EP1500639A2 - Pyrotechnisches Material und Verfahren zu deren Herstellung - Google Patents

Pyrotechnisches Material und Verfahren zu deren Herstellung Download PDF

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Publication number
EP1500639A2
EP1500639A2 EP04291798A EP04291798A EP1500639A2 EP 1500639 A2 EP1500639 A2 EP 1500639A2 EP 04291798 A EP04291798 A EP 04291798A EP 04291798 A EP04291798 A EP 04291798A EP 1500639 A2 EP1500639 A2 EP 1500639A2
Authority
EP
European Patent Office
Prior art keywords
nanometric
binder
pyrotechnic
aluminum
substance according
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
EP04291798A
Other languages
English (en)
French (fr)
Other versions
EP1500639B1 (de
EP1500639A3 (de
Inventor
Luc Brunet
Christophe Coulouarn
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.)
KNDS Ammo France SA
Original Assignee
Giat Industries SA
Nexter Munitions SA
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 Giat Industries SA, Nexter Munitions SA filed Critical Giat Industries SA
Publication of EP1500639A2 publication Critical patent/EP1500639A2/de
Publication of EP1500639A3 publication Critical patent/EP1500639A3/de
Application granted granted Critical
Publication of EP1500639B1 publication Critical patent/EP1500639B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • 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
    • C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic 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
    • C06B45/18—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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers

