WO2004011396A2 - Compositions d'allumage electrique exemptes de plomb - Google Patents

Compositions d'allumage electrique exemptes de plomb Download PDF

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Publication number
WO2004011396A2
WO2004011396A2 PCT/US2003/022831 US0322831W WO2004011396A2 WO 2004011396 A2 WO2004011396 A2 WO 2004011396A2 US 0322831 W US0322831 W US 0322831W WO 2004011396 A2 WO2004011396 A2 WO 2004011396A2
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
nanoscale
aluminum
metal
electric match
Prior art date
Application number
PCT/US2003/022831
Other languages
English (en)
Other versions
WO2004011396A3 (fr
Inventor
Darren Naud
Steven F. Son
Michael A. Hiskey
James R. Busse
Blaine W. Asay
Original Assignee
The Regents Of The University Of California
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 The Regents Of The University Of California filed Critical The Regents Of The University Of California
Priority to AU2003254091A priority Critical patent/AU2003254091A1/en
Publication of WO2004011396A2 publication Critical patent/WO2004011396A2/fr
Publication of WO2004011396A3 publication Critical patent/WO2004011396A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones
    • C06B45/14—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones a layer or zone containing an inorganic explosive or an inorganic explosive or an inorganic thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C15/00—Pyrophoric compositions; Flints
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B3/00—Blasting cartridges, i.e. case and explosive
    • F42B3/10—Initiators therefor
    • F42B3/11—Initiators therefor characterised by the material used, e.g. for initiator case or electric leads
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B3/00—Blasting cartridges, i.e. case and explosive
    • F42B3/10—Initiators therefor
    • F42B3/12—Bridge initiators
    • F42B3/128—Bridge initiators characterised by the composition of the pyrotechnic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B3/00—Blasting cartridges, i.e. case and explosive
    • F42B3/10—Initiators therefor
    • F42B3/195—Manufacture
    • F42B3/198—Manufacture of electric initiator heads e.g., testing, machines

