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WO2007067288A2 - Method of and system for inline formation, surface treatment and direct dispersion of nanomaterial into a collection media - Google Patents

Method of and system for inline formation, surface treatment and direct dispersion of nanomaterial into a collection media Download PDF

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Publication number
WO2007067288A2
WO2007067288A2 PCT/US2006/043253 US2006043253W WO2007067288A2 WO 2007067288 A2 WO2007067288 A2 WO 2007067288A2 US 2006043253 W US2006043253 W US 2006043253W WO 2007067288 A2 WO2007067288 A2 WO 2007067288A2
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Prior art keywords
metals
nanomaterials
ceramics
combinations
group
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PCT/US2006/043253
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French (fr)
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WO2007067288A3 (en
Inventor
Gregory T. Schueneman
Karen R. Brantl
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Henkel Corporation
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Publication of WO2007067288A2 publication Critical patent/WO2007067288A2/en
Publication of WO2007067288A3 publication Critical patent/WO2007067288A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0879—Solid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0886—Gas-solid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

Definitions

  • the present invention relates a method for forming and surface treating of nanosized materials and for incorporating the nanosized materials into a collection media, and a system for the same.
  • Nanosized materials which may also be referred to as nanomaterials, may be made from gas phase processes, such as flame pyrolysis, plasma synthesis, high temperature evaporation and the like, or from liquid or colloidal phase methods in which chemical reactions in solvents lead to the formation of
  • Nanosized particles are commercially available in powdered form or in a dispersed form, such as a colloidal solution.
  • Nanomaterials may be dispersed within a media such that individual nanomaterials exist to achieve maximum benefits.
  • Dispersed nanomaterials have a high surface area and are thermodynamically driven to reagglomerate in an effort to minimize surface area, i.e., a lower energy state for the system.
  • One method to provide for a stable dispersion is to coat nanomaterials such that their surfaces are hidden from each other by an outer shell of dissimilar material.
  • Current state-of-the-art processes to achieve well-dispersed nanomaterials that do not agglomerate are multi-step processes involving separate steps for nanomaterial production, surface treating and dispersion.
  • the dispersion step usually requires high-energy mixing processes, such as intense ultrasonication and ball milling. Such mixing
  • nanosized particles tend to agglomerate to form larger particles, often micron-sized or larger.
  • Incorporating nano-sized particles into a resin while maintaining the nanosize often involves complex
  • U.S. Patent Application Publication No. 2005/0084607 Al to Wang describes the use of ultrasonic irradiation and mechanical agitation to process nanosized aluminum oxide powder for inclusion in a resin.
  • Aluminum oxide powder having a particle size of 13 nanometers (“nm") is described as being mechanically dispersed into methanol.
  • the dispersed aluminum particles are described as reagglomerating to a particle size of 15-20 microns.
  • Ultrasonic irradiation and mechanical agitation were described as being applied to break the agglomerated particles to an average particle size of 121 run.
  • Neopentyl (diallyl) oxytriacryl zirconate was dissolved into methanol and was added to aluminum oxide dispersion to surface treat the aluminum oxide particles.
  • the nanosized particles may reagglomerate over time.
  • the reagglomerated particles usually require redispersion, such as grinding or mechanical agitation / prior to incorporation into a second material. Even if the nanosized particles are not reagglomerated, there may be
  • colloidal nanosized particles may be prohibitive or problematic as the colloidal solution may not be compatible with a particular desired surface treatment .
  • U.S. Patent Nos. 6,688,494 to Pozarnsky et al. and 6,689,190 to Pozarnsky describe a process where metal vapors are solidified in an inert gaseous stream and pumped by a dry mechanical or vacuum pump to a collection area where the resultant nanopowders are captured by electrostatic surface collectors, porous surfaces, wet scrubbers, electrostatic filter collectors or collection liquids.
  • the collection liquid is described as possibly being a solvent, a prepolymer or a
  • Liquid capturing is described as allowing post
  • the present invention is directed to a system for forming, surface treating and dispersing
  • the system includes a nanomaterial generator operable at or near ambient pressure for generating sintered or reacted nanomaterials freely falling through a gaseous environment; a surface treatment vessel for modifying surfaces of the freely falling nanomaterials to form freely falling surface-treated nanomaterials; and a vessel containing a media into which the surface-treated nanomaterials are deposited and dispersed.
  • nanomaterial forms include particles, platelets, tubes, films, laminates, spheres, cones, oval-shaped solids, cylinders, cubes, whiskers, monoclinic-shaped solids, parallelepipeds,
  • dumbbell-shaped solids hexagonal-shaped solids, truncated dodecahedron-shaped solids, irregular shapes, fibers and
  • the nanomaterials may include materials selected from inorganics, metals, organics compounds and mixtures or
  • Nonlimiting examples of inorganics may include elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics,
  • non-stoichiometric ceramics semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates, sulfides, natural or man made minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and the like.
  • Nonlimiting examples of metals may include alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and the like.
  • Nonlimiting examples of organics may include monomers, polymers, oligomers, and polymer segments, multi-functional monomers, oligomers, polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic compounds, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, mixtures or combinations thereof and the like.
  • the nanomaterial generator includes an ultrasonic spray nozzle for forming nanosized droplets and a sintering reactor for sintering or reacting the nanosized droplets into the nanomaterials .
  • the sintering reactor may be a microwave reactor.
  • the surface treatment vessel may include a microwave oven or a plasma chamber for depositing a coating of a material onto the surfaces of the nanomaterials.
  • the materials for the surface treatment of the nanomaterials may be selected from organic compounds, inorganic compounds, metallic compounds and mixtures or combinations thereof.
  • the materials for surface treatment may take the form of liquids, solids, powders, slurries, gases, vapors, droplets, mixtures or combinations thereof.
