EP3873690A1 - Deposing initiary compositions - Google Patents

Deposing initiary compositions

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Publication number
EP3873690A1
EP3873690A1 EP19798349.7A EP19798349A EP3873690A1 EP 3873690 A1 EP3873690 A1 EP 3873690A1 EP 19798349 A EP19798349 A EP 19798349A EP 3873690 A1 EP3873690 A1 EP 3873690A1
Authority
EP
European Patent Office
Prior art keywords
metal
oxide
complex
nanothermite
suspension
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
EP19798349.7A
Other languages
German (de)
French (fr)
Other versions
EP3873690B1 (en
Inventor
Andy Oden BURN
James WILGEROTH
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.)
BAE Systems PLC
Original Assignee
BAE Systems PLC
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Filing date
Publication date
Application filed by BAE Systems PLC filed Critical BAE Systems PLC
Publication of EP3873690A1 publication Critical patent/EP3873690A1/en
Application granted granted Critical
Publication of EP3873690B1 publication Critical patent/EP3873690B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • 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
    • B22F1/12—Metallic powder containing non-metallic particles
    • 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
    • C06B33/02—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 with an organic non-explosive or an organic non-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
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers
    • C06C7/02—Manufacture; Packing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42C—AMMUNITION FUZES; ARMING OR SAFETY MEANS THEREFOR
    • F42C19/00—Details of fuzes
    • F42C19/08—Primers; Detonators
    • F42C19/0803—Primers; Detonators characterised by the combination of per se known chemical composition in the priming substance
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • compositions and method of deposing initiatory compositions specifically for filling small devices such as caps, and ignitors.
  • Primers for medium and small calibre munitions are typically modest-sized components requiring no more than a few hundred milligrams of primary explosive or other initiating composition. Consequently, filling such components by hand requires significant dexterity. Filling processes involving dry powders are also prone to initiation via electrostatic discharge, which promotes safety concerns with regards to the operator.
  • a nanothermite initiatory composition comprising a:
  • said nanothermite suspension comprises a charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M ' ), to from a metal(M)oxide complex, and a metal (M’) complex, such that said metal(M)oxide complex and said metal (M ' ) complex repel each other in said suspension,
  • the admixture of the binder, nanothermite suspension charging reagent has been caused to be mixed under Resonant Acoustic Mixing to provide a stable suspension of a nanothermite complex; in a highly preferred arrangement the nanothermite suspension further comprises a non-ionic surfactant.
  • the repelling of said metal(M)oxide complex and a metal (M ' ) complex is caused by the charging reagent having the same electrostatic charge or providing steric hindrance. The effect will be determined by the choice of the charging reagent.
  • the nanothermite may be present in a stoichiometric ratio or fuel-rich ratio of fuel and oxidizer nanopowders.
  • the solvent may comprise a binder, in the range of from 0.1 to 16% w/w.
  • the binder may be any typically used binder in energetic material compositions.
  • the binder may be selected from a non-energetic binder and/or an energetic binder, present in the range of from 0.1 % to 16%wt, more preferably in the range of 0.5 to 5%wt.
  • the binder may be a mixture of an energetic and non-energetic binder.
  • suitable non-energetic binder materials are ethylene-vinyl acetate, esters, ego cellulose acetate, cellulose acetate butyrate, polyurethanes, polyesters, polybutadienes, polyethylenes, polyvinyl acetate and blends and/or copolymers thereof, or fluorinated binders.
  • the fluorinated binders may be mono- or per-fluorinated, such as, for example PTFE, Viton etc.
  • Suitable energetic binder materials which may be used alongside a non-energetic binder, may be nitrocellulose, polyvinylnitrate, nitroethylene, nitroallyl acetate, nitroethyl acrylate, nitroethylmethacrylate, trinitroethyl acrylate, din itropropyl acrylate, C-nitropolystyrene and its derivatives, polyurethanes with aliphatic C- and N- nitro groups, polyesters made from dinitrocarboxylic acids and dinitrodiol and homopolymers of 3-10 nitrato-3 methyl oxetane (PolyNIMMO).
  • the nanothermite initiatory composition may deposed directly into a device, or deposed to provide a loose composition that can be filled using conventional techniques, such as granules, rods, pellets, etc.
  • the device to be filled may be any munition or subsystem, typically this may be a primer cup, initiator, or part of the explosive train.
