Conductive nanocomposite films

• US 7,250,454 B2
• Filed: 05/09/2003
• Issued: 07/31/2007
• Est. Priority Date: 09/03/1996
• Status: Expired due to Fees

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: NanoProducts Corporation (Nouryon BV)
• Inventors: Yadav, Tapesh, Kostelecky, Clayton
• Primary Examiner(s): Yoon, Tae H
• Application Number:
  US10/434,828
• Publication Number:
  US 20030199624A1
• Time in Patent Office: 1,544 Days
• Field of Search: 523/210, 523/105, 523/113, 523/137, 523/200, 523/220, 523/375, 524/435, 524/436, 524/434, 524/413, 524/408, 524/406, 524/403
• 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 low resistivity nanocomposite layers that simultaneously offer optical clarity, wear resistance and superior functional performance. Nanofillers and a substance having a polymer are mixed. Both low-loaded and highly-loaded nanocomposites are included. Nanoscale coated and un-coated fillers may be used. Nanocomposite films may be coated on substrates.

Claims

1. A method for preparing an optically clear nanocomposite layer with resistivity less than 4.5×

10⁵ ohm·

cm comprising;

providing nanofillers;

providing a liquid polymer matrix;

mixing the nanofillers and the liquid polymer matrix below a loading of 80% by volume and processing the mixture to produce a nanocomposite; and

wherein the nanocomposite has a transparency to light that differs by more than 20% as compared with the transparency to light exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron.

2. The method of claim 1 wherein the mixing includes adding a secondary species material selected from the group consisting of:

dispersants, binders, modifiers, detergents, and additives.

3. The method of claim 1 wherein the loading is heterogeneous.

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

5. The method of claim 1 wherein the nanocomposite is wear resistant.

6. The method of claim 1 wherein the nanofillers comprise powders with an aspect ratio between 1 and 25.

7. The method of claim 1 wherein the nanofillers comprise carbide or metal.

8. 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.

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

antimony, boron, bromine, carbon, chlorine, fluorine, germanium, hydrogen, iodine, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and tellurium.

10. The method of claim 1 wherein the polymer matrix comprises oxygen.

12. The method of claim 1 further comprising a step wherein the nanofillers are chemically reduced prior to the mixing step.

11. A method for preparing an optically clear nanocomposite layer with resistivity less than 4.5×

10⁵ ohm·

cm comprising;

providing nanofillers;

providing a matrix;

mixing the nanofillers and the matrix below a loading of 80% by volume and processing the mixture to produce a nanocomposite, wherein the nanofillers are chemically reduced prior to the mixing; and

wherein the nanocomposite has a transparency to light that differs by more than 20% as compared with the transparency to light exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron.

13. A method for preparing a nanocomposite with resistivity between 1.09×

10⁴ ohm·

cm and 5.54×

10¹² ohm·

cm comprising;

providing nanofillers comprising domain size less than 100 nanometers;

providing a matrix;

mixing the nanofillers and the matrix below a loading of 80% by volume and processing the mixture to produce a nanocomposite, wherein the nanofillers are chemically reduced prior to the mixing; and

wherein the nanocomposite has a transparency to light at a specific wavelength of light that differs by more than 20% as compared with the transparency to light at the specific wavelength of light exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron.

14. The method of claim 13 wherein the nanofillers comprise one or more elements selected from the group consisting of:

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

15. The method of claim 13 wherein the nanofillers comprise powders with aspect ratio greater than one.