EP2215034A1 - Utilisation de nanoparticules dans des explosifs - Google Patents

Utilisation de nanoparticules dans des explosifs

Info

Publication number
EP2215034A1
EP2215034A1 EP08836328A EP08836328A EP2215034A1 EP 2215034 A1 EP2215034 A1 EP 2215034A1 EP 08836328 A EP08836328 A EP 08836328A EP 08836328 A EP08836328 A EP 08836328A EP 2215034 A1 EP2215034 A1 EP 2215034A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
nanometers
water
explosive
oxidizer solution
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.)
Withdrawn
Application number
EP08836328A
Other languages
German (de)
English (en)
Inventor
Jimmie R. Baran, Jr.
Bruce A. Holcomb
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.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP2215034A1 publication Critical patent/EP2215034A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • 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
    • 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
    • C06B47/14—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 comprising a solid component and an aqueous phase
    • 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
    • C06B47/14—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 comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase

Definitions

  • Water-based explosives are commonly classified into two types: emulsions and water gels or slurries.
  • the emulsion type explosives typically have a dispersed phase of an aqueous oxidizer solution and continuous phase of an organic fuel.
  • Water-gel and slurry types of water-based explosives typically have an organic fuel as the dispersed phase and oxidizer-saturated water as the continuous phase.
  • Both types of water-based explosives require a sensitizer to enable detonation to occur, usually in the form of small bubbles. These bubbles may be hollow microspheres or gas bubbles. It is generally known in the explosives art that smaller bubbles and uniform distribution of these bubbles throughout the explosive provides good performance.
  • Small gas bubbles can be introduced into the water-based explosive either by chemical or mechanical techniques (e.g., bubbling a gas into the liquid).
  • mechanically or chemically supplied gas bubbles are inherently unstable (i.e., the small bubbles coalesce and form progressively larger bubbles of gas).
  • Such coalescence provides a less uniform distribution of gas bubbles and larger gas bubbles, both of which are detrimental to explosive performance and shelf life of the explosive.
  • a sensitizer in the form of small hollow microspheres or bubbles to the water-based explosive. Examples of such microspheres include those made of glass, water glass, organic polymer, or perlite. These hollow microspheres eliminate the problem of bubble coalescence, but at a much higher cost than gas bubbles.
  • gas is often unintentionally incorporated into the explosive, affecting explosive performance and shelf life of the explosive.
  • the disclosure provides water-based explosives comprising aqueous oxidizer solution, fuel, and a nanoparticle-stabilized foam as the sensitizer.
  • the nanoparticle-stabilized foam comprises an aqueous oxidizer solution-fuel mixture, and nanoparticles disposed in said oxidizer-fuel mixture, the nanoparticles having a median particle diameter of up to 100 nanometers (in some embodiments, up to 50 nanometers; in some embodiments, from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers; in some embodiments, an average particle diameter from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers).
  • the disclosure provides a method of providing a liquid (e.g., water-based) explosive having a stabilized foam sensitizer comprising incorporating nanoparticles having a median particle diameter of up to 100 nanometers (in some embodiments, up to 50 nanometers; in some embodiments, from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers; in some embodiments, an average particle diameter from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers) into a liquid explosive, and foaming the liquid explosive, wherein the nanoparticles are incorporated into the liquid explosive in an amount sufficient to stabilize the foamed liquid explosive.
  • a liquid e.g., water-based
  • a stabilized foam sensitizer comprising incorporating nanoparticles having a median particle diameter of up to 100 nanometers (in some embodiments, up to 50 nanometers; in some embodiments, from 3
  • the disclosure provides a water-based explosive precursor comprising an aqueous oxidizer solution, fuel, and nanoparticles having a median particle diameter up to 100 nanometers (in some embodiments, up to 50 nanometers; in some embodiments, from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers; in some embodiments, an average particle diameter from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers).
  • the water-based explosive precursor composition further comprises an emulsifier.