  • Illustrative examples of useful surface-treating materials include, but are not limited to, water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds, polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers or polymers, plastics, crystalline organics,
  • initiators catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
  • semiconductors quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
  • multi-metals elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate,
  • a method for forming, surface treating and dispersing nanomaterials into a collection media composition may include the steps of sintering or reacting materials at or near ambient pressure to reduce the size of the materials to
  • nanomaterial scale to form nanomaterials; allowing the sintered or reacted nanomaterials to freely fall through a gaseous environment or be pushed by input gases or gases produced by formation of the nanomaterials; modifying surfaces of the freely falling sintered or reacted nanomaterials by depositing a surface-treating material to form freely falling surface-treated nanomaterials; and depositing and dispersing the surface-treated nanomaterials into a vessel containing a collection media.
  • the step of sintering or reacting includes providing micro-wave energy to sinter or react the nanodroplets .
  • the collection media composition includes sintered or reacted, and functionalized nanomaterials which have not been previously agglomerated.
  • the materials for the collection media may be selected from a group consisting of organic, inorganic, metallic compounds, and mixtures or combinations thereof. Collection media may also take the form of liquids, solids, powders, slurries, filters, wet scrubbers, flat or three dimensional surfaces and mixture or combinations thereof. Illustrative examples of useful
  • compositions include, but are not limited to, adhesive, sealant, anti-corrosive, or coating formulations, coating formulation products, coating formulation constituents, phenolic resins, vinyl resins, silicone resins, acrylic resins, epoxy resins, urethane resins, compositions of
  • cyanoacrylates resins or monomers curable by radiation, heat, moisture, anaerobic conditions, or contact with reactive species, diluents, plasticizers, initiators, catalysts,
  • solvents rubbers, water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones,
  • urethanes acrylics, resins, aliphatics, aror ⁇ atics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds, polymers, monomers, oligomers,
  • dendrimers plastics, crystalline organics, multi-component formulations, dispersants, peroxides, monomers, multi-functional monomers, polymers, or resins, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics, semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
  • multi-metals elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, graphite, carbon black, pigments, carbon nanotubes, fullerenes, methyl methacrylate, polyethylcyanoacrylate, polymethylcyanoacrylate, cyclic
  • FIG. 1 is a schematic of the system of the present invention for forming, surface treating, and dispersing
  • nanomaterials into a collection media composition are nanomaterials into a collection media composition.
  • FIG. 2 is a schematic of the method of the present invention for forming, surface treating and dispersing
  • the present invention is directed to a method for inline or series sintering or reacting of precursors into nanomaterials, followed by surface treatment of the
  • nanomaterials for compatibility, function, and dispersion, and subsequent direct dispersion of the treated nanomaterials into a collection media for example a composition such as a resin, an adhesive or a sealant composition.
  • the system 10 of the present invention advantageously allows for the rapid formation of nanomaterials in a single step with equipment not previously harnessed to operate in concert.
  • the system 10 of the present invention includes the combination of a nanomaterial generator 12, a surface treatment vessel 16 and a vessel 18 containing a collection media 38 for direct dispersion of surface treated nanomaterials 34 into the collection media 38, interrelated as shown.
  • the nanomaterial generator 12 may include a material mixer/injector 22, an ultrasonic spray nozzle 20, and a
  • the nanomaterial generator 12 mixes reactants, converts them into nanodroplets 26, and then quickly sinters or reacts the nanodroplets 26 into nanosized materials 28 all at or near atmospheric pressure. During sintering, the sizes of the particles and/or droplets are reduced to nanoparticle scale. Desirably, the system 10 may also operate with ambient air, i.e., without the need or
  • Gases may be introduced or produced in the nanomaterial generator 12 such that the nanomaterials are pushed into subsequent portions of the system. Gases may be produced in the nanomaterial generator 12 upon valorization of added materials.
  • ⁇ nanoparticle As used herein, the term ⁇ nanoparticle, ⁇ nanofiller", or nanomaterial refers to a nanosized solid particulate or matrix.
  • nanosized refers to substances having an average dimension of less than about 500 nanometers (nm) .
  • the nanomaterials of the present invention have a size from about 0.01 nm to about 500 nm. More desirably, the nanomaterials of the present invention have an average dimension from about 1 m to about 200 nm, for example from about 1 nm to about 100 nm. Nanosized materials having a dimensional range from about 1 nm to about 50 nm, including from about 1 nm to about 20 nm, are also useful with the present invention.
  • the nanomaterial generator 12 is not limited to a single material injector/mixer 22, and multiple material injectors/mixers, for example material injector/mixer 24, may suitably be used.
  • the use of multiple injectors/mixers 22, 24 allows for the introduction of different precursors from which the nanomaterials 28 may be formed.
  • the precursor or precursors are mixed and dispersed through a spray nozzle 20.
  • spray nozzle 20 is an ultrasonic spray nozzle which generates nanosized droplets 26.
  • the nanosized droplets 26 are sintered or reacted by a sintering reactor 14.
  • the sintering reactor 14 is a tubular microwave reactor. The tubular
  • microwave reactor 14 quickly sinters or reacts the nanodroplets 26 to form the nanomaterials 28.
  • the nanomaterials 28 exit the nanomaterial generator 12 and enter into the surface treatment vessel 16.
  • a material which typically may be a gas, liquid, vapor, slurry, dust or other form, is injected through the injection port 30.
  • the injected material deposits onto the nanomaterials 28 as they 28 are falling from the nanomaterial generator 12 to form the surface treated
  • the untreated nanomaterials 28 generally have a high surface area and a highly reactive surface.
  • deposited material may chemically react with the reactive surface to form surface-treated nanomaterials 32.
