Aerogels, calcined and crystalline articles and methods of making the same

Patent metadata

Field	Value
Publication number	US-9657152-B2
Application number	US-201214347382-A
Country	US
Kind code	B2
Filing date	Aug 3, 2012
Priority date	Oct 10, 2011
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

Aerogel, calcined articles, and crystalline articles comprising ZrO 2 . Exemplary uses of the crystalline metal oxide articles include dental articles (e.g., restoratives, replacements, inlays, onlays, veneers, full and partial crowns, bridges, implants, implant abutments, copings, anterior fillings, posterior fillings, and cavity liner, and bridge frameworks) and orthodontic appliances (e.g., brackets, buccal tubes, cleats, and buttons).

First claim

What is claimed is:

1. A method of making a crack-free, crystalline metal oxide article, the method comprising:
providing a monolithic aerogel comprising an organic material and crystalline metal oxide particles, wherein the crystalline metal oxide particles are in a range of 3 to 20 volume percent, based on the total volume percent of the aerogel, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 ;
heating the monolithic aerogel for a time and at a temperature sufficient to provide a crack-free, calcined metal oxide article, wherein the crack-free calcined metal oxide article has x, y, and z dimensions of at least 5 mm, a density in a range from 30 to 95 percent of theoretical density, and an average connected pore size in a range from 10 nm to 100 nm, wherein at least 70 mole percent of the metal oxide is crystalline ZrO 2 , and wherein the crystalline ZrO 2 has an average grain size less than 100 nm; and
heating the crack-free, calcined metal oxide article for a time and at one or more temperatures sufficient to provide the crack-free, crystalline metal oxide article having x, y, and z dimensions of at least 3 mm and a density of at least 98.5 percent of theoretical density, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 , and wherein the crystalline metal oxide has an average grain size less than 400 nanometers.

2. The method of claim 1 , wherein providing a monolithic aerogel comprises:
providing a first zirconia sol comprising crystalline metal oxide particles having an average primary particle size of not greater than 50 nanometers, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 ;
optionally concentrating the first zirconia sol to provide as concentrated zirconia sol;
adding a radically reactive surface modifier to the zirconia sol to provide a radically polymerizable surface-modified zirconia sol;
adding a radical initiator to the radically polymerizable surface-modified zirconia sol;
heating at a temperature for a time sufficient to polymerize the radically surface-modified zirconia sol comprising the radical initiator to form a gel;
optionally removing water, if present, from the gel via alcohol exchange to provide an at least partially de-watered gel; and
extracting alcohol, if present, from the gel via super critical extraction to provide the monolithic aerogel.

3. The method of claim 1 , wherein heating the crack-free, calcined metal oxide article is at a temperature in a range from 1150° C. to 1300° C.

4. The method of claim 1 , wherein providing a monolithic aerogel comprises:
providing a first zirconia sol comprising crystalline metal oxide particles having an average primary particle size of not greater than 50 nanometers, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 ;
optionally concentrating the first zirconia sol to provide as concentrated zirconia sol;
adding a radically reactive surface modifier to the zirconia sol to provide a radically polymerizable surface-modified zirconia sol;
adding a radical initiator to the radically polymerizable surface-modified zirconia sol;
radiating with actinic radiation for a time sufficient to polymerize the radically surface-modified zirconia sol comprising the radical initiator to form a gel;
optionally removing water, if present, from the gel via alcohol exchange to provide an at least partially de-watered gel; and
extracting alcohol, if present, from the gel via super critical extraction to provide the monolithic aerogel.

5. The method of claim 1 , the method further comprising chemically treating the crack-free, calcined metal oxide article to remove volatile ions.

6. The method of claim 1 , wherein 1 to 15 mole percent of the crystalline metal oxide in the monolithic aerogel is Y 2 O 3 .

7. The method of claim 1 , wherein the crystalline metal oxide in the monolithic aerogel further comprises at least one of Y 2 O 3 or La 2 O 3 .

8. The method of claim 1 , wherein the ZrO2 in the crack-free crystalline material is all tetragonal ZrO 2 or is all cubic ZrO 2 .

9. The method of claim 1 , wherein the ZrO2 comprises cubic and tetragonal ZrO 2 .

10. The method of claim 1 , wherein the crack-free, crystalline metal oxide article is translucent or opalescent.

11. The method of claim 1 , wherein heating the crack-free, calcined metal oxide article is conducted at less than 1.25 atmospheres of pressure.

12. The method of claim 2 , further comprising adding a radically reactive co-monomer to the radically polymerizable surface-modified zirconia sol.

13. The method of claim 4 , further comprising adding a radically reactive co-monomer to the radically polymerizable surface-modified zirconia sol.

14. The method of claim 2 , wherein the first zirconia sol comprises crystalline metal oxide particles having an average primary particle size of not greater than 15 nanometers.

15. The method of claim 2 , wherein the first zirconia sol comprises crystalline metal oxide particles having volume-average size up to 15 nanometers.

16. The method of claim 4 , wherein the first zirconia sol comprises crystalline metal oxide particles having an average primary particle size of not greater than 15 nanometers.

17. The method of claim 4 , wherein the first zirconia sol comprises crystalline metal oxide particles having volume-average size up to 15 nanometers.

18. A crack-free, crystalline metal oxide article having x, y, and z dimensions of at least 3 mm and a density of at least 98.5 percent of theoretical density, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 wherein the at least 6 mole percent of the crystalline metal oxide is Y 2 O 3 , and wherein the crystalline metal oxide has an average grain size in a range from 75 nanometers to 400 nanometers.

19. The crack-free, crystalline metal oxide article of claim 18 , wherein the crystalline metal oxide further comprises 6 to 9 mole percent Y 2 O 3 , and wherein the crystalline metal oxide has an average grain size in a range from 100 nanometers to 400 nanometers.

20. The crack-free, crystalline metal oxide article of claim 18 , wherein the article is translucent or opalescent.

21. A crack-free, crystalline metal oxide article having x, y, and z dimensions of at least 10 mm and a density of at least 98.5 percent of theoretical density, wherein at least 70 mole percent of the crystalline metal oxide is ZrO 2 , and wherein the crystalline metal oxide has an average grain size in a range from 75 nanometers to 400 nanometers.

22. The crack-free, crystalline metal oxide article of claim 21 , wherein 1 to 15 mole percent of the crystalline metal oxide is Y 2 O 3 .

Assignees

• Kolb Brant U
• Feisel Bryan C
• Goetzinger Martin
• Hall Philip S
• Hauptmann Holger
• Hendrickson Mark J
• Humpal Kathleen M
• Longabach John W
• Mathers James P
• Naujok Roberta R
• Pennington Paul D
• Schechner Gallus
• 3M Innovative Properties Co

Inventors

• Kolb Brant U
• Feisel Bryan C
• Goetzinger Martin
• Hall Philip S
• Hauptmann Holger
• Hendrickson Mark J
• Humpal Kathleen M
• Longabach John W
• Mathers James P
• Naujok Roberta R
• Pennington Paul D
• Schechner Gallus

Classifications

• A61K6/887

  Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• A61K6/17

  Particle size · CPC title

• A61K6/822

  comprising rare earth metal oxides · CPC title

• A61K6/15

  Compositions characterised by their physical properties · CPC title

• A61K6/824

  comprising transition metal oxides · CPC title