  • Exemplary nanoparticles include surface modified (i.e., nanoparticles that have a substance reacted to the respective surfaces thereof by at least one of covalent or acid/base bonding) (e.g., at least one of hydrophobically or hydrophilically surface-modified such that they are compatible with either an organic or aqueous continuous phase of a water- based explosive) and non-surface modified nanoparticles (i.e., nanoparticles that do not have a substance reacted to the respective surfaces thereof by at least one of covalent or acid/base bonding).
  • the nanoparticles include both surface modified nanoparticles and non- surface modified nanoparticles.
  • water-based explosive includes explosives that are in the form of a liquid, gel, slurry, suspension, emulsion, colloid, and the like, wherein the explosive contains an oxidizer dissolved in water.
  • the water may be the continuous phase (e.g., water-gels and slurries), or discontinuous phase in the case of emulsions.
  • Spensitizer means microbubbles of air, nitrogen, carbon dioxide, nitrogen monoxide and gaseous hydrocarbons and/or gas retained solid particles, such as hollow glass, water glass or organic microspheres or perlites or any other substance which provides density discontinuities within the explosive.
  • Persistent foam means the presence of gas voids in a composition for a period of greater than one minute after the composition has been foamed.
  • Water-based explosives comprise an aqueous oxidizer solution and fuel in the form of an emulsion, slurry, or gel.
  • oxidizers that are useful in water-based explosives described herein include nitrate, chlorate, or perchlorate salts of ammonium, sodium or potassium, hydrazines, organic amides (e.g., monomethyl amine nitrate, and combinations thereof).
  • Examples of fuels that are useful in water-based explosives include any fuel capable of being oxidized in a water-based explosive as defined herein. Specific examples include fuel oil, diesel fuel, gasoline, kerosene, jet fuel, white oil (e.g., mineral oil, etc.) vegetable oil (corn oil, etc.), animal oil (e.g., seal oil, whale oil, etc.), alcohols, waxes, as well as solid organic and metal particles (e.g., aluminum, and the like).
  • the water-based explosives described herein include nanoparticle-stabilized foam.
  • the nanoparticle-stabilized foam includes gas voids (i.e., bubbles), which are typically dispersed uniformly throughout the composition.
  • the foam is persistent and preferably includes a cellular structure in which the gas voids are in the form of closed cells.
  • the nanoparticles are individual, unassociated (i.e., non- aggregated) nanoparticles dispersed throughout the aqueous oxidizer solution- fuel mixture and preferably do not irreversibly associate with each other.
  • “associating with” includes covalent bonding, hydrogen bonding, electrostatic attraction, London forces, and/or hydrophobic interactions.
  • the nanoparticles can be inorganic and/or organic.
  • suitable inorganic nanoparticles include silica and metal oxide nanoparticles (e.g., zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide, tin oxide, alumina/silica, and combinations thereof).
  • the nanoparticles have a median particle diameter up to 100 nanometers (in some embodiments, up to 50 nanometers; in some embodiments, from 3 nanometers to 50 nanometers, from 3 nanometers to 20 nanometers, or even from 3 nanometers to 10 nanometers). If the nanoparticles are aggregated, the maximum cross sectional dimension of the aggregated particle is within any of these specified ranges.
  • the nanoparticles may be in the form of a colloidal dispersion.
  • useful commercially available non-modified silica nano-sized colloidal silicas include those under the trade designations "NALCO 1040,” “NALCO 1050,” “NALCO 1060,” “NALCO 2326,” “NALCO 2327,” and “NALCO 2329", from Nalco Chemical Co., Naperville, IL.
  • Useful metal oxide colloidal dispersions include colloidal zirconium oxide, suitable examples of which are described in U.S. Pat. No. 5,037,579 (Matchett) (the disclosure of which is incorporated herein by reference), and colloidal titanium oxide, useful examples of which are described, for example, in PCT Publication No. WO 00/06495 entitled, "Nanosize Metal Oxide Particles for Producing Transparent Metal
  • Exemplary organic nanoparticles also include buckminsterfullerenes (fullerenes), dendrimers, branched and hyperbranched "star” polymers such as 4, 6, or 8 armed polyethylene oxide (available, for example, from Aldrich Chemical Company, Milwaukee, WI or Shearwater Corporation, Huntsville, AL) whose surface has been chemically modified.
  • Specific examples of fullerenes include CgQ, C70, C ⁇ an d Cg ⁇
  • Specific examples of dendrimers include polyamidoamine (PAMAM) dendrimers of Generations 2 through 10 (G2 -GlO), available also, for example, from Aldrich Chemical Company.
  • organic nanoparticle materials include organic polymeric nanospheres, insoluble sugars such as lactose, trehalose, glucose or sucrose, and insoluble amino acids.
  • another class of organic polymeric nanospheres includes nanospheres that comprise polystyrene, such as those available from Bangs Laboratories, Inc. of Fishers, IN as powders or dispersions). Such organic polymeric nanospheres will generally have average particle sizes ranging from 10 nanometers to up to 60 nanometers.