  • the nanothermite suspension may be caused to be evaporated, to provide a powdered nanothermite encapsulated in the binder material.
  • the evaporation stage may be afforded in once in a filled device.
  • the admixture comprising, for example, nanothermite suspension, binder, adhesive, optinally any curative, may be directly applied to any substrate or device by means of either extrusion, deposition or spray process, e.g.
  • Plasticisers such as non-energetic, energetic plasticisers or a combination therefore may be used.
  • the nanothermite solids loading in the suspension may be greater than 10%w/w, preferably of from 10% to 70%w/w, most preferably 30-60%w/w, within the composition.
  • the device to be filled may be any munition or subsystem, typically this may be a primer cup, initiator, or part of the explosive train.
  • the metal(M)oxide and a metal (M ' ), may each have an average particle size of less than 1000nm, preferably less than 500nm, more preferably less than 100nm, yet more preferably less than 50nm.
  • the metal oxide(M) may be any oxide of a metal, preferably the metal is selected from a transition metal, Al, In, Sn, Mg, Be, B, and Si or a mixture thereof.
  • the transition metal may be selected from Sc, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo or Z.
  • the metal (M ' ) may be selected from a transition metal, Al, In, Sn, Mg, Be, B, Si or a mixture thereof, provided that the metal and the metal ion in the metal oxide are not selected from the same metal, ie (M) 1 (M’).
  • the transition metal for the (M’) may be selected from Sc, Ti, V, Cr, Mn, Fe,Co, Ni, Cu or Zn.
  • Particularly preferred mixtures may be bismuth (III) oxide / aluminium, iron (III) oxide / aluminium, and copper (II) oxide / aluminium, Molybdenum (VI) oxide / aluminium and manganese (III) oxide / aluminium.
  • the charging reagent may be selected from any reagent that is capable of forming a stable complex such as a chelate, ligand with the metal M’ and metal (M) oxide such that they repel each other in said suspension.
  • the repulsion may be caused by large steric hindrances and/or ionic repulsion.
  • the charging reagent may be monodentate, bidentate ligand oligomeric, polymeric, ionic, or polar organic compounds, such as halo, polyethylenimine, phosphate ester, poly(dimethyldiallylammonium chloride), trioxadecanoic acid and acrylate- acrylamide copolymers.
  • the suspension may comprise a non- ionic surfactant.
  • the non-ionic surfactant may assist to prevent aggregated particles from forming as well as enhancing adsorption on the particle.
  • the selection of the non-ionic surfactant may prepare the surface of the metal (M’) and metal(M) oxide particles to accept the charging reagent ligand, such as to facilitate the adsorption of the charging ligand, ie protons, iodide, conjugate systems, or ions on the particles surface.
  • a charging reagent may be iodine, acetone and deionized water in a polar organic solvent, with a non-ionic surfactant, such as acetylacetone or ethylene glycol.
  • the solvent is preferably an organic solvent, preferably a polar solvent, such as for example an Ci to C10 alcohol, such as alkyl, alkenyl, aromatic, straight or branch chained, and mixtures thereof.
  • a polar solvent such as for example an Ci to C10 alcohol, such as alkyl, alkenyl, aromatic, straight or branch chained, and mixtures thereof.
  • the use of large complex ligands may provide steric repulsion, electronic repulsion.
  • the surfactant may itself form a chelate or complex bonds with the metal (M’) and metal atom of the metal (M) oxide.
  • Examples of the non- ionic surfactants may be acetylacetone, ethylene glycol or similar compounds.
  • the device may be initiated by an electrical stimulus, such as an electric spark, potential difference, which requires the use of a conducting composition.
  • an electrical stimulus such as an electric spark, potential difference, which requires the use of a conducting composition.
  • the nanothermite suspension may be made
  • the composition may comprises a graphitic filler in the range of 1 -40% by weight, a graphitic filler greater than 20%, such as in the range of 20 to 40% w/w.
  • the graphitic filler had been found to further assist the complexing of the charging reagent and non-ionic surfactant with the metal and metal oxides.
  • the Resonant Acoustic Mixing stimulus process may be affected at different frequencies/power to provide homogeneous mixing of the composition.
  • Resonant acoustic mixing is far removed from sonification (or ultrasound) techniques.
  • Ultrasound employs very high frequencies, typically greater than 20KHz.