Definitions

  • the technical field of the invention is that of pulverulent substances and more particularly pyrotechnic substances incorporating a primary explosive.
  • Such pyrotechnic substances are commonly used for the manufacture of primers or detonators.
  • Patent FR2599361 thus describes a priming substance combining 40 to 70% by mass of lead trinitroresorcinate and 60 to 30% aluminum with less than 1% of a binder formed by gum arabic.
  • Aluminum is used in this component of allow the evacuation of the calories generated by heating of the primer filament under the effect of electromagnetic fields. This avoids a warm-up inopportune that may lead to the initiation of the composition and thus increases the security of the component.
  • the explosive and aluminum powders are associated under the form of a homogeneous mixture maintained by a binder.
  • the granulometry of the primary explosive and powder are of the same order of magnitude and less than 40 micrometers.
  • This pyrotechnic substance has the drawback to require a significant amount of aluminum for reduce the susceptibility of the component to radiation electromagnetic.
  • the relative percentage of primary explosive is correlatively reduced and the detonation efficiency of the component is therefore also reduced, except to increase the mass of primary explosive so the volume of the component.
  • the homogeneity of the explosive / aluminum mixture is difficult to ensure in a reproducible way. It results from variable performance from one batch to another of the point of view of sensitivity to electrostatic discharge or friction.
  • the object of the invention is to propose a substance pulverulent material having processing properties (especially improved flowability).
  • the object of the invention is more particularly to propose a pyrotechnic substance that retains its effectiveness while having reduced sensitivity, particularly to electric shocks and friction.
  • the subject of the invention is a powdery substance and in particular a pyrotechnic substance which is characterized in that it comprises at least a first material formed of grains coated with a binder layer incorporating granules of a second nanoscale material.
  • the second material may be made of aluminum or silicon.
  • Nanometric materials and in particular aluminum are known. It has already been proposed to implement them in the pyrotechnic components.
  • the US5717159 patent thus proposes a primer comprising 45% by weight of nanometric aluminum and 55% by weight of nanometric molybdenum trioxide.
  • the invention proposes instead to associate a material, in particular a pyrotechnic material, with granulometric classical micrometer (of the order of 100 micrometers) with a material with nanometric granulometry (from 0.05 to 0.1 microns).
  • nanoscale material granules surround the grains of the micrometric material.
  • a binder ensures the binding of granules and grains.
  • micrometric material So every grain of micrometric material has its surface externally practically covered (more than 90%) by nanoscale granules. There is no more segregation of materials despite their very different grain sizes and the micrometric material is protected.
  • the coating of a material pyrotechnics by a nanometric metal, in particular by aluminum makes the whole pyrotechnic substance conducted, both heat and electricity, which makes it easier to evacuate calories and therefore increases the resistance of the substance pyrotechnic to self ignition.
  • This pyrotechnic substance also sees its sensitivity to electrostatic discharge and friction diminished, which makes the industrial implementation of the safer pyrotechnic substance.
  • the coating also facilitates industrial implementation of the substance by reducing including sensitivity to friction and facilitating flowability.
  • nitrocellulose polyvinylidene fluoride (PVDF), vinyl chloroacetate (CVA) copolymer, copolymer of chlorofluoroethylene, polytetrafluoroethylene, polyvinyl alcohol (better known under the trademark "Rhodoviol”).
  • PVDF polyvinylidene fluoride
  • CVA vinyl chloroacetate copolymer
  • copolymer of chlorofluoroethylene polytetrafluoroethylene
  • polyvinyl alcohol better known under the trademark "Rhodoviol”
  • the nitrocellulose has the advantage of being an active binder which participate in the pyrotechnic reaction by bringing Energy.
  • the other binders mentioned are inert binders.
  • the proportion chosen for the binder will preferably be less than 3% of the total mass (that of the coated material plus that of the nanoscale material).
  • This will advantageously produce a substance pyrotechnic powder comprising from 95% to 60% by weight a first pyrotechnic material, 5 to 40% by weight of nanoscale aluminum and a binder in a proportion of 0.5% to 3% of the overall mass of the material mixture pyrotechnics / nanoscale aluminum.
  • the first pyrotechnic material may be an oxidant (such as copper oxide CuO, potassium nitrate or potassium perchlorate) or a secondary explosive (such as Octogen, or Hexogen).
  • oxidant such as copper oxide CuO, potassium nitrate or potassium perchlorate
  • secondary explosive such as Octogen, or Hexogen.
  • a secondary explosive is a explosive that requires significant activation energy to detonate (energy brought for example by an explosive primary).
  • the first pyrotechnic material can also be a detonating or explosive primary explosive.