  • the surface treated nanomaterials 28 exit from the surface treatment vessel 16 and enter directly into the
  • the vessel 18 may be a continuously operable reactor or vessel with an inlet port 40 for the ingress of a media and an outlet port 42 for the egress of the media 38 having a dispersion of surface treated nanomaterials 36.
  • the vessel 18 may be a continuously stirred vessel or reactor with stirring, which is depicted by the vectors 44.
  • Stirring may be accomplished through mechanical or fluid dynamic means.
  • the vessel 18 need not be operated as a continuous vessel or reactor and may be operated in a batchwise manner.
  • the ports 40 and 42 act to allow input of uncoated solid materials or objects and output of coated solid materials or objects.
  • the present invention is not limited to a system 10 having a separate surface treatment vessel 16.
  • the treatment of the nanomaterials 28 may be accomplished within the nanomaterial generator 12.
  • the material injection port 30 may enter directly into a portion, such as a terminal portion, of the nanomaterial generator 12.
  • the system of the present invention 10 is not necessarily limited to the use of a material or materials capable of forming nanomaterials, as described above.
  • nanomaterials may be mechanically dispersed in a solvent, for example a low viscosity solvent.
  • the nanomaterials and the solvent may be forwarded to the nanomaterial generator 12, where the solvent is vaporized, leaving the nanomaterials receptive for surface treatment.
  • Some nonlimiting examples of the advantages and/or benefits of the present invention include the ability to operate at or about ambient pressure in an open system; the potential for high throughput operation; removal of the need to handle dry nanopowders; wide variety of nanomaterials are possible along with the ability for forming hybrid, uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, core-shell, and the like materials; the ability to deposit uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, core-shell and the like coatings on individual particles with tailored specificity; dispersion of nanofillers directly into a collection media such as liquids, solids, powders, slurries, filters, wet scrubbers, flat or three dimensional surfaces, mixtures or combinations thereof without having to apply high energy grinding or shearing methods;
  • Nonlimiting examples of surface treatments of the present invention include surface treatment of nanomaterials with materials selected from a group consisting of organic, inorganic, metallic compounds, and mixtures or combinations thereof.
  • the materials for surface treatment may take the form of liquids, solids, powders, slurries, gases, vapors, droplets, mixtures or combinations thereof.
  • Illustrative examples of these include and are not limited by water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds,
  • polymers monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers or polymers, plastics, crystalline organics, multi-component formulations, dispersants, primer, chain extender, adhesion promoter, chain transfer agent, initiators, catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics, semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates,
  • carbonates carbonates, sulfides, natural or man made minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate,
  • the surface treatment may be applied to the nanomaterials in a manner such that it is uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, mixtures or combinations thereof and the like
  • the nanomaterials of the present invention may include or be made of a variety of materials.
  • Nonlimiting examples of useful materials may be selected from groups that include ceramics, metals, organics, and mixtures or combinations
  • Nonlimiting examples of the useful nanomaterial forms include particles, platelets, tubes, films, laminates, spheres, cones, ovals, cylinders, cubes, whiskers, monoclinic,
  • Nonlimiting examples of inorganics include elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
  • semiconductors quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates, sulfides, natural or man made minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and the like.
  • metals of interest include alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals,
  • Non-stoichiometric metals precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and the like.
  • organics include monomers, polymers, oligomers, and polymer segments, multi-functional monomers, oligomers, or polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic compounds, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, mixtures or combinations thereof and the like.
  • Curable collection media compositions useful with the present invention include any suitable coating, sealant or adhesive constituent, formulation or product such as, but not limited to, phenolic resins, vinyl resins, silicone resins, acrylic resins, epoxy resins, urethane resins, compositions of olefinically-functionalized compounds, olefin resins, cyanoacrylates, materials curable by radiation, heat, moisture, anaerobic conditions, or contact with reactive species, rubbers and mixtures or combinations thereof.
  • suitable coating, sealant or adhesive constituent, formulation or product such as, but not limited to, phenolic resins, vinyl resins, silicone resins, acrylic resins, epoxy resins, urethane resins, compositions of olefinically-functionalized compounds, olefin resins, cyanoacrylates, materials curable by radiation, heat, moisture, anaerobic conditions, or contact with reactive species, rubbers and mixtures or combinations thereof.
  • nanomaterials of the present invention may be used for composite applications where there is an interest in
  • nanomaterials that have tailored structure and chemical specificity such that they act in a targeted manner to initiate reactions under a given signal or condition, act to transform surfaces for example as primers for adhesion or cure, act as carriers of molecules and the like.
  • FIG. 2 is a schematic depiction of the process according to the present invention for forming and treating nanomaterials for direct dispersion into a collection media.
  • step 46 sintered or reacted nanomaterials are formed. During this step agglomeration of the nanomaterials is prevented.
  • step 48 the nanomaterials are surface treated. During this step, agglomeration of the treated nanomaterials is prevented.
  • step 50 the treated nanomaterials are directly dispersed into a collection media while preventing agglomeration of the treated nanomaterials.

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Abstract

A system for forming, surface treating and dispersing nanomaterials into a collection media includes a nanomaterial generator operable at or near ambient pressure for generating sintered or reacted nanomaterials freely falling through a gaseous environment; a surface treatment vessel for modifying surfaces of the freely falling nanomaterials to form freely falling surface-treated nanomaterials; and a vessel contaning a media into which the surface-treated nanomaterials are deposited and dispersed.

Description

METHOD OF AND SYSTEM FOR INLINE FORMATION, SURFACE TREATMENT AND DIRECT DISPERSION OF NANOMATERIAL INTO A
COLLECTION MEDIA
FIELD OF THE INVENTION:
[0001] The present invention relates a method for forming and surface treating of nanosized materials and for incorporating the nanosized materials into a collection media, and a system for the same.