Definitions

  • the present invention relates to electric match compositions, preferably lead-free electric match compositions and to electric matches, preferably lead-free electric matches.
  • Electric matches are used in the field of pyrotechnics to initiate devices by electrical means rather than by fuses. Fuses have the disadvantage of burning with a long delay before igniting a pyrotechnic device. Electric matches can instantaneously fire a device upon a user's command. In addition, electric matches can be fired remotely at a safe distance.
  • a typical electric match head consists of an electrically insulating substrate with copper foil cladding, similar to that used for printed circuit boards.
  • the size of the substrate is generally approximately 0.4 inches long by 0.1 inches wide and 30 mils thick.
  • the tip of the match has a small diameter nicrome wire soldered across the edge of the match. Insulated wire leads soldered at the base of the match provide the means of electrically firing the nicrome wire to produce the initiating spark.
  • the match head is coated with the lead-based composition to produce the spark-sensitive bead above the nicrome bridge wire. Normally, the bead is coated with a second layer of composition of a metal fuel such as a magnesium aluminum alloy or titanium with potassium perchlorate oxidizer. This secondary coat is generally necessary to produce the hot sparks to initiate black powder (or other primers) in pyrotechnic devices. Finally, the bead is generally coated with a nitrocellulose lacquer to provide strength and water resistance. Other similar match designs are well known.
  • the present invention provides an electric match composition including nanoscale particulates of an energetic material and a binder.
  • the electric match composition is lead-free.
  • the present invention further provides an electric match including a match head coated with an electric match composition including nanoscale particulates of an energetic material and a binder.
  • the electric match is lead-free.
  • the present invention is concerned with lead-free electric match compositions and preparation of lead-free electric matches.
  • the electric match materials include nanoscale energetic materials such as nanoscale thermite material mixtures, nanoscale intermetallic material mixtures, and nanoscale fuel and oxidant mixtures, preferably nanoscale thermite material mixtures.
  • nanoscale energetic materials are easily ignited, have good energy content and produce high temperature products.
  • the reaction rate is generally very rapid for nanoscale energetic materials such as nanoscale thermite materials and the reaction rate can be further tuned by control of the particle size.
  • the thermite material mixtures used in the present invention are metal/metal oxide compositions including a metal selected from the group consisting of aluminum, boron, lanthanum, magnesium, tantalum, titanium, yttrium and vanadium and a metal oxide selected from the group consisting of silver oxide, boron oxide, bismuth oxide, copper oxide, cobalt oxide, iron oxide, manganese oxide, molybdenum oxide, nickel oxide, silicon oxide, tin oxide, tantalum oxide, titanium oxide, tungsten oxide and vanadium oxide.
  • a metal selected from the group consisting of aluminum, boron, lanthanum, magnesium, tantalum, titanium, yttrium and vanadium
  • a metal oxide selected from the group consisting of silver oxide, boron oxide, bismuth oxide, copper oxide, cobalt oxide, iron oxide, manganese oxide, molybdenum oxide, nickel oxide, silicon oxide, tin oxide, tantalum oxide, titanium oxide, tungsten oxide and vanadium oxide
  • suitable thermite material mixtures can be included aluminum and silver oxide, aluminum and boron oxide, aluminum and bismuth oxide, aluminum and cobalt oxide, aluminum and copper oxide, aluminum and iron oxide, aluminum and manganese oxide, aluminum and molybdenum oxide, aluminum and niobium oxide, aluminum and nickel oxide, aluminum and palladium oxide, aluimnum and silicon oxide, aluminum and tin oxide, aluminum and tantalum oxide, aluminum and titanium oxide, aluminum and vanadium oxide, aluminum and tungsten oxide, boron and copper oxide, boron and iron oxide, boron and manganese oxide, boron and nickel oxide, boron and silicon oxide, boron and tin oxide, boron and tantalum oxide, boron and titanium oxide, boron and vanadium oxide, boron and tungsten oxide, lanthanum and silver oxide, lanthanum and copper oxide, lanthanum and iron oxide, lanthanum and manganese oxide, lanthanum and palladium oxide, lan
  • thermite material mixtures are aluminum and molybdenum oxide, aluminum and iron oxide, aluminum and copper oxide and aluminum and tungsten oxide.
  • the materials can be added in about stoichiometric amounts, although variations from stoichiometric amounts can be used as well.
  • the nanoscale intermetallic material mixtures used in the present invention may be material mixtures such as aluminum with nickel, cobalt, copper, iron, molybdenum, niobium, palladium, titamum, or zirconium, alloys of titanium with boron, nickel, cobalt and iron, zirconium boron, and hafnium boron.
  • the nanoscale intermetallic material mixtures are titanium boron or nickel aluminum.
  • the nanoscale fuel and oxidant mixtures used in the present invention may include a metal such as aluminum, boron, magnesium carbon, or silicon and an oxidant with a cation such potassium, sodium or ammonium and an anion such as nitrate, chlorate, perchlorate or peroxide.
  • Particular fuel and oxidant mixtures may include: aluminum and ammonium perchlorate; aluminum and ammonium chlorate; aluminum and ammonium nitrate; and, aluminum and potassium nitrate.
  • the nanoscale fuel and oxidant mixtures are aluminum and ammonium perchlorate, aluminum and ammonium chlorate, or alm num and ammonium nitrate.
  • the energetic materials of the electric match composition are nanoscale size materials.
  • the materials are particulates with predominant size distributions of from about 10 nm to 1000 nm in smallest dimension, e.g., diameter , thickness and the like, preferably from about 20 nm to 500 nm, more preferably from about 30 nm to 300 run.
  • Size distribution within a particular sample of material is another factor. Broader size distributions may be preferable to provide easier ignition and increased spark generation for consistent ignition oif the secondary pyrotechnic composition.
  • the binder for the nanoscale energetic materials can be any standard material used for binding paticles together.
  • the binder is nitrocellulose, but other binders are well known to those skilled in the art.
  • a nitrocellulose binder is also preferred for binding secondary pyrotechnic composition materials together within the match head as well.
  • a protective topcoat layer of a suitable waterproof polymer is over the entire match head.
  • Suitable waterproof polymers can include polymers and copolymers of vinyl based materials such as polyvinyl chloride, polyvinyl acetate, polystyrene, polymethyl methacrylate, polyacrylonitrile and the like.
  • Fig. 1 shows an electric match head in accordance with the present invention.
  • Match head 10 includes standard match parts such as a high resistance bridgewire 3, electrical insulator 5 with conductive foil cladding 4 and wire leads 6 soldered to the foil cladding
  • Primary coating layer 7 including the nanoscale particulates of an energetic material and a binder is on bridgewire 3. Over primary coating layer 7 is secondary pyrotechnic composition layer 2. Finally, a protective waterproof topcoat polymer layer 1 is over secondary pyrotechnic composition layer 2.
  • nanoscale particulates may be coated with a fluorosilane to provide protection from water and oxygen.
  • EXAMPLE 1 A bare electric match head was dipped into a sample composition for the primary layer.
  • the sample composition had been diluted with ethyl acetate containing 0.3 weight percent FC 430 (from 3M) surfactant.
  • the primary layer included about 6 milligrams
  • NC nanosize aluminum
  • 132 nm nanosize aluminum from Technanogy, Inc.
  • a thin barrier coating of nitrocellulose was deposited by dipping the match head into a nitrocellulose/ethyl acetate lacquer.
  • a secondary pyrotechnic composition included 56 percent by weight finely ground potassium perchlorate, 27 percent by weight 12 micron black aluminum, 8 percent by weight titanium (80-100 mesh), 0.3 percent by weight superfine iron oxide, 8.7 percent by weight nitrocellulose and sufficient ethyl acetate solvent to form a viscous slurry.
  • the match head was dipped into this secondary material several times with intermediate drying to build up the quantity of secondary pyrotechnic composition, followed again by a protective coat of nitrocellulose using the same nitrocellulose/ethyl acetate lacquer as with the primary layer.
  • a protective waterproof topcoat polymer layer was finally deposited onto the match head by dipping each match head into a composition of a copolymer of polyvinyl chloride, polyvinyl acetate and 2,3-epoxypropyl methacrylate dissolved in a mixture of methyl ethyl ketone and toluene.
  • the resultant electric match head was found to have reasonable mechanical strength.
  • EXAMPLE 2 Aging tests were conducted on the final electric match heads.
  • the protective topcoating had been used to keep moisture from contact with the nanosize aluminum.
  • the final electric match heads were submerged in water for three weeks and continued to perform reliably.
  • EXAMPLE 3 Impact tests (2.5 kg weight onto bare anvil) were conducted on the lead-free matches by placing the match head sample between two sheets of thick paper card stock and allowing a 1-kg drop weight to fall onto the sample. It was determined from twenty samples that the 50% probability of ignition (as described by Paine et al., hiorg. Chem., vol.38, pp. 3738-3743 (1999) ) was approximately 56 kg-cm. Identical tests on seven other commercially available electric matches of standard construction and performance gave results that ranged between 9 kg-cm and 23 kg-cm.
  • lead-free match heads in accordance with the present invention had properties comparable or exceeding those of commercially available electric matches of standard construction and performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Air Bags (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un allumage électrique comprenant des substances particulaires à l'échelle nanométrique d'un matériau énergétique et d'un liant. Le matériau énergétique peut être un mélange de métal de thermite/oxyde métallique à l'échelle nanométrique, un mélange de matériau intermétallique à l'échelle nanométrique ou un mélange de combustible et d'oxydant à l'échelle nanométrique.
PCT/US2003/022831 2002-07-29 2003-07-21 Compositions d'allumage electrique exemptes de plomb WO2004011396A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003254091A AU2003254091A1 (en) 2002-07-29 2003-07-21 Lead-free electric match compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20869602A 2002-07-29 2002-07-29
US10/208,696 2002-07-29