  • the nanoparticles are selected such that the composition formed therewith is free from a degree of particle agglomeration or aggregation that would interfere with the desired properties of the composition including the ability of the composition to foam.
  • the nanoparticles are selected to be compatible with the aqueous oxidizer solution-fuel mixture to be foamed.
  • the nanoparticles may be selected to be compatible with at least one component of the aqueous oxidizer solution- fuel mixture.
  • One method of assessing the compatibility of the nanoparticles with the aqueous oxidizer solution-fuel mixture includes determining whether the resulting composition forms a persistent foam when a foaming agent is introduced into the composition.
  • one useful method of assessing the compatibility of the nanoparticles with the transparent aqueous oxidizer solution- fuel mixture includes combining the nanoparticles and the aqueous oxidizer solution-fuel mixture and observing whether the nanoparticles appear to dissolve in the aqueous oxidizer solution-fuel mixture such that the resulting composition is transparent.
  • the nature of the inorganic particle component of the particle will prevent the particle from actually dissolving in the aqueous oxidizer solution-fuel mixture (i.e., the nanoparticles will be dispersed in the aqueous oxidizer solution-fuel mixture), however, the compatibility of the nanoparticles with the aqueous oxidizer solution- fuel mixture will give the nanoparticles the appearance of dissolving in the aqueous oxidizer solution- fuel mixture. As the size of the nanoparticles increases, the haziness of the aqueous oxidizer solution-fuel mixture generally increases. In some embodiments, nanoparticles are selected such that they do not settle out of the aqueous oxidizer solution-fuel mixture.
  • the further step in assessing the compatibility of the aqueous oxidizer solution-fuel mixture and the nanoparticles includes determining whether, upon subsequent introduction of a foaming agent, the composition foams.
  • the nanoparticles include surface-modified nanoparticles.
  • the surface-modified nanoparticles have surface groups that modify the solubility characteristics of the nanoparticles.
  • the surface groups are selected to render the particle compatible with the aqueous oxidizer solution-fuel mixture (e.g., a component of the aqueous oxidizer solution-fuel mixture), in which the particle is disposed such that the resulting composition, upon foaming, forms a persistent foam.
  • Suitable surface groups can also be selected based upon the solubility parameter of the surface group and the aqueous oxidizer solution-fuel mixture.
  • the surface group, or the agent from which the surface group is a reaction product of has a solubility parameter similar to the solubility parameter of the aqueous oxidizer solution- fuel mixture to be foamed.
  • the aqueous oxidizer solution- fuel mixture to be foamed is hydrophobic, for example, one skilled in the art can select from among various hydrophobic surface groups to achieve a surface-modified particle that is compatible with the hydrophobic aqueous oxidizer solution-fuel mixture.
  • the aqueous oxidizer solution-fuel mixture to be foamed is hydrophilic
  • hydrophilic surface groups one skilled in the art can select from hydrophilic surface groups.
  • the particle can also include at least two different surface groups that combine to provide a particle having a solubility parameter that is similar to the solubility parameter of the aqueous oxidizer solution- fuel mixture.
  • the surface groups may be selected to provide a statistically averaged, randomly surface-modified particle.
  • the surface groups are present on the surface of the particle in an amount sufficient to provide surface-modified nanoparticles that are capable of being subsequently dispersed in the aqueous oxidizer solution-fuel mixture without aggregation.
  • the surface groups in some embodiments are present in an amount sufficient to form a monolayer, preferably a continuous monolayer, on the surface of the particle.
  • Surface modifying groups may be a reaction product of a surface modifying agent.
  • surface modifying agents can be represented by the formula A-B, where the A group is capable of attaching to the surface of the particle and the B group is a compatibilizing group that may be reactive or non-reactive with a component of the composition.
  • Compatibilizing groups can be selected to render the particle relatively more hydrophilic or hydrophobic.
  • Suitable classes of surface-modifying agents include silanes, organic acids, organic bases, and alcohols.
  • Particularly useful surface-modifying agents include silanes.
  • useful silanes include organosilanes including alkylchlorosilanes; alkoxysilanes (e.g., methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3 -mercaptopropyltrimethoxysilane, n-octyltriethoxysilane, phenyltriethoxysilane, polytriethoxysilane