  • An explosive says primary is an explosive material that is characterized by a great sensitivity under at least one of the solicitations following: shock, friction, flame, electric spark.
  • the primary explosive detonators have a decomposition that goes very quickly to the same detonation without confinement. Explosive primary explosives have a decomposition regime that only detonates in certain conditions of confinement or initiation.
  • the first pyrotechnic material primary explosive from the following materials: dinitrobenzofuroxane, lead azide, silver azide, diazodinitrophenol (DDNP), lead styphnate.
  • KDNBF potassium salt
  • RbDNBF Sodium
  • CsDNBF Cesium
  • BaDNBF Barium
  • a substance can be made combining: 79% by weight of dinitrobenzofuroxane potassium (KDNBF), 18% of nanometric aluminum, and 3% mass of nitrocellulose.
  • KDNBF dinitrobenzofuroxane potassium
  • the subject of the invention is also a method of preparation of a powdery substance, in particular a pyrotechnic substance, comprising at least a first material formed of grains coated with a layer of binder incorporating granules of a second material of nanometric particle size.
  • a powdery substance in particular a pyrotechnic substance
  • the process according to the invention making it easy and safe to prepare such substance.
  • the carrier liquid may be silicone oil, binding being nitrocellulose and the first solvent being the methyl ethyl ketone.
  • the surfactant may be a sugar ester.
  • the first micrometric material can then be a detonating or explosive primary explosive and the second nanometric material be made of aluminum.
  • This particle 1 is formed by a grain 2 of a first material which is coated with a binder layer 3 incorporating granules 4 of a second granulometry material nanometric (for example nanometric aluminum).
  • Nanoscale materials are easy to obtain commercially. These materials can be obtained for example from the company Technanogy (2146 Michelson Drive Irvine California USA).
  • nanometric material having a particle size between 50 and 100 nanometers (or between 0.05 micrometers and 0.1 micrometers).
  • the granules 4 thus surround virtually the entire external surface of the grains 2 of the first material.
  • the different particles 1 thus constituted and which form the powdery substance are therefore always in contact mutually with each other through the intermediary of granules 4.
  • the contact between the granules makes the conductive pyrotechnic substance.
  • the first material coated with aluminum may be a pyrotechnic material such as a primary explosive.
  • a pyrotechnic material such as a primary explosive.
  • the starting pyrotechnic powdery substance obtained will have improved behavior. She will be more resistant to electrostatic discharge, friction and heating.
  • the first pyrotechnic material may be an explosive secondary such as hexogen or octogen.
  • the coating of the grains of explosives may, in addition to conductivity of the composition, give a breath effect complementary to the explosive charge that will be made with such a substance.
  • the first pyrotechnic material may be an oxidant (such as copper oxide, potassium nitrate or potassium perchlorate).
  • an oxidant such as copper oxide, potassium nitrate or potassium perchlorate.
  • a suitable nanoscale reducer such as aluminum for copper oxide, boron for nitrate of potassium or Zirconium for perchlorate potassium, will ensure a more intimate contact between oxidizing and reducing agent.
  • a coating of a material micrometric with nanometric silica will allow improve the flowability of the powdery substance.
  • the coating of grains with a granulometry material micrometric with nanoscale granules is a operation a priori delicate.
  • the very fine granules disperse in suspension in air during a dry implementation. They can also be charge in static electricity and stick to the tools of loading.
  • nanometric aluminum powder reacts strongly in the presence of moisture and is therefore dangerous To manipulate.
  • the invention also aims to propose a method to ensure in a safe and reproducible way that coating.
  • the material according to the invention is thus produced by a coating process in emulsion.
  • the first material is suspended micrometric and the second nano material within a liquid carrier.
  • An adjustment of the temperature of the liquid support will allow to control the size of the droplets of the emulsion. More the temperature will be high plus the droplets will be fines.
  • the first solvent is then extracted by adding to the emulsion a second solvent.
  • the latter is chosen from so that the first solvent has a higher affinity great with him than he has for the binding material.
  • This operation has the effect of removing the solvent from the binding, so harden the one that traps the granules nanoscale around the grains of the first material micrometer.
  • the substance obtained will be implemented in a conventional manner in a pyrotechnic component, for example a component to hot wire, exploded wire or percussion wire ...
  • the first pyrotechnic material is an explosive secondary school, it will be implemented later conventional loading techniques (casting, compression, polymerization).
  • the invention adds to the solvent / binder emulsion in the carrier liquid a surfactant for stabilizing it.
  • surfactant molecules reduce surface tension between two liquids.