Publications (2)

Publication Number Publication Date
WO2004011396A2 true WO2004011396A2 (fr) 2004-02-05
WO2004011396A3 WO2004011396A3 (fr) 2012-02-02

Family

ID=31186874

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Country Status (3)

Country Link
US (1) US20080011398A9 (fr)
AU (1) AU2003254091A1 (fr)
WO (1) WO2004011396A2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004106268A2 (fr) * 2003-05-30 2004-12-09 Qinetiq Nanomaterials Limited Dispositifs explosifs
WO2005118510A1 (fr) * 2004-05-20 2005-12-15 Alexza Pharmaceuticals, Inc. Compositions d’amorcage stables et allumeurs
CN100395219C (zh) * 2006-04-29 2008-06-18 松原市大和化工有限责任公司 混敏硝铵炸药
GB2441151B (en) * 2006-01-23 2008-07-16 Schlumberger Holdings Wellbore tools
US7650840B2 (en) 2005-02-08 2010-01-26 Dyno Nobel Inc. Delay units and methods of making the same
WO2011106803A1 (fr) * 2010-02-24 2011-09-01 African Explosives Limited Amorceur de détonateur
US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making
US8991387B2 (en) 2003-05-21 2015-03-31 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10017429B2 (en) 2013-10-10 2018-07-10 Battelle Energy Alliance, Llc Methods of reducing ignition sensitivity of energetic materials
US9481614B2 (en) * 2013-10-10 2016-11-01 Battelle Energy Alliance, Llc Energetic materials and methods of tailoring electrostatic discharge sensitivity of energetic materials
US10173945B1 (en) 2014-04-23 2019-01-08 nanoMetallix LLC Nanocomposite for combustion applications
US10501385B1 (en) 2014-04-23 2019-12-10 Saint Louis University Nanocomposite enhanced fuel grains
US10494315B1 (en) * 2014-04-23 2019-12-03 Saint Louis University Method for making a novel nanocomposite for combustion applications
FR3042032B1 (fr) 2015-10-06 2017-12-15 Commissariat Energie Atomique Inflammateur non pyrotechnique
US11845904B1 (en) * 2021-07-23 2023-12-19 Advanced Defense Components Inc. Thermite fire starter kits
US11912636B1 (en) * 2021-07-23 2024-02-27 Advanced Defense Components Inc Thermite matches
CN114835538B (zh) * 2022-04-28 2023-02-14 西安近代化学研究所 一种双金属氧化物改性硼燃料及制备方法

