Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers

• US 6,329,058 B1
• Filed: 05/27/1999
• Issued: 12/11/2001
• Est. Priority Date: 07/30/1998
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Wood, Thomas E., Arney, David S.
• Primary Examiner(s): Le, Hoa T.
• Application Number:
  US09/319,057
• Time in Patent Office: 929 Days
• Field of Search: 428/403, 428/404, 428/405, 428/406, 428/328, 427/220, 427/372.2, 427/384, 427/444
• US Class Current: 428/403
• CPC Class Codes: C01P 2002/60 Compounds characterised by their crystallite size
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09C 1/3684 Treatment with organo-silicon compounds
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/268 Monolayer with structurally defined element
• CPC Class Codes: Y10T 428/269 including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 428/2949 Glass, ceramic or metal oxide in coating
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2995 Silane, siloxane or silicone coating
• CPC Class Codes: Y10T 428/2996 Glass particles or spheres
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The present invention relates to metal oxide particles capable of being highly dispersed in organic materials to form transparent colloids and ceramers. The metal oxide particles of the present invention have surfaces attached to a dispersing aid and a degree of crystallinity of greater than 55 percent. The crystallite diameter of the metal oxide particles is greater than about 4 nanometers and less than about 20 nanometers. The present invention also relates to the colloids and ceramers prepared using these metal oxide particles and the methods associated with the preparation of the particles, colloids, and ceramers.

Claims

1. Inorganic particles capable of being combined with at least one transparent organic composition without substantially diminishing the transparency thereof comprising:

(a) titanium based oxide particles having a dispersing aid attached thereto and having a degree of crystallinity of greater than 55 percent;

(b) a crystallite diameter greater than about 4 nanometers and less than about 20 nanometers; and

(c) an absorptivity of less than about 3.00 as a colloid.

2. The inorganic particles of claim 1, wherein the titanium based oxide particles are selected from the group consisting of barium titanium oxide, titanium oxide, and combinations thereof.

3. The inorganic particles of claim 2, wherein the titanium-based particles are titanium oxide.

4. The inorganic particles of claim 1, wherein the inorganic particles are substantially free of silica.

5. The inorganic particles of claim 1, wherein the metal oxide particles have a crystallinity index greater than about 8.0 and less than about 10.0.

6. The inorganic particles of claim 1, wherein the titanium based oxide particles have a tetragonal crystal structure.

7. The inorganic particles of claim 1, wherein the titanium-based particles have a cubic crystal structure.

8. The inorganic particles of claim 1, wherein the degree of crystallinity is greater than about 60 percent and less than about 86 percent.

9. The inorganic particles of claim 1, wherein the dispersing aid is selected from the group consisting of alkoxyorganosilanes, carboxylic acids, and combinations thereof.

10. The inorganic particles of claim 9, wherein the dispersing aid is at least one alkoxyorganosilane.

11. The inorganic particles of claim 10, wherein the alkoxyorganosilane is selected from the group consisting of octyltriethoxysilane, octadecyltrimethoxy silane, hexadecyltrimethoxysilane, and combinations thereof.

12. The inorganic particles of claim 1, wherein the colloid has an absorptivity measurement in the range of about −

0.649 to about 2.72.

13. The inorganic particles of claim 1, wherein the colloid has an absorptivity measurement less than 1.17.

14. The inorganic particles of claim 1, wherein the size of the metal oxide particles is greater than about 5 nanometers and less than about 15 nanometers.

15. The inorganic particles of claim 1, wherein the titanium based particles are prepared from a metal alkoxide combined with a complexing agent to form a mixture.

16. The inorganic particles of claim 15, wherein the mixture is hydrolyzed using a substoichiometric amount of water.

17. A colloid comprising the inorganic particles of claim 1 dispersed in an organic solvent, wherein the colloid is a stable dispersion.

18. A ceramer composition comprising the inorganic particles of claim 1 dispersed in at least one polymer precursor.

19. A method of making dispersible crystalline metal oxide nanoparticles, comprising the steps of:

(a) providing a metal alkoxide;

(b) reacting the metal alkoxide with a substoichiometric amount of a complexing agent;

(c) partially hydrolyzing the product of step (b) by the addition of substoichiometric amounts of water; and

(d) thermally treating the partially hydrolyzed mixture by heating under pressure at a temperature in the range of about 150°

C. to about 265°

C. for an amount of time sufficient to form crystalline particles having a crystallite diameter greater than about 4 nanometers and less than about 20 nanometers and having a degree of crystallinity greater than 55 percent.

20. The method of claim 19, wherein the complexing agent includes carboxylic acids having a carbon chain of about 3 carbon atoms to about 18 carbon atoms.

21. The method of claim 19, comprising the steps of:

(e) combining the crystalline particles with an organic solvent to form a mixture; and

(f) combining the mixture with a dispersing aid to form metal oxide particles that are dispersible in organic solvent.

22. The method of claim 21, wherein the dispersing aid is combined with the particles prior to the introduction of additional water.

23. The method of claim 21, wherein the method is free of a seed.