  • the resonant acoustic mixing may be caused at a frequency in the range of less than 200Hz, preferably less than 100 Hz, preferably from 20 Hz to 100Hz, more preferably in the range of from 50Hz to 70Hz, yet more preferably 58Hz to 60hz.
  • the resonant acoustic mixing occurs at very low frequencies, in the order of tens of hertz, compared to those used in sonification (ultrasound), which is tens of thousands of hertz.
  • the resonant acoustic mixing stimulus may apply an acceleration force of up to 100g.
  • Resonant acoustic mixing induces microscale turbulence by propagating acoustic waves of a low frequency throughout a mixture.
  • the resonant acoustic mixing system has a lower frequency of acoustic energy and can be more readily applied to larger scale of mixing than ultrasonic agitation.
  • the mixing time for typical shear force mixers may be in the order of several hours to ensure homogenous mixing, in resonant acoustic mixing the stimulus may cause the time to be reduced to less than hour, more preferably less than 20 mins or even less than 5 minutes.
  • the use of conventional mixing techniques with nanometric scale powders, particularly those in suspension often causes high viscosity suspensions, the use of Resonant Acoustic Mixing is particularly suited to mixing high viscosity suspensions.
  • a deposed nanothermite energetic material comprising a
  • metal (M) and metal (M’) are complexed with a reagent such that said metal(M)oxide in said metal(M) oxide complex, and the metal (M ' ) in the metal (M’) complex have the same electrostatic charge.
  • a method of filling explosive devices with a nanothermite initiatory composition comprising the steps of:
  • nanothermite composition comprising
  • a charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M ' ), such that said metal(M) in said metal(M)oxide complex, and the metal(M ' ) in the metal (M’) complex have the same electrostatic charge or are sterically hindered, such that said metal(M)oxide complex and a metal (M ' ) complex repel each other,
  • the above suspension was prepared with a nanothermite loading of 40%w/w.
  • the suspension was substantially devoid of aggregated particulates, the suspension was capable of being deposed onto a substrate and dried.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Paints Or Removers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

There is provided a composition and method of deposing an initiatory composition, said composition, comprisinga: (i) ananothermite suspension ofa metal(M)oxide and a metal (M´) in a solvent, wherein the average particle size of the metal(M)oxide and a metal (M´) is less than 1000 nm, provided that (M) ≠ (M´), (ii) wherein said nanothermite suspension comprisesa charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M´), to from a metal(M)oxide complex, and a metal (M') complex that have the same electrostatic charge, such that said metal(M)oxide complex and a metal (M´) complex repel each other in said suspension, wherein the admixture of the binder, nanothermite suspension charging reagent, has been caused to be mixed under Resonant Acoustic Mixingto provide a stable suspension of a nanothermite complex

Description

DEPOSING INITIARY COMPOSITIONS
There is provided a composition and method of deposing initiatory compositions , specifically for filling small devices such as caps, and ignitors.
There is a desire to move away from typical sensitive initiatory compositions, and specifically those that require the use of lead based compositions.
Primers for medium and small calibre munitions are typically modest-sized components requiring no more than a few hundred milligrams of primary explosive or other initiating composition. Consequently, filling such components by hand requires significant dexterity. Filling processes involving dry powders are also prone to initiation via electrostatic discharge, which promotes safety concerns with regards to the operator.
According to a first aspect of present invention there is provided a nanothermite initiatory composition, comprising a:
(i) a nanothermite suspension of a metal(M)oxide and a metal (M') in a solvent, wherein the average particle size of the metal(M)oxide and a metal (M') is less than 1000 nm, provided that (M) ¹ (M'),
(ii) wherein said nanothermite suspension comprises a charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M'), to from a metal(M)oxide complex, and a metal (M’) complex, such that said metal(M)oxide complex and said metal (M') complex repel each other in said suspension,
wherein the admixture of the binder, nanothermite suspension charging reagent, has been caused to be mixed under Resonant Acoustic Mixing to provide a stable suspension of a nanothermite complex; in a highly preferred arrangement the nanothermite suspension further comprises a non-ionic surfactant. The repelling of said metal(M)oxide complex and a metal (M') complex is caused by the charging reagent having the same electrostatic charge or providing steric hindrance. The effect will be determined by the choice of the charging reagent.
The nanothermite may be present in a stoichiometric ratio or fuel-rich ratio of fuel and oxidizer nanopowders. Stoichiometric ratio is defined as Equivalence Ratio (ER or f) = 1.0. Fuel-rich ratios, for example, may be ER (f) = 1 .2.