BRIEF DESCRIPTION OF RELATED TECHNOLOGY:
[0002] Nanosized materials, which may also be referred to as nanomaterials, may be made from gas phase processes, such as flame pyrolysis, plasma synthesis, high temperature evaporation and the like, or from liquid or colloidal phase methods in which chemical reactions in solvents lead to the formation of
colloids. Nanosized particles are commercially available in powdered form or in a dispersed form, such as a colloidal solution.
[0003] Nanomaterials may be dispersed within a media such that individual nanomaterials exist to achieve maximum benefits.
Additionally, it is some times desirable that the surface of the nanomaterials be capable of bonding or strongly interacting with the collection media for optimum performance. Dispersed nanomaterials have a high surface area and are thermodynamically driven to reagglomerate in an effort to minimize surface area, i.e., a lower energy state for the system. One method to provide for a stable dispersion is to coat nanomaterials such that their surfaces are hidden from each other by an outer shell of dissimilar material. Current state-of-the-art processes to achieve well-dispersed nanomaterials that do not agglomerate are multi-step processes involving separate steps for nanomaterial production, surface treating and dispersion. The dispersion step usually requires high-energy mixing processes, such as intense ultrasonication and ball milling. Such mixing
processes, however, are not typically present in most
manufacturing sites where nanomaterials have not been
traditionally used.
[0004] For example, in the powder form, nanosized particles tend to agglomerate to form larger particles, often micron-sized or larger. Incorporating nano-sized particles into a resin while maintaining the nanosize often involves complex
operations. For example, U.S. Patent Application Publication No. 2005/0084607 Al to Wang describes the use of ultrasonic irradiation and mechanical agitation to process nanosized aluminum oxide powder for inclusion in a resin. Aluminum oxide powder having a particle size of 13 nanometers ("nm") is described as being mechanically dispersed into methanol. The dispersed aluminum particles are described as reagglomerating to a particle size of 15-20 microns. Ultrasonic irradiation and mechanical agitation were described as being applied to break the agglomerated particles to an average particle size of 121 run. Neopentyl (diallyl) oxytriacryl zirconate was dissolved into methanol and was added to aluminum oxide dispersion to surface treat the aluminum oxide particles. The methanol was then described as being evaporated under vacuum or reduced pressure conditions. The dried nanoparticles were described as being stable, i.e., no significant reagglomeration and were then added into a resin. [0005] In colloidal form, the nanosized particles may reagglomerate over time. The reagglomerated particles usually require redispersion, such as grinding or mechanical agitation/ prior to incorporation into a second material. Even if the nanosized particles are not reagglomerated, there may be
compatibility and/or dilution concerns with the liquid portion of the colloidal as it may be incorporated into a material.
Further, possible surface treatment of the colloidal nanosized particles may be prohibitive or problematic as the colloidal solution may not be compatible with a particular desired surface treatment .
[0006] Additionally, U.S. Patent Nos. 6,688,494 to Pozarnsky et al. and 6,689,190 to Pozarnsky describe a process where metal vapors are solidified in an inert gaseous stream and pumped by a dry mechanical or vacuum pump to a collection area where the resultant nanopowders are captured by electrostatic surface collectors, porous surfaces, wet scrubbers, electrostatic filter collectors or collection liquids. The collection liquid is described as possibly being a solvent, a prepolymer or a
monomer. Liquid capturing is described as allowing post
treatment and polymer coating via in situ polymerization. A similar method is also described in U.S. Patent No. 5,030,669 to Hendrickson et al . where vaporized pigments are described as being pumped directly into a medium. The disadvantage of such methods is that the nanomaterials must be carried by a gas and pumped under pressure into a collection media. Additionally, there is no provision in this techniques that allows for surface treatment of the nanomaterials in the gas state where .
agglomeration or reagglomeration is less likely. [0007] Despite the state of the art, there remains a need for a method that allows in-line forming, surface treating and incorporating nanosized materials into a media without the concerns of reagglomeration or handling of the nanopowders.
Further, there is a need in the art to provide different surface treatment coatings on the nanosized materials to alleviate concerns of reagglomeration and compatibility, and to provide for bonding with a media.
SUMMARY OF THE INVENTION:
[0008] In one aspect, the present invention is directed to a system for forming, surface treating and dispersing
nanomaterials into a media. The system includes a nanomaterial generator operable at or near ambient pressure for generating sintered or reacted nanomaterials freely falling through a gaseous environment; a surface treatment vessel for modifying surfaces of the freely falling nanomaterials to form freely falling surface-treated nanomaterials; and a vessel containing a media into which the surface-treated nanomaterials are deposited and dispersed.
[0009] Illustrative and nonlimiting examples of suitable nanomaterial forms include particles, platelets, tubes, films, laminates, spheres, cones, oval-shaped solids, cylinders, cubes, whiskers, monoclinic-shaped solids, parallelepipeds,
dumbbell-shaped solids, hexagonal-shaped solids, truncated dodecahedron-shaped solids, irregular shapes, fibers and
mixtures or combinations thereof.
[0010] The nanomaterials may include materials selected from inorganics, metals, organics compounds and mixtures or
combinations of these. Nonlimiting examples of inorganics may include elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics,
non-stoichiometric ceramics, semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates, sulfides, natural or man made minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and the like. Nonlimiting examples of metals may include alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and the like. Nonlimiting examples of organics may include monomers, polymers, oligomers, and polymer segments, multi-functional monomers, oligomers, polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic compounds, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, mixtures or combinations thereof and the like.
