 1975-02-27 Garphytte Bruk Ab Methode zur herstellung von misch-u. befoerderungsgeraeten
US3987967A (en) * 1974-12-19 1976-10-26 Jury Nikolaevich Kuznetsov Method of working materials and device for effecting same
US4247494A (en) * 1977-08-16 1981-01-27 Imi Kynoch Limited Case priming
JPS5876151A (ja) * 1981-10-30 1983-05-09 富士電機株式会社 電磁式粉砕，混合，撹拌等処理装置の運転方法
FR2601125B1 (fr) * 1986-07-02 1988-10-21 Soucaze Soudat Jean Cartouche explosive a armement chimique automatique
GB9511263D0 (en) * 1995-06-03 1995-07-26 Ici Plc Process for the production of a pyrotechnic or explosive device
US5699842A (en) * 1996-04-12 1997-12-23 Xerox Corporation Magnetic filling and mixing apparatus and processes thereof
US6666935B1 (en) 1997-09-09 2003-12-23 The Regents Of The University Of California Sol-gel manufactured energetic materials
US7585381B1 (en) * 2003-08-07 2009-09-08 Pioneer Astronautics Nitrous oxide based explosives and methods for making same
SE531342C2 (sv) * 2007-07-06 2009-03-03 Bae Systems Bofors Ab Förfarande och anordning för blandning och initiering av en pyroteknisk sats

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FR2985726B1 (fr) 2014-02-07
FR2985726A1 (fr) 2013-07-19
ES2817786T3 (es) 2021-04-08
EP2615077A1 (de) 2013-07-17

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