In a highly preferred arrangement the solvent may comprise a binder, in the range of from 0.1 to 16% w/w.
The binder may be any typically used binder in energetic material compositions. The binder may be selected from a non-energetic binder and/or an energetic binder, present in the range of from 0.1 % to 16%wt, more preferably in the range of 0.5 to 5%wt.
The binder may be a mixture of an energetic and non-energetic binder. Examples of suitable non-energetic binder materials are ethylene-vinyl acetate, esters, ego cellulose acetate, cellulose acetate butyrate, polyurethanes, polyesters, polybutadienes, polyethylenes, polyvinyl acetate and blends and/or copolymers thereof, or fluorinated binders. The fluorinated binders may be mono- or per-fluorinated, such as, for example PTFE, Viton etc. Examples of suitable energetic binder materials which may be used alongside a non-energetic binder, may be nitrocellulose, polyvinylnitrate, nitroethylene, nitroallyl acetate, nitroethyl acrylate, nitroethylmethacrylate, trinitroethyl acrylate, din itropropyl acrylate, C-nitropolystyrene and its derivatives, polyurethanes with aliphatic C- and N- nitro groups, polyesters made from dinitrocarboxylic acids and dinitrodiol and homopolymers of 3-10 nitrato-3 methyl oxetane (PolyNIMMO).
The nanothermite initiatory composition may deposed directly into a device, or deposed to provide a loose composition that can be filled using conventional techniques, such as granules, rods, pellets, etc. The device to be filled may be any munition or subsystem, typically this may be a primer cup, initiator, or part of the explosive train.
In a preferred arrangement the nanothermite suspension may be caused to be evaporated, to provide a powdered nanothermite encapsulated in the binder material. The evaporation stage may be afforded in once in a filled device.
The admixture, comprising, for example, nanothermite suspension, binder, adhesive, optinally any curative, may be directly applied to any substrate or device by means of either extrusion, deposition or spray process, e.g.
aerosol , nozzle printing or vapour deposition.
Plasticisers, such as non-energetic, energetic plasticisers or a combination therefore may be used.
The nanothermite solids loading in the suspension may be greater than 10%w/w, preferably of from 10% to 70%w/w, most preferably 30-60%w/w, within the composition.
The device to be filled may be any munition or subsystem, typically this may be a primer cup, initiator, or part of the explosive train.
The metal(M)oxide and a metal (M'), may each have an average particle size of less than 1000nm, preferably less than 500nm, more preferably less than 100nm, yet more preferably less than 50nm.
The metal oxide(M) may be any oxide of a metal, preferably the metal is selected from a transition metal, Al, In, Sn, Mg, Be, B, and Si or a mixture thereof. Preferably the transition metal may be selected from Sc, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo or Z.
The metal (M') may be selected from a transition metal, Al, In, Sn, Mg, Be, B, Si or a mixture thereof, provided that the metal and the metal ion in the metal oxide are not selected from the same metal, ie (M) ¹ (M’). The transition metal for the (M’) may be selected from Sc, Ti, V, Cr, Mn, Fe,Co, Ni, Cu or Zn.
Particularly preferred mixtures may be bismuth (III) oxide / aluminium, iron (III) oxide / aluminium, and copper (II) oxide / aluminium, Molybdenum (VI) oxide / aluminium and manganese (III) oxide / aluminium.
The charging reagent may be selected from any reagent that is capable of forming a stable complex such as a chelate, ligand with the metal M’ and metal (M) oxide such that they repel each other in said suspension. The repulsion may be caused by large steric hindrances and/or ionic repulsion. The charging reagent may be monodentate, bidentate ligand oligomeric, polymeric, ionic, or polar organic compounds, such as halo, polyethylenimine, phosphate ester, poly(dimethyldiallylammonium chloride), trioxadecanoic acid and acrylate- acrylamide copolymers.
In a highly preferred arrangement the suspension may comprise a non- ionic surfactant. The non-ionic surfactant may assist to prevent aggregated particles from forming as well as enhancing adsorption on the particle.
The selection of the non-ionic surfactant may prepare the surface of the metal (M’) and metal(M) oxide particles to accept the charging reagent ligand, such as to facilitate the adsorption of the charging ligand, ie protons, iodide, conjugate systems, or ions on the particles surface. A preferred example of a charging reagent may be iodine, acetone and deionized water in a polar organic solvent, with a non-ionic surfactant, such as acetylacetone or ethylene glycol.
