Metal oxide ceramic nanomaterials and methods of making and using same

Patent metadata

Field	Value
Publication number	US-9822039-B1
Application number	US-201615240673-A
Country	US
Kind code	B1
Filing date	Aug 18, 2016
Priority date	Aug 18, 2016
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

Provided are metal oxide ceramic materials and intermediate materials thereof (e.g., nanozirconia gels, nanozirconia green bodies, pre-sintered ceramic bodies, zirconia dental ceramic materials, and dental articles). The nanozirconia gels are formable gels. Also provided are methods of making and using the metal oxide materials and intermediate materials. The nanozirconia gels can be made using, for example, osmotic processing. The nanozirconia gels can be used to make nanozirconia green bodies, pre-sintered ceramic bodies, zirconia dental ceramic materials, and dental article. The nanozirconia green bodies, pre-sintered ceramic bodies, zirconia dental ceramic materials, and dental articles have desirable properties (e.g., optical properties and mechanical properties).

First claim

The invention claimed is:

1. A method of making a gel comprising a plurality of zirconia nanoparticles and water, wherein the zirconia nanoparticles have an average size of 10 to 30 nm, 95% or more of the zirconia nanoparticles by volume have a size of 45 nm or less, the zirconia nanoparticles are present at 70 to 85% by weight based on the total weight of the gel, and the gel is a formable gel, wherein the gel exhibits a viscosity at yield point of 1×10 9 to 12×10 9 mPa·s and a yield stress of 1×10 3 to 9×10 3 Pa, the method comprising:
a) providing an aqueous suspension comprising zirconia nanoparticles having an average size of 10 to 30 nm and 95% or more of the zirconia nanoparticles by volume have a size of 45 nm or less, wherein the zirconia nanoparticles are present at less than 70% by weight of the aqueous suspension; and
b) concentrating the aqueous suspension by removing water from the aqueous suspension with a semipermeable membrane, wherein the water removal is driven by intrinsically induced pressure or externally imposed pressure, until the suspension has zirconia nanoparticles present at 70 to 85% by weight of the aqueous suspension, whereby the gel is formed.

2. The method of claim 1 , wherein the aqueous suspension further comprises a processing agent.

3. The method of claim 1 , further comprising:
attrition milling a starting aqueous suspension comprising zirconia nanoparticles having an average size greater than 50 nm, wherein the zirconia nanoparticles are present at 50% or greater by weight of the starting aqueous suspension based on the total weight of the starting aqueous suspension, and,
optionally, subjecting the attrition milled starting aqueous suspension to centrifugation, to provide the aqueous suspension of a).

4. The method of claim 3 , wherein the starting aqueous suspension prior to attrition milling further comprises a colloidal stabilizer and/or a particle interaction strengthening agent is added to the starting aqueous suspension after attrition milling.

5. The method of claim 1 , wherein a starting aqueous suspension comprises zirconia nanoparticles having an average size greater than 50 nm, wherein the zirconia nanoparticles are present at less than 50% by weight of the starting aqueous suspension based on the total weight of the starting aqueous suspension and the method further comprises:
i) concentrating the starting aqueous suspension by heating and/or applying sub-ambient pressure to the starting aqueous solution until the zirconia nanoparticles are present at 50% or greater by weight based on the total weight of the starting aqueous suspension; and
ii) attrition milling the concentrated starting aqueous suspension from i) and, optionally, subjecting the attrition milled starting aqueous suspension to centrifugation, to provide the aqueous suspension of a).

6. The method of claim 5 , wherein a colloidal stabilizer is added to the starting aqueous suspension prior to the concentration of the starting aqueous suspension and/or a particle interaction strengthening agent is added to the starting aqueous suspension after attrition milling.

7. The method of claim 1 , wherein the concentrating is carried out by an osmotic process comprising an osmotic solution.

8. The method of claim 7 , wherein the osmotic solution is an aqueous polymer solution.

9. The method of claim 7 , wherein the osmotic process is carried out with physical agitation of the aqueous suspension.

10. The method of claim 7 , wherein the osmotic process comprises:
a) placing the aqueous suspension comprising zirconia nanoparticles in an enclosure at least a portion of an external surface of which is a semipermeable membrane;
b) contacting the enclosure with an osmotic solution such that the osmotic solution and the aqueous suspension are in fluid contact;
c) agitating the aqueous suspension; and
d) optionally, heating the osmotic solution.

11. The method of claim 1 , wherein the concentrating is carried out by a tangential flow filtration process.

12. The method of claim 11 wherein the tangential flow filtration process comprises:
a) flowing the aqueous suspension comprising zirconia nanoparticles through a channel at least a portion an external surface of which is the semipermeable membrane;
b) repeating a) until the a desired amount of water is removed from the aqueous suspension comprising zirconia nanoparticles; and
c) optionally, heating the aqueous suspension comprising zirconia nanoparticles.

13. The method of claim 12 , wherein the semipermeable membrane is contacted with an osmotic solution.

14. The method of claim 1 , wherein:
i) 99% of nanoparticles by volume have a size less than 60 nm±10 nm;
ii) 95% of nanoparticles by volume have a size less than 40 nm±5 nm;
iii) 50% of nanoparticles by volume have a size less than 20 nm±5 nm; and
iv.) 5% of nanoparticles by volume have a size less than 12 nm±3 nm.

Assignees

• Ivoclar Vivadent Ag

Inventors

• Xu Wei
• Wang Yijun
• Brodkin Dmitri

Classifications

• A61K6/17

  Particle size · CPC title

• A61K6/818

  comprising zirconium oxide · CPC title

• C04B35/63488

  Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO] · CPC title

• C04B35/624

  Sol-gel processing · CPC title

• C04B2235/77

  Density · CPC title