[0011] Desirably, the nanomaterial generator includes an ultrasonic spray nozzle for forming nanosized droplets and a sintering reactor for sintering or reacting the nanosized droplets into the nanomaterials . The sintering reactor may be a microwave reactor. The surface treatment vessel may include a microwave oven or a plasma chamber for depositing a coating of a material onto the surfaces of the nanomaterials.
[0012] The materials for the surface treatment of the nanomaterials may be selected from organic compounds, inorganic compounds, metallic compounds and mixtures or combinations thereof. The materials for surface treatment may take the form of liquids, solids, powders, slurries, gases, vapors, droplets, mixtures or combinations thereof. Illustrative examples of useful surface-treating materials include, but are not limited to, water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds, polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers or polymers, plastics, crystalline organics,
multi-component formulations, dispersants, primers, chain extenders, adhesion promoters, chain transfer agents,
initiators, catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural or man-made minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals,
multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate,
polymethylcyanoacrylate, cyclic azasilanes, nanomaterials, mixtures or combinations of these and the like. The surface treatment may be applied to the nanomaterials in a manner such that it is uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, mixtures or combinations thereof and the like [0013] In another aspect of the present invention, a method for forming, surface treating and dispersing nanomaterials into a collection media composition is provided. The method may include the steps of sintering or reacting materials at or near ambient pressure to reduce the size of the materials to
nanomaterial scale to form nanomaterials; allowing the sintered or reacted nanomaterials to freely fall through a gaseous environment or be pushed by input gases or gases produced by formation of the nanomaterials; modifying surfaces of the freely falling sintered or reacted nanomaterials by depositing a surface-treating material to form freely falling surface-treated nanomaterials; and depositing and dispersing the surface-treated nanomaterials into a vessel containing a collection media.
Desirably, the step of sintering or reacting includes providing micro-wave energy to sinter or react the nanodroplets .
[0014] In another aspect of the present invention a
collection media composition is provided. The collection media composition includes sintered or reacted, and functionalized nanomaterials which have not been previously agglomerated. The materials for the collection media may be selected from a group consisting of organic, inorganic, metallic compounds, and mixtures or combinations thereof. Collection media may also take the form of liquids, solids, powders, slurries, filters, wet scrubbers, flat or three dimensional surfaces and mixture or combinations thereof. Illustrative examples of useful
collection media compositions include, but are not limited to, adhesive, sealant, anti-corrosive, or coating formulations, coating formulation products, coating formulation constituents, phenolic resins, vinyl resins, silicone resins, acrylic resins, epoxy resins, urethane resins, compositions of
olefinically-functionalized compounds, olefin resins,
cyanoacrylates, resins or monomers curable by radiation, heat, moisture, anaerobic conditions, or contact with reactive species, diluents, plasticizers, initiators, catalysts,
solvents, rubbers, water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones,
urethanes, acrylics, resins, aliphatics, arorαatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds, polymers, monomers, oligomers,
dendrimers, plastics, crystalline organics, multi-component formulations, dispersants, peroxides, monomers, multi-functional monomers, polymers, or resins, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics, semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural minerals, manmade minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals,
multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, graphite, carbon black, pigments, carbon nanotubes, fullerenes, methyl methacrylate, polyethylcyanoacrylate, polymethylcyanoacrylate, cyclic
azasilanes, mixtures or combinations of these and the like.
BRIEF DESCRIPTION OF THE DRAWINGS:
[0015] FIG. 1 is a schematic of the system of the present invention for forming, surface treating, and dispersing
nanomaterials into a collection media composition.
[0016] FIG. 2 is a schematic of the method of the present invention for forming, surface treating and dispersing
nanomaterials into a collection media composition. DETAILED DESCRIPTION OF THE INVENTION:
[0017] The present invention is directed to a method for inline or series sintering or reacting of precursors into nanomaterials, followed by surface treatment of the
nanomaterials for compatibility, function, and dispersion, and subsequent direct dispersion of the treated nanomaterials into a collection media, for example a composition such as a resin, an adhesive or a sealant composition.
[0018] The system for the present invention advantageously allows for the rapid formation of nanomaterials in a single step with equipment not previously harnessed to operate in concert. As depicted in FIG. 1, the system 10 of the present invention includes the combination of a nanomaterial generator 12, a surface treatment vessel 16 and a vessel 18 containing a collection media 38 for direct dispersion of surface treated nanomaterials 34 into the collection media 38, interrelated as shown. The nanomaterial generator 12 may include a material mixer/injector 22, an ultrasonic spray nozzle 20, and a
sintering/reacting reactor 14. The nanomaterial generator 12 mixes reactants, converts them into nanodroplets 26, and then quickly sinters or reacts the nanodroplets 26 into nanosized materials 28 all at or near atmospheric pressure. During sintering, the sizes of the particles and/or droplets are reduced to nanoparticle scale. Desirably, the system 10 may also operate with ambient air, i.e., without the need or
substantial need for reducing or inerting gases. Gases may be introduced or produced in the nanomaterial generator 12 such that the nanomaterials are pushed into subsequent portions of the system. Gases may be produced in the nanomaterial generator 12 upon valorization of added materials. [Oθi9] As used herein, the term ΛΛnanoparticle", ΛΛnanofiller", or nanomaterial refers to a nanosized solid particulate or matrix. The term "nanosized" refers to substances having an average dimension of less than about 500 nanometers (nm) .
Desirably, the nanomaterials of the present invention have a size from about 0.01 nm to about 500 nm. More desirably, the nanomaterials of the present invention have an average dimension from about 1 m to about 200 nm, for example from about 1 nm to about 100 nm. Nanosized materials having a dimensional range from about 1 nm to about 50 nm, including from about 1 nm to about 20 nm, are also useful with the present invention.