  • the surfactant for role of creating binder bubbles / volume solvent equivalent In the process according to the invention, the surfactant for role of creating binder bubbles / volume solvent equivalent.
  • the surfactant makes it possible to stabilize this step before hardening of the grains by the addition of the second solvent.
  • This control also makes it possible to control the quantity of granules of nanoscale material present in each bubble of binder / solvent, so also to control the coating of the grains of the first material with the material nanoscale.
  • surfactant will depend on the nature of the solvents as well as that of the carrier liquid.
  • a surfactant comprising a polar head soluble in the first solvent and a fatty carbon chain soluble in the carrier liquid.
  • the advantage of the process according to the invention is that it avoids dry mixing of the powders. This increases the security implementation. If the first material is an explosive primary, it is phlegmatized by the liquid support. By besides the nano aluminum which is highly reactive to the open air (because of the humidity of the air) is mixed safely in the carrier liquid (for example silicone oil).
  • the carrier liquid for example silicone oil
  • binder according to the nature of the material to coat and so that it is not miscible in the liquid carrier.
  • a binder such as nitrocellulose methyl ethyl ketone will be used as the first solvent and will adopt Heptane as the second solvent harden the grains.
  • the carrier liquid chosen is the oil of silicone and the appropriate surfactant is a sugar ester.
  • Such an ester has a long carbon chain which has more affinity with silicone oil than with the methyl ethyl ketone. It has a polar head formed by many OH groups that form hydrogen bonds with the C-Os of methyl ethyl ketone.
  • the sugar ester is so has the interphase between the first solvent and silicone oil, ensuring the stabilization of droplets.
  • PVDF formamide polyvinyl
  • polyvinyl alcohol we can choose as the first solvent acetone.
  • the method according to the invention can also be used to coat a non-pyrotechnic material with granules nanoscale.
  • the skilled person will easily choose the different solvents depending on the materials used.
  • a substance has been produced powdery pyrotechnics associating 78% of potassium dinitrobenzofuroxane (KDNBF) (granulometry) average 85 micrometers), 19% of nanometric aluminum (particle size between 50 nanometers and 100 nanometers) and 3% nitrocellulose.
  • KDNBF potassium dinitrobenzofuroxane
  • a solution of the binder is first prepared in a first solvent.
  • a first solvent for this purpose, between 0.1 g and 0.25 g is mixed of nitrocellulose in 40 to 60 ml of methyl ethyl ketone.
  • the temperature of the silicone oil bath is maintained between 18 ° C and 30 ° C.
  • An agitator is present in the beaker.
  • the mixture is stirred for 5 minutes.
  • the binder solution is then introduced into the beaker. previously prepared, then 1 to 5 ml of a surfactant solution (sugar ester).
  • Heptane rinsing can be repeated once or twice time then we recover the composition on a buchner. We squeeze a few minutes then we recover the composition coated which can be stored.
  • Tests have been conducted to compare the pyrotechnic substance thus obtained with the KDNBF alone, and with a coated composition associating the KDNBF with micrometric aluminum (particle size between 40 microns and 80 microns).
  • This last composition was prepared by putting into the same process as that described above.
  • the KDNBF can not be coated with micrometric aluminum.
  • the composition obtained is rather close to a dry mix of both products in which there are no conductive paths through aluminum particles.
  • This classic test is conducted according to the procedure following: a quantity of pyrotechnic substance of approximately 15 mm3 is disposed in a conductive cup. A needle is placed above the substance (without contact). We applied between the bucket containing the pyrotechnic substance and the needle discharging a capacitor with a capacitance 1000 pF charged at 25 kV with a resistance of 10 kilo Ohms serial.
  • the pyrotechnic substance the invention has a higher initiation threshold. His sensitivity to electric shocks is therefore less.
  • the pyrotechnic substance implementing micrometric aluminum is not homogeneous from one batch to the other. The results are not reproducible for a such substance.
  • the threshold varies from 2.88 kV (KDNBF only) to non-initiationn (aluminum only).
  • a sample of the order of 10 mg of the pyrotechnic substance to be tested is deposited in the form a small pile in the middle of a ceramic plate rough. This plate is then fixed on the carriage mobile device that can print a movement linear reproducible speed and amplitude.
  • the pyrotechnic substance the invention is much more resistant to friction than the KDNBF alone. Indeed it takes a force greater than 1.2 kg for get initiation. Such behavior is due to a improvement of the external surface of the grain (assured smoothing by the nanometric material).
  • the pyrotechnic substance implementing micrometric aluminum is not homogeneous from one batch to the other, the results of the friction tests are very variables. Such a composition is not reproducible.
  • compositions can be made with the same process teaming up :

