Thermal nanocomposites

• US 8,389,603 B2
• Filed: 05/09/2003
• Issued: 03/05/2013
• Est. Priority Date: 09/03/1996
• Status: Expired due to Fees

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Yadav, Tapesh, Kostelecky, Clayton, Franke, Evan, Miremadi, Bijan, Au, Ming, Vigliotti, Anthony
• Primary Examiner(s): Yoon, Tae H
• Application Number:
  US10/435,222
• Publication Number:
  US 20030207976A1
• Time in Patent Office: 3,588 Days
• Field of Search: 523/210, 523/113, 523/137, 523/200, 523/220, 523/375, 524/435, 524/436, 524/434, 524/413, 524/408, 524/406, 524/403, 524/424, 524/439, 524/404, 524/414, 524/428
• US Class Current: 523/200
• CPC Class Codes: B01J 12/005 carried out at high temperatures, e.g. by pyrolysis
• CPC Class Codes: B01J 12/02 for obtaining at least one reaction product which, at normal temperature, is in the solid state
• CPC Class Codes: B01J 19/24 Stationary reactors without moving elements inside B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02
• CPC Class Codes: B01J 2219/00094 Jackets
• CPC Class Codes: B01J 2219/00135 Electric resistance heaters
• CPC Class Codes: B01J 2219/00155 using insulating materials or refractories
• CPC Class Codes: B01J 2219/00177 controlling the pH
• CPC Class Codes: B01J 2219/0018 controlling the conductivity
• CPC Class Codes: B01J 2219/0894 Processes carried out in the presence of a plasma
• CPC Class Codes: B05B 1/12 capable of producing different kinds of discharge, e.g. either jet or spray having selectively-effective outlets B05B1/16
• CPC Class Codes: B22F 1/054 Nanosized particles
• CPC Class Codes: B22F 1/07 Metallic powder characterised by particles having a nanoscale microstructure nanosized particles B22F1/054
• CPC Class Codes: B22F 1/09 Mixtures of metallic powders
• CPC Class Codes: B22F 1/10 Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
• CPC Class Codes: B22F 1/102 Metallic powder coated with organic material
• CPC Class Codes: B22F 1/12 Metallic powder containing non-metallic particles containing lubricating or binding agents or organic material B22F1/10
• CPC Class Codes: B22F 2202/13 Use of plasma
• CPC Class Codes: B22F 2999/00 Aspects linked to processes or compositions used in powder metallurgy
• CPC Class Codes: B22F 9/12 starting from gaseous material
• CPC Class Codes: B29C 70/58 comprising fillers only , e.g. particles, powder, beads, flakes, spheres B29C70/025 takes precedence, agglomerating hollow spheres to produce synthetic foam B29C70/66; compounding ingredients per se C08K
• CPC Class Codes: B82B 1/00 : Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• CPC Class Codes: B82Y 20/00 : Nanooptics, e.g. quantum optics or photonic crystals
• CPC Class Codes: B82Y 25/00 : Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/145 : After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
• CPC Class Codes: C01B 13/363 : Mixtures of oxides or hydroxides by precipitation
• CPC Class Codes: C01B 19/007 : Tellurides or selenides of metals C01B19/002 takes precedence
• CPC Class Codes: C01B 21/062 : with chromium, molybdenum or tungsten
• CPC Class Codes: C01B 25/08 : Other phosphides
• CPC Class Codes: C01B 32/90 : Carbides
• CPC Class Codes: C01B 32/914 : Carbides of single elements
• CPC Class Codes: C01B 35/04 : Metal borides
• CPC Class Codes: C01F 11/06 : of carbonates
• CPC Class Codes: C01F 5/06 : by thermal decomposition of magnesium compounds calcining magnesite or dolomite C04B2/10
• CPC Class Codes: C01G 15/00 : Compounds of gallium, indium or thallium
• CPC Class Codes: C01G 19/00 : Compounds of tin
• CPC Class Codes: C01G 19/006 : Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 19/02 : Oxides
• CPC Class Codes: C01G 23/006 : Alkaline earth titanates
• CPC Class Codes: C01G 41/02 : Oxides; Hydroxides
• CPC Class Codes: C01G 49/0018 : Mixed oxides or hydroxides, C01G49/0009 takes precedence
• CPC Class Codes: C01G 49/0063 : containing zinc
• CPC Class Codes: C01G 53/006 : Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen nickelates C01G53/40
• CPC Class Codes: C01P 2002/01 : depicted by a TEM-image
• CPC Class Codes: C01P 2002/02 : Amorphous compounds
• CPC Class Codes: C01P 2002/34 : perovskite-type (ABO3)
