Nanostructured fillers and carriers

• US 6,228,904 B1
• Filed: 05/22/1998
• Issued: 05/08/2001
• Est. Priority Date: 09/03/1996
• Status: Expired due to Term

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: Nanomaterials Research Corp.
• Inventors: Kostelecky, Clayton, Franke, Evan, Miremadi, Bijan, Au, Ming, Yadav, Tapesh
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US09/083,893
• Time in Patent Office: 1,082 Days
• Field of Search: 106/400, 106/401, 106/419, 106/425, 106/436, 106/437, 106/450, 106/451, 106/456, 106/452, 106/459, 106/461, 106/479, 106/480, 428/403, 428/404, 428/458, 428/461, 428/462, 428/463, 428/469, 428/515, 428/689, 428/704, 428/539.5, 523/206, 523/210, 523/105, 523/113, 523/137, 523/200, 523/220, 523/375, 524/401, 524/403, 524/406, 524/408, 524/413, 524/434, 524/435, 524/436, 524/437, 524/439, 524/440, 524/441, 252/22.54, 252/301.36, 252/62.33, 252/582, 252/512-517, 252/518.1, 252/517.33, 252/517.5, 252/520.1, 252/520.2, 252/517.1, 252/517.12 , 252/320.21, 252/320.3, 252/320.4, 252/320.5, 252/521.1, 252/521.2, 429/212, 429/221, 429/232
• US Class Current: 523/210
• 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: B22F 1/054 Nanosized particles
• 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 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: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C01B 13/145 After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
• 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 32/956 : Silicon carbide
• 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 23/006 : Alkaline earth titanates
• CPC Class Codes: C01G 41/02 : Oxides; Hydroxides
• 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 2002/54 : 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 2004/38 : cube-like
• CPC Class Codes: C01P 2004/51 : Particles with a specific particle 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 2004/82 : two phases having the same anion, e.g. both oxidic phases
• CPC Class Codes: C01P 2006/10 : Solid density
• CPC Class Codes: C01P 2006/12 : Surface area
• CPC Class Codes: C01P 2006/40 : Electric properties
• CPC Class Codes: C01P 2006/60 : Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/80 : Compositional purity
• 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 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 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: C08J 5/005 : Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• CPC Class Codes: C08K 2201/011 : Nanostructured additives
• CPC Class Codes: C08K 3/01 : characterized by their specific function
• CPC Class Codes: C08K 3/08 : Metals
• 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: 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 4/9066 : of metal-ceramic composites or mixtures, e.g. cermets
• 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 977/89 : Deposition of materials, e.g. coating, cvd, or ald
• CPC Class Codes: Y10T 29/49002 : Electrical device making
• CPC Class Codes: Y10T 29/49082 : Resistor making
• CPC Class Codes: Y10T 428/26 : Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Abstract

A nanocomposite structure comprising a nanostructured filler or carrier intimately mixed with a matrix, and methods of making such a structure. The nanostructured filler has a domain size sufficiently small to alter an electrical, magnetic, optical, electrochemical, chemical, thermal, biomedical, or tribological property of either filler or composite by at least 20%.

Claims

1. A method of producing a composite material, comprising:

providing a polymer matrix material;

providing a nanostructured filler in powder form having a domain size of less than about 100 nanometers, wherein the nanostructured filler comprises a material selected from the group consisting of indium tin oxide, reduced indium tin oxide, dielectrics, ferrites, manganates; and

mixing the nanostructured filler intimately with the matrix material at a filler loading selected to cause the composite material to have a resistivity that differs by more than 20% as compared with the resistivity exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron;

wherein the providing of the nanostructured filler includes applying a coating material to the exterior surface of the nanostructured filler and wherein the coating material comprises the matrix material.

2. The method of claim 1, wherein the nanostructured filler material and the filler loading are selected such that the composite material has a resistivity that differs by more than about 20 percent from a resistivity of a composite having a similar matrix and filler composition with the filler having an average domain size of at least about 1 micron.

3. The method of claim 1, wherein the mixing comprises mechanical mixing.

4. 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.

5. The method of claim 1, wherein the applying of the coating material includes suspending the nanostructured filler in a solvent, measuring the pH level of the suspension, adjusting the pH level to produce a charged state on the exterior surface of the nanostructured filler, introducing the coating material having an opposite charge to the charged state into the suspension, and separating the solvent and the nanostructured filler.