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US4002122A (en) * 1961-03-02 1977-01-11 Mb Associates Microjet fuse
US4989515A (en) * 1989-08-08 1991-02-05 The United States Of America As Represented By The United States Department Of Energy Ignitor with stable low-energy thermite igniting system
US5717159A (en) * 1997-02-19 1998-02-10 The United States Of America As Represented By The Secretary Of The Navy Lead-free precussion primer mixes based on metastable interstitial composite (MIC) technology
US5885321A (en) * 1996-07-22 1999-03-23 The United States Of America As Represented By The Secretary Of The Navy Preparation of fine aluminum powders by solution methods

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US3415189A (en) * 1967-03-24 1968-12-10 Atlas Chem Ind Water destructible electric match
US4152988A (en) * 1977-09-19 1979-05-08 The United States Of America As Represented By The Secretary Of The Navy Electric match with epoxy coated fluorocarbon containing pyrotechnic composition
SE456939B (sv) * 1987-02-16 1988-11-14 Nitro Nobel Ab Spraengkapsel
US6298784B1 (en) * 1999-10-27 2001-10-09 Talley Defense Systems, Inc. Heat transfer delay
US6591752B2 (en) * 2001-02-12 2003-07-15 Trw Inc. Ignition material for an igniter
US7402777B2 (en) * 2004-05-20 2008-07-22 Alexza Pharmaceuticals, Inc. Stable initiator compositions and igniters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002122A (en) * 1961-03-02 1977-01-11 Mb Associates Microjet fuse
US4989515A (en) * 1989-08-08 1991-02-05 The United States Of America As Represented By The United States Department Of Energy Ignitor with stable low-energy thermite igniting system
US5885321A (en) * 1996-07-22 1999-03-23 The United States Of America As Represented By The Secretary Of The Navy Preparation of fine aluminum powders by solution methods
US5717159A (en) * 1997-02-19 1998-02-10 The United States Of America As Represented By The Secretary Of The Navy Lead-free precussion primer mixes based on metastable interstitial composite (MIC) technology

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8991387B2 (en) 2003-05-21 2015-03-31 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same
US9370629B2 (en) 2003-05-21 2016-06-21 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same
WO2004106268A3 (fr) * 2003-05-30 2005-03-24 Qinetiq Nanomaterials Ltd Dispositifs explosifs
GB2416350A (en) * 2003-05-30 2006-01-25 Qinetiq Nanomaterials Ltd Explosive devices
GB2416350B (en) * 2003-05-30 2006-09-20 Qinetiq Nanomaterials Ltd Explosive devices
JP2007511453A (ja) * 2003-05-30 2007-05-10 キネテイツク・ナノマテリアルズ・リミテツド 爆発デバイス
WO2004106268A2 (fr) * 2003-05-30 2004-12-09 Qinetiq Nanomaterials Limited Dispositifs explosifs
JP2007537967A (ja) * 2004-05-20 2007-12-27 アレックザ ファーマシューティカルズ， インコーポレイテッド 安定した開始剤組成物及び点火装置
WO2005118510A1 (fr) * 2004-05-20 2005-12-15 Alexza Pharmaceuticals, Inc. Compositions d’amorcage stables et allumeurs
US7650840B2 (en) 2005-02-08 2010-01-26 Dyno Nobel Inc. Delay units and methods of making the same
US8245643B2 (en) 2005-02-08 2012-08-21 Dyno Nobel Inc. Delay units and methods of making the same
GB2441151B (en) * 2006-01-23 2008-07-16 Schlumberger Holdings Wellbore tools
CN100395219C (zh) * 2006-04-29 2008-06-18 松原市大和化工有限责任公司 混敏硝铵炸药
WO2011106803A1 (fr) * 2010-02-24 2011-09-01 African Explosives Limited Amorceur de détonateur
US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making

Also Published As

Publication number Publication date
AU2003254091A1 (en) 2004-02-16
WO2004011396A3 (fr) 2012-02-02
US20060060272A1 (en) 2006-03-23
US20080011398A9 (en) 2008-01-17
AU2003254091A8 (en) 2012-02-23

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