  • polydialkylsiloxanes e.g., polydimethylsiloxane
  • arylsilanes e.g., substituted and unsubstituted arylsilanes
  • alkylsilanes e.g., substituted and unsubstituted alkyl silanes (e.g., methoxy and hydroxy substituted alkyl silanes)
  • silica nanoparticles include silica nanoparticles surface-modified with silane surface modifying agents (e.g., acryloyloxypropyl trimethoxysilane, 3 -methacryloyloxypropyltrimethoxy silane,
  • Silica nanoparticles can be treated with a number of surface modifying agents (e.g., alcohol, organosilane (e.g., alkyltrichlorosilanes, trialkoxyarylsilanes, trialkoxy(alkyl)silanes, and combinations thereof), organotitanates, and mixtures thereof).
  • surface modifying agents e.g., alcohol, organosilane (e.g., alkyltrichlorosilanes, trialkoxyarylsilanes, trialkoxy(alkyl)silanes, and combinations thereof), organotitanates, and mixtures thereof).
  • polar surface-modifying agents e.g., oxyacids of carbon (e.g., carboxylic acid), sulfur and phosphorus, and combinations thereof.
  • polar surface-modifying agents having carboxylic acid functionality include CH 3 O(CH 2 CH 2 O) 2 CH 2 COOH (hereafter MEEAA) and 2-(2- methoxyethoxy)acetic acid having the chemical structure CH 3 OCH 2 CH 2 OCH 2 COOH (hereafter MEAA) and mono(polyethylene glycol) succinate.
  • non-polar surface-modifying agents having carboxylic acid functionality include octanoic acid, dodecanoic acid, and oleic acid.
  • Suitable phosphorus containing acids include phosphonic acids (e.g., octylphosphonic acid, laurylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, and octadecylphosphonic acid).
  • phosphonic acids e.g., octylphosphonic acid, laurylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, and octadecylphosphonic acid.
  • Useful organic base surface-modifying agents include alkylamines (e.g., octylamine, decylamine, dodecylamine, and octadecylamine).
  • alkylamines e.g., octylamine, decylamine, dodecylamine, and octadecylamine.
  • Examples of other useful non-silane surface modifying agents include acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, mono-2-(methacryloyloxyethyl) succinate, and combinations thereof.
  • a useful surface modifying agent that imparts both polar character and reactivity to the nanoparticles is mono(methacryloyloxypolyethyleneglycol) succinate.
  • Suitable surface-modifying alcohols include aliphatic alcohols (e.g., octadecyl, dodecyl, lauryl and furfuryl alcohol), alicyclic alcohols (e.g., cyclohexanol), and aromatic alcohols (e.g., phenol and benzyl alcohol), and combinations thereof.
  • aliphatic alcohols e.g., octadecyl, dodecyl, lauryl and furfuryl alcohol
  • alicyclic alcohols e.g., cyclohexanol
  • aromatic alcohols e.g., phenol and benzyl alcohol
  • a variety of methods are available for modifying the surface of nanoparticles (e.g., adding a surface modifying agent to nanoparticles (e.g., in the form of a powder or a colloidal dispersion) and allowing the surface modifying agent to react with the nanoparticles).
  • a surface modifying agent e.g., in the form of a powder or a colloidal dispersion
  • Other useful surface modification processes are described in, for example, U.S. Pat. Nos. 2,801,185 (Her) and 4,522,958 (Das et al), the disclosures of which are incorporated herein by reference.
  • Useful surface-modified zirconia nanoparticles include a combination of oleic acid and acrylic acid adsorbed onto the surface of the particle.
  • the nanoparticles can also function as an emulsion stabilizer (i.e., no additional emulsifier is required).
  • explosive precursor compositions described herein comprise aqueous oxidizer solution, fuel, nanoparticles, and emulsifier.
  • Emulsifier is added to create an emulsion of a supersaturated aqueous solution of aqueous oxidizer solution salt(s) into the fuel phase.
  • Useful emulsif ⁇ ers include sorbitol esters, stearates, derivatives of polyisobutylene anhydrides, and combinations thereof.
  • Useful emulsif ⁇ ers are also described in U.S. Pat. No. 4,594,118 (Curtin et al.) (the disclosure of which is incorporated herein by reference) for the description of emulsifiers.
  • emulsifiers can be used in the explosive precursor compositions in an amount of from typically 0.5% - 2.5% by weight.
  • Various methods may be employed to combine the nanoparticles and the aqueous oxidizer solution-fuel mixture.
  • a colloidal dispersion of nanoparticles and fuel mixture are combined.
  • the nanoparticle-fuel mixture is blended with the aqueous oxidizer solution.
  • a cosolvent e.g., methoxy-2-propanol or N-methylpyrrolidone
  • the water and cosolvent are removed.
  • Another method for incorporating colloidal dispersions of nanoparticles into an aqueous oxidizer solution-fuel mixture includes drying the colloidal dispersion of nanoparticles to a powder, followed by addition of the aqueous oxidizer solution-fuel mixture or at least one component of the aqueous oxidizer solution- fuel mixture into which the nanoparticles are to be dispersed.
  • the drying step may be accomplished by conventional means such as oven drying or spray drying.