The solvent is preferably an organic solvent, preferably a polar solvent, such as for example an Ci to C10 alcohol, such as alkyl, alkenyl, aromatic, straight or branch chained, and mixtures thereof.
The use of large complex ligands, may provide steric repulsion, electronic repulsion. The surfactant may itself form a chelate or complex bonds with the metal (M’) and metal atom of the metal (M) oxide. Examples of the non- ionic surfactants may be acetylacetone, ethylene glycol or similar compounds.
In one arrangement the device may be initiated by an electrical stimulus, such as an electric spark, potential difference, which requires the use of a conducting composition. The nanothermite suspension may be made
conducting by the inclusion of conducting particles, such that the composition may comprises a graphitic filler in the range of 1 -40% by weight, a graphitic filler greater than 20%, such as in the range of 20 to 40% w/w. The graphitic filler had been found to further assist the complexing of the charging reagent and non-ionic surfactant with the metal and metal oxides.
The Resonant Acoustic Mixing stimulus process may be affected at different frequencies/power to provide homogeneous mixing of the composition. Resonant acoustic mixing is far removed from sonification (or ultrasound) techniques. Ultrasound employs very high frequencies, typically greater than 20KHz.
In a highly preferred arrangement the resonant acoustic mixing may be caused at a frequency in the range of less than 200Hz, preferably less than 100 Hz, preferably from 20 Hz to 100Hz, more preferably in the range of from 50Hz to 70Hz, yet more preferably 58Hz to 60hz. The resonant acoustic mixing occurs at very low frequencies, in the order of tens of hertz, compared to those used in sonification (ultrasound), which is tens of thousands of hertz. Typically the resonant acoustic mixing stimulus may apply an acceleration force of up to 100g.
Resonant acoustic mixing induces microscale turbulence by propagating acoustic waves of a low frequency throughout a mixture. The resonant acoustic mixing system has a lower frequency of acoustic energy and can be more readily applied to larger scale of mixing than ultrasonic agitation. The mixing time for typical shear force mixers may be in the order of several hours to ensure homogenous mixing, in resonant acoustic mixing the stimulus may cause the time to be reduced to less than hour, more preferably less than 20 mins or even less than 5 minutes. The use of conventional mixing techniques with nanometric scale powders, particularly those in suspension, often causes high viscosity suspensions, the use of Resonant Acoustic Mixing is particularly suited to mixing high viscosity suspensions.
According to a further aspect of the invention there is provided a deposed nanothermite energetic material comprising a
i) a binder,
ii) a metal(M)oxide and a metal (M'), wherein the average particle size of the metal(M)oxide and a metal (M') is less than 100nm,
wherein said metal (M) and metal (M’) are complexed with a reagent such that said metal(M)oxide in said metal(M) oxide complex, and the metal (M') in the metal (M’) complex have the same electrostatic charge.
According to a further aspect of the invention there is provided a method of filling explosive devices with a nanothermite initiatory composition, comprising the steps of:
forming a nanothermite composition comprising
(i) a binder,
(ii) a thermite suspension of a metal(M)oxide and a metal (M') in a solvent, wherein the average particle size of the metal(M)oxide and a metal (M') is less than 1000nm, provided that M ¹ M',
(iii) forming a charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M'), such that said metal(M) in said metal(M)oxide complex, and the metal(M') in the metal (M’) complex have the same electrostatic charge or are sterically hindered, such that said metal(M)oxide complex and a metal (M') complex repel each other,
forming an admixture of the binder, thermite suspension and charging reagent , causing said admixture to be mixed under Resonant Acoustic Mixing to provide a stable suspension of an admixture of a nanothermite complex,
(iii) filling the device with the admixture of nanothermite complex.. Experimental
Table 1
The above suspension was prepared with a nanothermite loading of 40%w/w. The suspension was substantially devoid of aggregated particulates, the suspension was capable of being deposed onto a substrate and dried.

Claims

Claims
1 ) A nanothermite initiatory composition, comprising a:
(i) a nanothermite suspension of a metal(M)oxide and a metal (M') in a solvent, wherein the average particle size of the metal(M)oxide and a metal (M') is less than 1000 nm, provided that (M) ¹ (M'),
(ii) wherein said nanothermite suspension comprises a charging reagent, comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M'), to from a metal(M)oxide complex, and a metal (M’) complex, such that said metal(M)oxide complex and said metal (M') complex repel each other in said suspension,
wherein the admixture of the nanothermite suspension, charging reagent, has been caused to be mixed under Resonant Acoustic Mixing to provide a stable suspension of the nanothermite composition.