• CPC Class Codes: C01P 2002/52 : containing elements as dopants
• CPC Class Codes: C01P 2002/54 : one element only
• CPC Class Codes: C01P 2002/60 : Compounds characterised by their crystallite size
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 : obtained by SEM
• CPC Class Codes: C01P 2004/04 : obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/10 : extending in one dimension, e.g. needle-like
• CPC Class Codes: C01P 2004/16 : Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
• CPC Class Codes: C01P 2004/20 : extending in two dimensions, e.g. plate-like
• CPC Class Codes: C01P 2004/38 : cube-like
• CPC Class Codes: C01P 2004/51 : Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/52 : highly monodisperse size distribution
• CPC Class Codes: C01P 2004/54 : Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
• CPC Class Codes: C01P 2004/61 : Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 : Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 : Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2004/84 : one phase coated with the other
• CPC Class Codes: C01P 2004/86 : Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
• CPC Class Codes: C01P 2006/10 : Solid density
• CPC Class Codes: C01P 2006/12 : Surface area
• CPC Class Codes: C01P 2006/42 : Magnetic properties
• CPC Class Codes: C04B 14/30 : Oxides other than silica ferrites C04B14/363
• CPC Class Codes: C04B 14/322 : Carbides
• CPC Class Codes: C04B 14/325 : Nitrides
• CPC Class Codes: C04B 14/38 : Fibrous materials; Whiskers
• CPC Class Codes: C04B 2/10 : Preheating, burning calcining or cooling decarbonation during burning of cement raw materials C04B7/43; obtaining CaO or MgO otherwise than by thermal decomposition of the corresponding carbonates C01F11/02, C01F5/02
• CPC Class Codes: C04B 20/0004 : Microcomposites or nanocomposites, e.g. composite particles obtained by polymerising monomers onto inorganic materials
• CPC Class Codes: C04B 20/008 : Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder colloidal silica C04B14/062 ; silica fume C04B18/146
• CPC Class Codes: C04B 20/1018 : with organic materials pigments or dyes C04B20/1096
• CPC Class Codes: C04B 20/1029 : Macromolecular compounds
• CPC Class Codes: C04B 2103/40 : Surface-active agents, dispersants
• CPC Class Codes: C04B 2103/408 : Dispersants
• CPC Class Codes: C04B 2111/00008 : Obtaining or using nanotechnology related materials
• CPC Class Codes: C04B 2111/00482 : Coating or impregnation materials
• CPC Class Codes: C04B 2111/00844 : for electronic applications
• CPC Class Codes: C04B 2235/3201 : Alkali metal oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3206 : Magnesium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3241 : Chromium oxides, chromates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3262 : Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
• CPC Class Codes: C04B 2235/3275 : Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
• CPC Class Codes: C04B 2235/3279 : Nickel oxides, nickalates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3284 : Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• CPC Class Codes: C04B 2235/3286 : Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
• CPC Class Codes: C04B 2235/3298 : Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
• CPC Class Codes: C04B 2235/3418 : Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint glass constituents C04B2235/36
• CPC Class Codes: C04B 2235/444 : Halide containing anions, e.g. bromide, iodate, chlorite
• CPC Class Codes: C04B 2235/5409 : expressed by specific surface values
• CPC Class Codes: C04B 2235/5454 : nanometer sized, i.e. below 100 nm
• CPC Class Codes: C04B 2235/549 : the particle size being expressed by crystallite size or primary particle size
• CPC Class Codes: C04B 2235/6562 : Heating rate
• CPC Class Codes: C04B 2235/6565 : Cooling rate
• CPC Class Codes: C04B 24/2623 : Polyvinylalcohols; Polyvinylacetates
• CPC Class Codes: C04B 26/02 : Macromolecular compounds
• CPC Class Codes: C04B 26/06 : Acrylates
• CPC Class Codes: C04B 35/01 : based on oxide ceramics
• CPC Class Codes: C04B 35/10 : based on aluminium oxide