  • the surface-modified nanoparticles preferably have a sufficient amount of surface groups to prevent irreversible agglomeration or irreversible aggregation upon drying.
  • the drying time and the drying temperature is preferably minimized for nanoparticles having less than 100% surface coverage.
  • Colloidal dispersions of nanoparticles can be added to the aqueous oxidizer solution- fuel mixture in amounts sufficient to provide a composition capable of foaming, preferably in amounts sufficient to provide a composition capable of forming a persistent foam.
  • Nanoparticles may be present in the aqueous oxidizer solution- fuel mixture in varying amounts (e.g., from about 0.01% by dry weight to about 30% by dry weight, in some embodiments, from about 0.01% by dry weight to about 10% by dry weight, and from about 0.01% by dry weight to about 5% by dry weight based on the total weight of the composition). It is to be understood that the ranges of amounts of nanoparticles also include any whole or fractional amount between 0.01 and 30 dry weight percent.
  • the nanoparticles are dispersed throughout the aqueous oxidizer solution- fuel mixture (in some embodiments, dispersed homogeneously throughout the aqueous oxidizer solution-fuel mixture).
  • a cosolvent can be added to the composition to improve the compatibility (e.g., solubility or miscibility) of the surface modifying agent and the nanoparticles with the other components of the composition.
  • the composition is foamed after the nanoparticles have become dispersed throughout the aqueous oxidizer solution- fuel mixture (in some embodiments, after the nanoparticles are homogeneously dispersed throughout the aqueous oxidizer solution- fuel mixture).
  • the composition is foamed by forming gas voids in the composition using a variety of mechanisms (e.g., mechanical mechanisms, chemical mechanisms, and combinations thereof).
  • mechanisms e.g., mechanical mechanisms, chemical mechanisms, and combinations thereof.
  • Useful mechanical foaming mechanisms e.g., agitating (e.g., shaking, stirring, or whipping) the composition, injecting gas into the composition (e.g., inserting a nozzle beneath the surface of the composition and blowing gas into the composition), and combinations thereof).
  • Useful chemical foaming mechanisms e.g., producing gas in situ through a chemical reaction, decomposition of a component of the composition (e.g., a component that liberates gas upon thermal decomposition), evaporating a component of the composition (e.g., a liquid gas, volatilizing a gas in the composition by decreasing the pressure on the composition or heating the composition), and combinations thereof).
  • any foaming agent may be used to foam the composition (e.g., chemical foaming agents and physical foaming agents (e.g., inorganic and organic foaming agents).
  • Examples of chemical foaming agents include water and azo-, carbonate- and hydrazide-based molecules (e.g., 4,4'-oxybis (benzenesulfonyl)hydrazide, 4,4'-oxybenzenesulfonyl semicarbazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, azodiisobutyronitrile, benzenesulfonhydrazide, trihydrazinotriazine, metal salts of azodicarboxylic acids, oxalic acid hydrazide, hydrazocarboxylates, diphenyloxide-4,4'-disulphohydrazide, tetrazole compounds, sodium bicarbonate, ammonium bicarbonate, preparations of carbonate compounds and polycarbonic acids, mixtures of citric acid and sodium bicarbonate, N,N'-dimethyl
  • Suitable inorganic physical foaming agents include nitrogen, argon, oxygen, water, air, helium, sulfur hexafluoride, and combinations thereof. Additionally, inorganic chemical foaming agents such as sodium nitrite either alone or with promoters such as sodium thiocyanate, ethanolamine nitrate, acrylamide, and urea may be used.
  • Useful organic physical foaming agents include carbon dioxide, aliphatic hydrocarbons, aliphatic alcohols, aliphatic ethers, fully and partially halogenated aliphatic hydrocarbons, and combinations thereof.
  • suitable aliphatic hydrocarbon foaming agents include members of the alkane series of hydrocarbons (e.g., methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, and blends thereof).
  • Useful aliphatic alcohols e.g., methanol, ethanol, n-propanol, and isopropanol, and combinations thereof).
  • Useful aliphatic ethers include dimethylether.
  • Suitable fully and partially halogenated aliphatic hydrocarbons e.g., fluorocarbons, chlorocarbons, and chlorofluorocarbons, and combinations thereof).
  • fluorocarbon foaming agents include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC- 152a), fluoroethane (HFC- 161), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafiuoroethane (HFC-134a), 1,1,2,2 tetrafluoroethane (HFC-134), 1,1,1,3,3-pentafluoropropane, pentafluoroethane
  • HFC- 125 difluoromethane (HFC-32), perfluoroethane, 2,2-difluoropropane, 1,1,1- trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane, and combinations thereof.
  • the foaming agents may be used as single components, in mixtures and in combinations thereof.
  • the foaming agent is added to the composition in an amount sufficient to achieve a desired foam density.