2). A composition according to claim 1 , wherein the repelling of said
metal(M)oxide complex and a metal (M') complex is caused by the charging reagent having the same electrostatic charge and/or providing steric hindrance therebetween.
3). A composition according to any one of the preceding claims, wherein the nanothermite suspension comprises a binder, in the range of from 0.1 to 16% w/w.
4). A composition according to any one of the preceding claims, wherein the nanothermite suspension comprises a non-ionic surfactant.
5). A composition according to any one of the preceding claims, wherein the composition is deposed in a primer cup, initiator, or explosive train.
6). A composition according to any one of the preceding claims, wherein the metal oxide(M) is an oxide of a metal selected from a transition metal, Al, In,
Sn, Mg, Be, B, and Si or a mixture thereof. 7). A composition of claim 6, wherein the transition metal is Sc, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo or Zn. 8). The composition of according to any one of the preceding claims wherein the metal (M') is selected from a transition metal, Al, In, Sn, Mg, Be, B, Si or a mixture thereof.
9). A composition of claim 8, wherein the transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn.
10) A composition according to anyone of the preceding claims, wherein the composition comprises a graphitic filler in the range of 20-40% by weight. 11 ) A composition according to any one of the preceding claims wherein the solvent is a polar organic solvent.
12) A method of filling explosive devices with a nanothermite initiatory
composition, comprising the steps of:
forming a nanothermite composition comprising
(i) a binder,
(ii) a thermite suspension of a metal(M)oxide and a metal (M') in a solvent, wherein the average particle size of the metal(M)oxide and a metal (M') is less than 1000nm, provided that M ¹ M',
(iii) forming a charging reagent comprising a reagent capable of forming a stable complex with each of the metal(M)oxide and the metal (M'), such that said metal(M) in said metal(M)oxide complex, and the metal(M') in the metal (M’) complex have the same electrostatic charge or are sterically hindered, such that said metal(M)oxide complex and a metal (M') complex repel each other,
forming an admixture of the binder, thermite suspension and charging reagent , causing said admixture to be mixed under Resonant Acoustic Mixing to provide a stable suspension of an admixture of a nanothermite complex,
(iii) filling the device with the admixture of nanothermite complex. 13). A composition according to any one of the preceding claims, wherein the nanothermite suspension comprises a binder, in the range of from 0.1 to 16% w/w.
14). A composition according to any one of the preceding claims, wherein the nanothermite suspension comprises a non-ionic surfactant.
15) A deposed nanothermite energetic material comprising a
i) a binder,
ii) a metal(M)oxide and a metal (M'), wherein the average particle size of the metal(M)oxide and a metal (M') is less than 100nm,
wherein said metal (M) and metal (M’) are complexed with a reagent such that said metal(M)oxide in said metal(M) oxide complex, and the metal (M') in the metal (M’) complex have the same electrostatic charge.
EP19798349.7A 2018-11-02 2019-10-30 Deposing initiary compositions Active EP3873690B1 (en)

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US4013491A (en) * 1975-05-14 1977-03-22 Thiokol Corporation Incendiary compositions of magnesium and fluoroalkyl phosphate esters
US5248425A (en) * 1992-10-28 1993-09-28 Corning Incorporated Aqueous thermite coated filter
FR2905882B1 (en) * 2006-09-14 2008-10-31 Saint Louis Inst PROCESS FOR MANUFACTURING MICRO AND / OR NANOTHERMITES AND ASSOCIATED NANOTHERMITES
US8048242B1 (en) * 2007-04-05 2011-11-01 Sandia Corporation Nanocomposite thermite ink
US9187519B1 (en) * 2012-12-28 2015-11-17 The United States Of America As Represented By The Secretary Of The Air Force Reactive nanocomposites and methods of making the same
CN104551005B (en) * 2015-01-07 2017-01-04 北京化工大学 A kind of nanoscale nucleocapsid structure thermite and preparation method thereof
EP3606892B1 (en) * 2017-04-03 2022-01-05 BAE Systems PLC Improved process for making and filling a pbx composition

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