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
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  • Glanulating (AREA)
EP04291798.9A 2003-07-25 2004-07-15 Pyrotechnisches Material und Verfahren zu deren Herstellung Expired - Lifetime EP1500639B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0309260 2003-07-25
FR0309260A FR2857963B1 (fr) 2003-07-25 2003-07-25 Substance pulverulente et procede de fabrication d'une telle substance.

Publications (3)

Publication Number Publication Date
EP1500639A2 true EP1500639A2 (de) 2005-01-26
EP1500639A3 EP1500639A3 (de) 2011-11-30
EP1500639B1 EP1500639B1 (de) 2014-03-26

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EP (1) EP1500639B1 (de)
FR (1) FR2857963B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2905882A1 (fr) * 2006-09-14 2008-03-21 Saint Louis Inst Procede de fabrication de micro et/ou nanothermites et nanothermites associees.
WO2009081048A3 (fr) * 2007-12-19 2010-04-08 Snpe Materiaux Energetiques Desensibilisation par enrobage de cristaux de substances energetiques explosives; cristaux de telles substances enrobes; materiaux energetiques.

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019143865A1 (en) * 2018-01-18 2019-07-25 Armtec Defense Products Co. Method for making pyrotechnic material and related technology

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DE1105784B (de) * 1960-02-06 1961-04-27 Deutsch Franz Forsch Inst Verfahren zur Herstellung leitfaehiger Initialsprengstoffe fuer elektrische Zuender
FR2031677A5 (en) * 1969-02-04 1970-11-20 France Etat Explosive mixtures contg metals prepn
US3652350A (en) * 1969-06-23 1972-03-28 Hi Shear Corp Method of blending pyrotechnic mixtures
AU5250073A (en) * 1972-03-10 1974-08-22 Ici Australia Ltd Compositions of matter
IN165908B (de) * 1985-10-25 1990-02-10 Merck Patent Gmbh
US4994125A (en) * 1989-05-08 1991-02-19 Olin Corporation Electric primer with intrinsic conductive mix
JP2875600B2 (ja) * 1990-07-06 1999-03-31 ポーラ化成工業株式会社 被覆力に優れた着色基剤を配合して成る化粧料
DE4117718C1 (en) * 1991-05-30 1992-07-02 Dynamit Nobel Ag, 5210 Troisdorf, De Surface coating prim. and/or sec. explosives with flame extinguishable material - by homogeneously treating with nonionic surfactant liq., contacting with material and blending
JP2998633B2 (ja) * 1996-04-01 2000-01-11 富士ゼロックス株式会社 静電潜像現像剤用キャリア、その製造方法、静電潜像現像剤、画像形成方法及び画像形成装置
US5750921A (en) * 1997-07-07 1998-05-12 Chan; May L. Waste-free method of making molding powder
US5879079A (en) * 1997-08-20 1999-03-09 The United States Of America As Represented By The Administrator, Of The National Aeronautics And Space Administration Automated propellant blending
AU4639600A (en) * 1999-01-29 2000-08-18 Cordant Technologies, Inc. Water-free preparation of igniter granules for waterless extrusion processes
US6503350B2 (en) * 1999-11-23 2003-01-07 Technanogy, Llc Variable burn-rate propellant
US6605167B1 (en) * 2000-09-01 2003-08-12 Trw Inc. Autoignition material for a vehicle occupant protection apparatus

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2905882A1 (fr) * 2006-09-14 2008-03-21 Saint Louis Inst Procede de fabrication de micro et/ou nanothermites et nanothermites associees.
WO2009081048A3 (fr) * 2007-12-19 2010-04-08 Snpe Materiaux Energetiques Desensibilisation par enrobage de cristaux de substances energetiques explosives; cristaux de telles substances enrobes; materiaux energetiques.
JP2011506262A (ja) * 2007-12-19 2011-03-03 エスエヌペーウー マテリオー エネルジェティク 爆発エネルギー材の複数の結晶にコーティングを施すことにより感度を抑制する方法、このような物質のコーティングが施された結晶、及びエネルギー材

Also Published As

Publication number Publication date
EP1500639B1 (de) 2014-03-26
FR2857963A1 (fr) 2005-01-28
FR2857963B1 (fr) 2006-09-08
EP1500639A3 (de) 2011-11-30

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