  • the aqueous oxidizer solution- fuel mixture may also include a nucleating agent.
  • a nucleating agent can be any conventional nucleating agent. The amount of nucleating agent to be added depends upon the desired cell size, the selected foaming agent, and the density of the aqueous oxidizer solution-fuel mixture. Examples of inorganic nucleating agents in small particulate form include clay, talc, fumed silica, precipitated silica, and diatomaceous earth. Organic nucleating agents can decompose or react at a given temperature.
  • an organic nucleating agent is a combination of an alkali metal salt of a polycarboxylic acid with a carbonate or bicarbonate.
  • alkali metal salts of a polycarboxylic acid include the monosodium salt of 2,3-dihydroxy-butanedioic acid (i.e., sodium hydrogen tartrate), the monopotassium salt of butanedioic acid (i.e., potassium hydrogen succinate), the trisodium and tripotassium salts of 2-hydroxy- 1,2, 3- propanetricarboxylic acid (i.e., sodium and potassium citrate, respectively), and the disodium salt of ethanedioic acid (i.e., sodium oxalate), and polycarboxylic acid such as 2-hydroxy- 1,2,3-propanetricarboxylic acid, and combinations thereof.
  • carbonate and bicarbonate examples include sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and calcium carbonate, and combinations thereof.
  • One contemplated combination is a monoalkali metal salt of a polycarboxylic acid, such as monosodium citrate or monosodium tartrate, with a carbonate or bicarbonate.
  • a monoalkali metal salt of a polycarboxylic acid such as monosodium citrate or monosodium tartrate
  • mixtures of different nucleating agents may be added to the aqueous oxidizer solution-fuel mixture.
  • Other useful nucleating agents include a stoichiometric mixture of citric acid and sodium bicarbonate.
  • Silane Coupling Agent A was prepared by combining 25.20 grams of tris(2- methoxyethoxy)vinylsilane (obtained from Sigma- Aldrich, Milwaukee, WI) and 20.00 grams of heptamethyldisiloxane (obtained from Gelest, Inc., Tullytown, PA) with mixing in heptane (30 grams).
  • a platinum(O) divinyltetramethyldisiloxane catalyst prepared as described in Example 1 of U.S. Pat. No.
  • colloidal silica (15% by weight solids ammonia stabilized colloidal silica having an average particle size of 5 nm and a surface area of about 600 m ⁇ /g, obtained from Nalco Chemical Co., Naperville, IL under the trade designation "NALCO 2326")
  • Silane Coupling Agent A 37.38 grams
  • Silane Coupling Agent A 388 grams
  • l-methoxy-2- propanol obtained from Sigma- Aldrich
  • the beaker was rinsed with an additional amount of methoxypropanol (52.5 grams), which was subsequently added to the stirred mixture. After complete addition, the open port in the flask was stoppered and the flask placed in an oil bath. The oil bath was then heated to 8O 0 C and the reaction allowed to proceed for 16.5 hours. The solvents were removed in a flow through oven at 9O 0 C. A viscous yellow liquid was recovered ("Material II").
  • a surface-modified nanoparticle dispersion (5 nm size, isooctyl/methyl surface modified) was prepared using the method described in U.S. Pat. No. 6,586,483 (KoIb et al.), under the heading "Preparation of isooctyl Surface Modified Silica Nanoparticles"
  • VASSA LP90 biodegradable hydrogenated oil
  • VASSA LP90 biodegradable hydrogenated oil
  • An aqueous solution of ammonium nitrate can be prepared by charging a stainless steel beaker with ammonium nitrate (7550 parts by weight)(available from Sigma-
  • Material III can be can be added with stirring, into #2 fuel oil (380 parts by weight; available from Exxon Mobil Corp, Fairfax, VA) and sorbitan mono-oleate (100 parts by weight; available from BASF, mount Olive, NJ). The mixture can be stirred until the nanoparticles are uniformly dispersed and the #2 fuel oil is clear to provide an Oil Phase.
  • #2 fuel oil 380 parts by weight; available from Exxon Mobil Corp, Fairfax, VA
  • sorbitan mono-oleate 100 parts by weight; available from BASF, mount Olive, NJ.
  • the Water Phase (at 7O 0 C) can be slowly added to a rapidly stirred blend of the Oil Phase (at 2O 0 C) and further stirred for 1 minute.
  • sodium nitrite (20 parts by weight of a 1 :2 sodium nitrite to water solution) can be added, and with stirring continuing for 10 seconds.
  • the density of the final emulsion can be in the range from 1.05 to 1.25 g/ml.
  • the fuel to oxidizer weight ratio of the emulsion would be 96.2 to 4.8, although a more typical desired ratio would be 94.5 to 5.5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur des explosifs contenant une solution aqueuse d'oxydant, un combustible et un sensibilisateur de mousse stabilisée par des nanoparticules. Les explosifs peuvent également contenir un émulsifiant.
EP08836328A 2007-10-01 2008-09-17 Utilisation de nanoparticules dans des explosifs Withdrawn EP2215034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97665407P 2007-10-01 2007-10-01
PCT/US2008/076645 WO2009045723A1 (fr) 2007-10-01 2008-09-17 Utilisation de nanoparticules dans des explosifs