6. The method of claim 5, wherein the mixing of the nanostructured filler and the matrix material comprises dissolving the matrix material in the suspension during the applying of the coating material.

7. The method of claim 1, wherein the matrix material is selected from the group consisting of poly(methyl methacrylate), poly(vinyl alcohol), polycarbonates, polyalkenes, and polyaryls.

8. A composite material, comprising:

a solid matrix material; and

a powder filler mechanically assembled with the matrix material such that the matrix material and the filler retain their identifying properties, wherein the filler comprises particles with a domain size less than about 100 nanometers, the particles comprising reduced indium tin oxide.

9. The composite material of claim 8, wherein the amount of filler is selected to be higher than about the percolation limit of the filler in the matrix material.

10. The composite material of claim 8, wherein the matrix material is bioabsorbable.

11. The composite material of claim 8, wherein the filler particle is coated with a polymer that is water soluble or water insoluble.

12. The composite material of claim 8, wherein the matrix material and the filler are powders and wherein the mechanical assembly of the matrix material and the filler is achieved on a micro scale by mixing the matrix material and the filler, pressing the mixture, and sintering the pressed mixture.

13. The composite material of claim 8, wherein the matrix material is a ceramic or a ceramic blend.

14. A composite material, comprising:

a matrix material; and

a nanostructured filler comprising manganate intimately mixed with the matrix material, wherein the nanostructured filler comprises particles with a domain size of less than about 100 nanometers and is selected to cause the composite material to have a resistivity that differs by more than 20% as compared with the resistivity exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron.

15. The composite material of claim 14, wherein the nanostructured filler is coated with a polymer.

16. A varistor device with a current-voltage response defined by a varistor power-law equation, I=n*V^α

, where a is a voltage parameter, the varistor device comprising;

a pair of electrodes; and

a composite material interposed between the electrodes, the composite material including an matrix material intimately mixed with a nanostructured filler comprising particles having domain sizes of less than about 100 nanometers;

wherein the nanostructured filler and a filler loading in the composite material are selected such that the voltage parameter, α

, for the varistor device is at least 20 percent greater than a varistor device having a composite material of similar composition with filler particles having an average domain size of at least 1 micron.

17. The varistor device of claim 16, wherein the nanostructured filler comprises an oxide.

18. A battery, comprising:

an anode; and

a nanocomposite cathode comprising a composite material including a matrix and a nanostructured filler of particles having a domain size of less than about 100 nanometers;

wherein the battery has a power density that is greater by more than 100 percent as compared with the power density exhibited by a battery having a cathode fabricated from composite materials of equivalent composition and average filler domain sizes greater than about 1 micron.

19. The battery of claim 18, wherein the cathode nanostructured filler comprises iron disulfide.

20. The battery of claim 19, wherein the battery is a thermal battery.

21. A composite material, comprising:

a solid matrix material; and

a powder filler mechanically assembled with the matrix material such that the matrix material and the filler retain their identifying properties, wherein the filler comprises particles with a domain size less than about 100 nanometers, the particles comprising a material selected from the group consisting of multimetal oxide, hydroxides, borides, phosphides, and silicides and being coated with a polymer that is water soluble or water insoluble.

22. The composite material of claim 21, wherein the amount of filler is selected to be higher than about the percolation limit of the filler in the matrix material.

23. The composite material of claim 21, wherein the matrix material is a ceramic or a ceramic blend.

24. A composite material, comprising:

a matrix material; and

a nanostructured filler comprising reduced indium tin oxide intimately mixed with the matrix material, wherein the nanostructured filler comprises particles with a domain size of less than about 100 nanometers and is selected to cause the composite material to have a resistivity that differs by more than 20% as compared with the resistivity exhibited by a composite material of similar composition with filler particles having a domain size of at least one micron.

25. The composite material of claim 24, wherein the nanostructured filler is coated with a polymer.

26. A method of producing a composite material comprising the acts of:

providing a matrix material; and

providing a nanostructured filler in powder form having a domain size of less than about 100 nanometers, wherein the nanostructured filler comprises reduced indium tin oxide.