• CPC Class Codes: C04B 35/265 : Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
• CPC Class Codes: C04B 35/453 : based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
• CPC Class Codes: C04B 35/457 : based on tin oxides or stannates
• CPC Class Codes: C04B 35/547 : based on sulfides or selenides or tellurides
• CPC Class Codes: C04B 35/62222 : obtaining ceramic coatings coating of mortars, concrete, artificial or natural stone or ceramics C04B41/45; laminated ceramic products B32B18/00; coating metallic materials C23; coating of glass C03C17/00, applying ceramic coatings on silicon for semi-conductor purposes H01L
• CPC Class Codes: C04B 35/6265 : involving reduction or oxidation
• CPC Class Codes: C04B 35/628 : Coating the powders or the macroscopic reinforcing agents
• CPC Class Codes: C04B 35/63456 : Polyurethanes; Polyisocyanates
• CPC Class Codes: C04B 35/653 : Processes involving a melting step
• CPC Class Codes: C04B 41/009 : characterised by the material treated
• CPC Class Codes: C04B 41/4539 : as a emulsion, dispersion or suspension
• CPC Class Codes: C04B 41/4549 : Nanometer-sized particles
• CPC Class Codes: C04B 41/5027 : Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
• CPC Class Codes: C04B 41/5049 : Zinc or bismuth oxides
• CPC Class Codes: C04B 41/5116 : Ag or Au
• CPC Class Codes: C04B 41/5122 : Pd or Pt
• CPC Class Codes: C04B 41/52 : Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• CPC Class Codes: C04B 41/89 : for obtaining at least two superposed coatings having different compositions
• CPC Class Codes: C04B 41/90 : at least one coating being a metal
• CPC Class Codes: C08K 2201/011 : Nanostructured additives
• CPC Class Codes: C08K 3/01 : characterized by their specific function
• CPC Class Codes: C08K 3/013 : Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 3/08 : Metals
• CPC Class Codes: C08K 9/02 : Ingredients treated with inorganic substances
• CPC Class Codes: C09C 1/00 : Treatment of specific inorganic materials other than fibrous fillers tenebrescent materials C09K9/00; luminescent materials C09K11/00; Preparation of carbon black
• CPC Class Codes: C09C 1/0081 : Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/22 : Compounds of iron C09C1/0009, C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/627 : Copper
• CPC Class Codes: C09C 3/08 : Treatment with low-molecular-weight non-polymer organic compounds C09C3/006, C09C3/048 take precedence
• CPC Class Codes: C09C 3/10 : Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: H01B 1/22 : the conductive material comprising metals or alloys
• CPC Class Codes: H01C 7/105 : Varistor cores H01C7/12 takes precedence
• CPC Class Codes: H01C 7/112 : ZnO type
• CPC Class Codes: H01F 1/0063 : in a non-magnetic matrix, e.g. granular solids granular films H01F10/007
• CPC Class Codes: H01F 1/344 : Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
• CPC Class Codes: H01F 1/36 : in the form of particles H01F1/346, H01F1/348 and H01F1/38 take precedence
• CPC Class Codes: H01G 4/12 : Ceramic dielectrics H01G4/085 takes precedence
• CPC Class Codes: H01G 4/33 : Thin- or thick-film capacitors thin- or thick-film circuits H01L27/00; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor H01L28/40
• CPC Class Codes: H01M 2004/021 : Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/5815 : Sulfides
• CPC Class Codes: H01M 4/9066 : of metal-ceramic composites or mixtures, e.g. cermets
• CPC Class Codes: H01M 6/20 : working at high temperature deferred-action thermal cells H01M6/36
• CPC Class Codes: H01M 6/36 : containing electrolyte and made operational by physical means, e.g. thermal cells
• CPC Class Codes: H01M 8/1213 : characterised by the electrode/electrolyte combination or the supporting material
• CPC Class Codes: H01M 8/1246 : the electrolyte consisting of oxides
• CPC Class Codes: H01M 8/1253 : the electrolyte containing zirconium oxide
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 40/40 : Production or processing of lime, e.g. limestone regeneration of lime in pulp and sugar mills
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10T 428/2998 : including synthetic resin or polymer
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane

Abstract

Methods for preparing nanocomposites with thermal properties modified by powder size below 100 nanometers. Both low-loaded and highly-loaded nanocomposites are included. Nanoscale coated, un-coated, whisker type fillers are taught. Thermal nanocomposite layers may be prepared on substrates.

Claims

1. A method for preparing a thermal nanocomposite comprising:

processing a nanocomposite mixture to form a thermal nanocomposite comprising less than or equal to 80% nanofillers by volume in a solid polymer matrix, having a connectivity of nanofillers in 1, 2, and/or 3 dimensions, and having a thermal conductivity that differs by more than 20% as compared with the thermal conductivity exhibited by a composite material of a similar composition with filler particles having a domain size of 1 micron,

the nanocomposite mixture comprising;

nanofillers comprising surface treated nanoparticles and having a domain size equal to or less than the mean free path of phonons, wherein the nanofillers comprise a composition selected from the group consisting of carbides, nitrides, borides, phosphides, and silicides, with the proviso that the nanofillers do not comprise oxygen; and

a polymer matrix.

2. The method of claim 1 further comprising mixing the nanofillers, the polymer matrix, and a secondary species material selected from the group consisting of:

solvents, dispersants, binders, modifiers, detergents, and additives.

3. The method of claim 1 wherein the solid thermal nanocomposite comprises heterogeneous loading of the nanofillers.

4. The method of claim 1 further comprising depositing the nanocomposite on a substrate.

5. The method of claim 1 further comprising applying the nanocomposite as a layer over another substance.

6. The method of claim 1 wherein the nanofillers comprise a surface consisting of a thin layer of a phase that is compatible with the matrix composition or a surface wherein a precursor has been reacted with the surface of the nanofillers.

7. The method of claim 1 wherein the nanofillers comprise one or more elements selected from the group consisting of:

aluminum, barium, bismuth, cadmium, calcium, cerium, cesium, cobalt, copper, europium, gallium, gold, indium, iron, lanthanum, lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, palladium, platinum, potassium, praseodymium, scandium, silver, sodium, strontium, tantalum, tin, titanium, tungsten, vanadium, ytterbium, yttrium, zinc, and zirconium.

8. The method of claim 1 wherein the nanofillers comprise one or more elements selected from the group consisting of:

antimony, boron, bromine, carbon, fluorine, germanium, hydrogen, iodine, nitrogen, phosphorus, and silicon.

9. The method of claim 1 wherein the nanofillers comprise whiskers.

23. The method of claim 1, wherein the polymer matrix is dissolved in the solvent and the processing removes the solvent.

25. The method of claim 1, wherein the nanocomposite comprises 20% to 80% nanofillers by volume.

10. A method for preparing a thermal nanocomposite comprising:

processing a nanocomposite mixture to form a solid thermal nanocomposite comprising less than or equal to 80% nanofillers by volume in a solid polymer matrix, having a connectivity of nanofillers in 1, 2, and/or 3 dimensions, and having a thermal conductivity that differs by more than 20% as compared with the thermal conductivity exhibited by a composite material of a similar composition with filler particles having a domain size of 1 micron,

the nanocomposite mixture comprising;

nanofillers comprising coated nanoparticles and having a domain size equal to or less than the mean free path of phonons, wherein the nanofillers comprise a composition selected from the group consisting of carbides, nitrides, borides, phosphides, and silicides, with the proviso that the nanofillers do not comprise oxygen; and

a polymer matrix.

11. The method of claim 10 further comprising mixing the nanofillers, the polymer matrix, and a secondary species material selected from the group consisting of:

solvents, dispersants, binders, modifiers, detergents, and additives.

12. The method of claim 10 wherein the solid thermal nanocomposite comprises heterogeneous loading of the nanofillers.

13. The method of claim 10 further comprising depositing the nanocomposite on a substrate.

14. The method of claim 10 further comprising depositing the nanocomposite as a layer over another substance.

15. The method of claim 10 wherein the nanofillers comprise a surface consisting of a thin layer of a phase that is compatible with the matrix composition or a surface wherein a precursor has been reacted with the surface of the nanofillers.

16. The method of claim 10 wherein the nanofillers comprise one or more elements selected from the group consisting of:

aluminum, barium, bismuth, cadmium, calcium, cerium, cesium, cobalt, copper, europium, gallium, gold, indium, iron, lanthanum, lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, palladium, platinum, potassium, praseodymium, scandium, silver, sodium, strontium, tantalum, tin, titanium, tungsten, vanadium, ytterbium, yttrium, zinc, and zirconium.

17. The method of claim 10 wherein the nanofillers comprise one or more elements selected from the group consisting of:

antimony, boron, bromine, carbon, fluorine, germanium, hydrogen, iodine, nitrogen, phosphorus, and silicon.

18. The method of claim 10 wherein the nanofillers comprise whiskers.

19. The method of claim 10 wherein the nanofillers comprise nanoparticles comprising a polymer coating or a monomer coating.

20. The method of claim 10 wherein the nanofillers comprise surface treated particles.

21. The method of claim 10 wherein the nanofillers comprise two or more elements selected from the group consisting of:

aluminum, barium, bismuth, cadmium, calcium, cerium, cesium, cobalt, copper, europium, gallium, gold, indium, iron, lanthanum, lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, palladium, platinum, potassium, praseodymium, scandium, silver, sodium, strontium, tantalum, tin, titanium, tungsten, vanadium, ytterbium, yttrium, zinc, and zirconium.

22. The method of claim 10 wherein the nanofillers comprise two or more elements selected from the group consisting of:

antimony, boron, bromine, carbon, fluorine, germanium, hydrogen, iodine, nitrogen, phosphorus, and silicon.

24. The method of claim 10, wherein the polymer matrix is dissolved in the solvent and the processing removes the solvent.

26. The method of claim 10, wherein the nanocomposite comprises 20% to 80% nanofillers by volume.