Publications (1)

Publication Number Publication Date
EP2215034A1 true EP2215034A1 (fr) 2010-08-11

Family

ID=40526610

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08836328A Withdrawn EP2215034A1 (fr) 2007-10-01 2008-09-17 Utilisation de nanoparticules dans des explosifs

Country Status (7)

Country Link
US (1) US20100206441A1 (fr)
EP (1) EP2215034A1 (fr)
CN (1) CN101808959A (fr)
AU (1) AU2008307285B2 (fr)
BR (1) BRPI0817190A2 (fr)
CA (1) CA2700384A1 (fr)
WO (1) WO2009045723A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2927291B1 (fr) * 2008-02-07 2016-03-04 Livbag Generateur de gaz pour un dispositif de securite, dont la charge est initiee par un moyen generateur de chaleur.
US9970740B2 (en) * 2011-03-14 2018-05-15 Rocket Lab Usa, Inc. Viscous liquid monopropellant
FR2987279A1 (fr) * 2012-02-29 2013-08-30 Saint Louis Inst Procede d'elaboration de nanoparticules de tailles ultimes par detonation de charges explosives nano-et/ou submicrostructurees
CN104788269B (zh) * 2014-01-21 2018-05-08 比亚迪股份有限公司 一种气体发生剂组合物及其制备方法、安全气囊
AU2015290110B2 (en) * 2014-07-18 2019-09-12 Jeffrey S. Senules Noble gas infused emulsion explosive
EP3894376A4 (fr) 2018-12-11 2022-09-07 Stt-Surfex Technology & trading Pty Ltd Explosif à base d'eau
US11851382B1 (en) * 2019-08-29 2023-12-26 The United States Of America As Represented By The Secretary Of The Navy Flexible halocarbon pyrolant
CN112409112B (zh) * 2020-11-12 2021-10-01 西安近代化学研究所 一种催化型高热值粘结剂、制备方法及相关炸药
EP4119525A1 (fr) * 2021-07-12 2023-01-18 Sika Technology AG Mousse liquide ayant des pores de gaz