[0020] The nanomaterial generator 12, however, is not limited to a single material injector/mixer 22, and multiple material injectors/mixers, for example material injector/mixer 24, may suitably be used. The use of multiple injectors/mixers 22, 24 allows for the introduction of different precursors from which the nanomaterials 28 may be formed. The precursor or precursors are mixed and dispersed through a spray nozzle 20. Desirably, spray nozzle 20 is an ultrasonic spray nozzle which generates nanosized droplets 26. The nanosized droplets 26 are sintered or reacted by a sintering reactor 14. Desirably, the sintering reactor 14 is a tubular microwave reactor. The tubular
microwave reactor 14 quickly sinters or reacts the nanodroplets 26 to form the nanomaterials 28.
[0021] The nanomaterials 28 exit the nanomaterial generator 12 and enter into the surface treatment vessel 16. In the surface treatment vessel 16, a material, which typically may be a gas, liquid, vapor, slurry, dust or other form, is injected through the injection port 30. The injected material deposits onto the nanomaterials 28 as they 28 are falling from the nanomaterial generator 12 to form the surface treated
nanomaterials 32. The untreated nanomaterials 28 generally have a high surface area and a highly reactive surface. The
deposited material may chemically react with the reactive surface to form surface-treated nanomaterials 32.
[0022] The surface treated nanomaterials 28 exit from the surface treatment vessel 16 and enter directly into the
collection media vessel 18. The vessel 18 may be a continuously operable reactor or vessel with an inlet port 40 for the ingress of a media and an outlet port 42 for the egress of the media 38 having a dispersion of surface treated nanomaterials 36.
Further, the vessel 18 may be a continuously stirred vessel or reactor with stirring, which is depicted by the vectors 44.
Stirring may be accomplished through mechanical or fluid dynamic means. The vessel 18 need not be operated as a continuous vessel or reactor and may be operated in a batchwise manner. In the case of the collection media being a solid surface that is either flat or three dimensional, the ports 40 and 42 act to allow input of uncoated solid materials or objects and output of coated solid materials or objects.
[0023] The present invention is not limited to a system 10 having a separate surface treatment vessel 16. Surface
treatment of the nanomaterials 28 may be accomplished within the nanomaterial generator 12. For example, the material injection port 30 may enter directly into a portion, such as a terminal portion, of the nanomaterial generator 12.
[0024] Further, the system of the present invention 10 is not necessarily limited to the use of a material or materials capable of forming nanomaterials, as described above. In an alternate embodiment of the present invention, nanomaterials may be mechanically dispersed in a solvent, for example a low viscosity solvent. The nanomaterials and the solvent may be forwarded to the nanomaterial generator 12, where the solvent is vaporized, leaving the nanomaterials receptive for surface treatment.
[0025] Some nonlimiting examples of the advantages and/or benefits of the present invention include the ability to operate at or about ambient pressure in an open system; the potential for high throughput operation; removal of the need to handle dry nanopowders; wide variety of nanomaterials are possible along with the ability for forming hybrid, uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, core-shell, and the like materials; the ability to deposit uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, core-shell and the like coatings on individual particles with tailored specificity; dispersion of nanofillers directly into a collection media such as liquids, solids, powders, slurries, filters, wet scrubbers, flat or three dimensional surfaces, mixtures or combinations thereof without having to apply high energy grinding or shearing methods;
instant achievement of uniform dispersions; operation in a batch or continuous process; and the like.
[0026] Nonlimiting examples of surface treatments of the present invention include surface treatment of nanomaterials with materials selected from a group consisting of organic, inorganic, metallic compounds, and mixtures or combinations thereof. The materials for surface treatment may take the form of liquids, solids, powders, slurries, gases, vapors, droplets, mixtures or combinations thereof. Illustrative examples of these include and are not limited by water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds,
polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers or polymers, plastics, crystalline organics, multi-component formulations, dispersants, primer, chain extender, adhesion promoter, chain transfer agent, initiators, catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics, semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates,
carbonates, sulfides, natural or man made minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate,
polymethylcyanoacrylate, cyclic azasilanes, nanomaterials, mixtures or combinations thereof and the like. The surface treatment may be applied to the nanomaterials in a manner such that it is uniform, non-uniform, single layer, multi-layer, symmetric, asymmetric, porous, dense, mixtures or combinations thereof and the like
[0027] The nanomaterials of the present invention may include or be made of a variety of materials. Nonlimiting examples of useful materials may be selected from groups that include ceramics, metals, organics, and mixtures or combinations
thereof. Nonlimiting examples of the useful nanomaterial forms include particles, platelets, tubes, films, laminates, spheres, cones, ovals, cylinders, cubes, whiskers, monoclinic,
parallelepipeds, dumbbells, hexagons, truncated dodecahedrons, irregular shapes, fibers, and mixtures or combinations thereof. Nonlimiting examples of inorganics include elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates, sulfides, natural or man made minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and the like. Nonlimiting examples of metals of interest include alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals,
non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and the like. Nonlimiting examples of organics include monomers, polymers, oligomers, and polymer segments, multi-functional monomers, oligomers, or polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic compounds, carbon based compounds such as graphite, carbon black, carbon nanotubes or fullerenes, pigments, mixtures or combinations thereof and the like.
[0028] Curable collection media compositions useful with the present invention include any suitable coating, sealant or adhesive constituent, formulation or product such as, but not limited to, phenolic resins, vinyl resins, silicone resins, acrylic resins, epoxy resins, urethane resins, compositions of olefinically-functionalized compounds, olefin resins, cyanoacrylates, materials curable by radiation, heat, moisture, anaerobic conditions, or contact with reactive species, rubbers and mixtures or combinations thereof.