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2801185A (en) * 1952-05-16 1957-07-30 Du Pont Silica hydrosol powder
US3814730A (en) * 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US4478876A (en) * 1980-12-18 1984-10-23 General Electric Company Process of coating a substrate with an abrasion resistant ultraviolet curable composition
US4491508A (en) * 1981-06-01 1985-01-01 General Electric Company Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer
US4455205A (en) * 1981-06-01 1984-06-19 General Electric Company UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator
US4486504A (en) * 1982-03-19 1984-12-04 General Electric Company Solventless, ultraviolet radiation-curable silicone coating compositions
US4522958A (en) * 1983-09-06 1985-06-11 Ppg Industries, Inc. High-solids coating composition for improved rheology control containing chemically modified inorganic microparticles
AU578460B2 (en) * 1984-04-19 1988-10-27 Ici Australia Limited Water in oil emulsion explosives and stabilizers therefor
US5037579A (en) * 1990-02-12 1991-08-06 Nalco Chemical Company Hydrothermal process for producing zirconia sol
US5258225A (en) * 1990-02-16 1993-11-02 General Electric Company Acrylic coated thermoplastic substrate
US6586483B2 (en) * 2001-01-08 2003-07-01 3M Innovative Properties Company Foam including surface-modified nanoparticles
WO2004026783A1 (fr) * 2002-09-17 2004-04-01 3M Innovative Properties Company Films d'oxyde métallique poreux médiés par tensioactif
US7129277B2 (en) * 2002-12-31 2006-10-31 3M Innovative Properties Company Emulsions including surface-modified inorganic nanoparticles
US20040242729A1 (en) * 2003-05-30 2004-12-02 3M Innovative Properties Company Stabilized particle dispersions containing surface-modified inorganic nanoparticles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009045723A1 *

Also Published As

Publication number Publication date
AU2008307285A1 (en) 2009-04-09
BRPI0817190A2 (pt) 2015-03-17
CA2700384A1 (fr) 2009-04-09
CN101808959A (zh) 2010-08-18
US20100206441A1 (en) 2010-08-19
AU2008307285B2 (en) 2011-10-27
WO2009045723A1 (fr) 2009-04-09

Similar Documents

Publication Publication Date Title
AU2008307285B2 (en) Use of nanoparticles in explosives
EP1509676B1 (fr) Utilisation de nanoparticules a surface modifiee pour la recuperation du petrole
US7129277B2 (en) Emulsions including surface-modified inorganic nanoparticles
JP2528101B2 (ja) 爆発組成物
JPS5938182B2 (ja) 乳化爆発組成物
BR112019011806A2 (pt) composição de explosivo, método para preparar uma composição de explosivo, e, uso de uma composição de explosivo.
JPS5992991A (ja) 乳濁爆発性組成物及びその製造方法
US5076867A (en) Stabilized emulsion explosive and method
US5500062A (en) Emulsion explosive
AU2010241443B2 (en) Low Density Explosive Emulsion
JPS5997589A (ja) 乳濁爆発性組成物及びその製造方法
ZA200608317B (en) Ammonium nitrate crystals, ammonium nitrate blasting agent and method of production
JPS62162685A (ja) 油中水滴型エマルジヨン爆薬
US4115165A (en) Hydrophobic aluminum sensitizing agents for explosives
CA2040346C (fr) Explosif utilisant un sensibilisant en mousse
JP3649868B2 (ja) バルク装填用油中水型エマルション爆薬組成物
JPS60161386A (ja) 界面活性剤組合せ組成物を使用する乳化速度の増強
US20020124917A1 (en) Preparation of emulsions by pH adjustments
EP4334269A1 (fr) Composition de formation d'un explosif à émulsion à base de peroxyde d'hydrogène
AU2022269827A1 (en) Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
JPS58120589A (ja) 油中水型エマルシヨン爆薬組成物
JP2004161524A (ja) 油中水滴型エマルション爆薬組成物
JP2000119087A (ja) バルク装填用油中水型エマルション爆薬組成物
KR20030085479A (ko) 주조 입자를 포함하는 고 에너지 폭발물
JP2004051448A (ja) 油中水滴型エマルション爆薬

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100429

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20111012