[0029] The nanomaterials of the present invention may be used for composite applications where there is an interest in
creating nanomaterials that have tailored structure and chemical specificity such that they act in a targeted manner to initiate reactions under a given signal or condition, act to transform surfaces for example as primers for adhesion or cure, act as carriers of molecules and the like.
[0030] FIG. 2 is a schematic depiction of the process according to the present invention for forming and treating nanomaterials for direct dispersion into a collection media.
[0031] At step 46, sintered or reacted nanomaterials are formed. During this step agglomeration of the nanomaterials is prevented. At step 48, the nanomaterials are surface treated. During this step, agglomeration of the treated nanomaterials is prevented. At step 50, the treated nanomaterials are directly dispersed into a collection media while preventing agglomeration of the treated nanomaterials.

Claims

WHAT IS CLAIMED IS :
1. A system for forming, surface treating and dispersing nanomaterials into a collection media, comprising:
a nanomaterial generator operable at or near ambient pressure for generating sintered or reacted nanomaterials freely falling through a gaseous environment;
a surface treatment vessel for modifying surfaces of the freely falling nanomaterials to form freely falling
surface-treated nanomaterials; and
a vessel containing a media into which the surface-treated nanomaterials are deposited and dispersed.
2. The system of claim 1, wherein the nanomaterial generator comprises an ultrasonic spray nozzle for forming nanosized droplets.
3. The system of claim 2, wherein the nanomaterial generator comprises a sintering reactor for sintering or
reacting the nanosized droplets into the sintered or reacted nanomaterials .
4. The system of claim 2, wherein the sintering reactor is a microwave reactor.
5. The system of claim 1, wherein the surface treatment vessel comprises a microwave oven or a plasma chamber for depositing a material onto the surfaces of the sintered
nanomaterials .
6. The system of claim 1, wherein the nanomaterials comprise materials selected from the group consisting of
inorganics, metals, organics and combinations thereof.
7. The system of claim 6, wherein the inorganics are selected from the group consisting of elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural or manmade minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and combinations thereof.
8. The system of claim 6, wherein the metals are selected from the group consisting of alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals,
organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and combinations thereof.
9. The system of claim 6, wherein the organics are
selected from the group consisting of monomers, polymers, oligomers, polymer segments, multi-functional monomers,
oligomers, polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic
compounds, carbon based compounds, carbon nanotubes, fullerenes, pigments and combinations thereof.
10. The system of claim 5, wherein the surface treatment material is selected from the group consisting of organic compounds, inorganic compounds, metallic compounds and
combinations thereof.
11. The system of claim 5, wherein the surface 'treatment material has a form, wherein the form is selected from the group consisting of a liquid, a solid, a powder, a slurry, a gas, a vapor, a droplet and combinations thereof.
12. The system of claim 5, wherein the surface treatment material is selected from the group consisting of water,
hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate,
halogenated compounds, polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers, polymers, plastics, crystalline organics,
multi-component formulations, dispersants, primers, chain extenders, adhesion promoters, chain transfer agents,
initiators, catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural minerals, manmade minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals,
multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds, graphite, carbon black, carbon nanotubes, fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate, polymethylcyanoacrylate, cyclic azasilanes and combinations thereof.
13. The system of claim 5, wherein the surface treatment material is applied to the nanomaterials as a coating, wherein the coating is selected from the group consisting of a uniform coating, a non-uniform coating, a single layer coating, a multi-layer coating, a symmetric coating, a asymmetric coating, a porous coating, a dense coating and combinations thereof.
14. The system of claim 1, wherein the nanomaterials comprise materials having a form, wherein the form is selected from the group consisting of particles, platelets, tubes, films, laminates, spheres, cones, oval-shaped solids, cylinders, cubes, whiskers, monoclinic-shaped solids, parallelepipeds,
dumbbell-shaped solids, hexagonal-shaped solids, truncated dodecahedron-shaped solids, irregular-shaped solids, fibers and combinations thereof.
15. A method for forming, surface treating and dispersing nanomaterials into a collection media, comprising:
sintering or reacting materials at or near ambient pressure to reduce the size of the materials to nanomaterial scale to form nanomaterials;
allowing the sintered or reacted nanomaterials to freely fall through a gaseous environment or be pushed by input gases or gases produced by formation of the nanomaterials;
modifying surfaces of the freely falling sintered or reacted nanomaterials by depositing a surface-treating material to form freely falling surface-treated nanomaterials; and
depositing and dispersing the surface-treated nanomaterials into a vessel containing a collection media.
16. The method of claim 15, further comprising the step of forming nanosized droplets through an ultrasonic spray nozzle, wherein the nanosized droplets are sintered or reacted to form the nanomaterials .
17. The method of claim 15, wherein the step of sintering includes providing microwave energy to sinter or react the nanomaterials .
18. The method of claim 15, wherein the nanomaterials comprise materials selected from the group consisting of inorganics, metals, organics and combinations thereof.
19. The method of claim 18, wherein the inorganics are selected from the group consisting of elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates, sulfides, natural minerals, manmade minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay mica and combinations thereof.
20. The method of claim 18, wherein the metals are
selected from the group consisting of alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals,
non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and combinations thereof.
21. The method of claim 18, wherein the organics are selected from the group consisting of monomers, polymers, oligomers, polymer segments, multi-functional monomers,
oligomers, polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic
compounds, carbon based compounds, graphite, carbon black, carbon nanotubes, fullerenes, pigments and combinations thereof.
22. The method of claim 15, wherein the surface-treatment material is selected from the group consisting of organic compounds, inorganic compounds, metallic compounds and
combinations thereof.
23. The method of claim 15, wherein the surface-treatment material is selected from the group consisting of water,
hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics, phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate,
halogenated compounds, polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers or polymers, plastics, crystalline organics,
multi-component formulations, dispersants, primer, chain
extender, adhesion promoter, chain transfer agent, initiators, catalysts, multi-element ceramics, complex ceramics,
stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural minerals, manmade minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals,
multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds, graphite, carbon black, carbon nanotubes, fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate,
polymethylcyanoacrylate, cyclic azasilanes and combinations thereof.
24. The method of claim 15, wherein the surface-treatment material is applied to the nanomaterials as a coating; wherein the coating is selected from the group consisting of a uniform coating, a non-uniform coating, a single layer coating, a multi-layer, a symmetric coating, an asymmetric coating, a porous coating, a dense coating and combinations thereof.
25. The method of claim 15, wherein the nanomaterials have forms, wherein the forms are selected from the group consisting of particles, platelets, tubes, films, laminates, spheres, cones, oval-shaped solids, cylinders, cubes, whiskers,
monoclinic-shaped solids, parallelepipeds, dumbbell-shaped solids, hexagonal-shaped solids, truncated dodecahedron-shaped solids, irregular shaped solids, fibers and combinations
thereof.
26. The method of claim 15, wherein the surface-treatment material has a form, wherein the form is selected from the group consisting of a liquids, a solid, a powder, a slurry, a gas, a vapor, a droplet and combinations thereof.
27. A collection media composition, comprising:
sintered or reacted, and functionalized nanomaterials which have not been previously agglomerated.
28. The composition of claim 27, wherein the nanomaterials are surface treated with a material selected from the group consisting of organic compounds, inorganic compounds, metallic compounds and combinations thereof.
29. The composition of claim 28, wherein the material for surface treatment has a form, wherein the form is selected from the group consisting of a liquid, a solid, a powder, a slurry, a gas, a vapor, a droplet and combinations thereof.
30. The composition of claim 28, wherein the material for surface treatment is selected from the group consisting of water, hydrocarbons, alcohols, ethers, ketones, aldehydes, esters, amides, epoxies, silicones, urethanes, acrylics,
phenolic resins, cyanoacrylates, aromatics, aliphatics, acids, sulfides, thiols, phosphines, phosphates, cyanates, isocyanate, halogenated compounds, polymers, monomers, block copolymers, surfactants, oligomers, dendrimers, multi-functional monomers, oligomers, polymers, plastics, crystalline organics,
multi-component formulations, dispersants, primers, chain extenders, adhesion promoters, chain transfer agents,
initiators, catalysts, multi-element ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural minerals, manmade minerals, glasses, halides, alloys, superalloys, intermetalics, transition metals, •
multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, carbon based compounds, graphite, carbon black, carbon nanotubes, fullerenes, pigments, methyl methacrylate, polyethylcyanoacrylate, polyinethylcyanoacrylate, cyclic azasilanes and combinations thereof.
31. The composition of claim 28, wherein the material for surface treatment is applied to the nanomaterials as a coating, wherein the coating is selected from the group consisting of a uniform coating, a non-uniform coating, a single layer coating, a multi-layer coating, a symmetric coating, an asymmetric coating, a porous coating, a dense coating and combinations thereof.
32. The composition of 27, wherein the nanomaterials comprise materials selected from the group consisting of
ceramics, metals, organics and combinations thereof.
33. The composition of 32, wherein the inorganics are selected from the group consisting of elemental ceramics, multi-element ceramics, mixed ceramics, complex ceramics, stoichiometric ceramics, non-stoichiometric ceramics,
semiconductors, quantum dots, ionic species, oxides, nitrides, carbides, borides, chalcogenides, silicates, carbonates,
sulfides, natural minerals, manmade minerals, glasses, halides, silica, alumina, iron oxide, copper oxide, diamond, antimony tin oxide, indium tin oxide, zirconia, tungsten carbide, boron carbide, silicon nitride, clay, mica and combinations thereof.
34. The composition of 32, wherein the metals are selected from the group consisting of alloys, superalloys, intermetalics, transition metals, multi-metals, elemental metals, complex metals, stoichiometric metals, non-stoichiometric metals, precious metals, rare earth metals, semi-metals, organometallics, nickel, aluminum, copper, iron, gold, silver, tungsten and combinations thereof.
35. The composition of 32, wherein the organics are selected from the group consisting of monomers, polymers, oligomers, polymer segments, multi-functional monomers,
oligomers, polymers, catalysts, initiators, rubbers, silicones, amides, block copolymers, plastics, crystalline organic
compounds', carbon based compounds, graphite, carbon black, carbon nanotubes, fullerenes, pigments and combinations thereof.
36. The composition of 27, wherein the composition is selected from the group consisting of an adhesive, a sealant, an anti-corrosive formulation, a coating formulation, phenolic resin, vinyl resin, silicone resin, acrylic resin, epoxy resin, urethane resin, a composition of olefinically-functionalized compound, olefin resin, cyanoacrylate, a resin or monomer curable by radiation, a resin or monomer curable by heat, a resin or monomer curable by moisture, a resin or monomer curable by anaerobic conditions, a resin or monomer curable by contact with a reactive specie and combinations thereof.
37. The composition of 27, wherein the nanomaterials have a form, wherein the form is selected from the group consisting particles, platelets, tubes, films, laminates, spheres, cones, oval-shaped solids, cylinders, cubes, whiskers,
monoclinic-shaped solids, parallelepipeds, dumbbell-shaped solids, hexagonal-shaped solids, truncated dodecahedron-shaped solids, irregular shapes, fibers and combinations thereof.
PCT/US2006/043253 2005-11-04 2006-11-03 Method of and system for inline formation, surface treatment and direct dispersion of nanomaterial into a collection media WO2007067288A2 (en)

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