IP Library › Granted Patent US 12,441,661
Granted Patent B2
US 12,441,661 · App. 17/543,630 · Granted Oct 14, 2025

Metal oxide ceramic nanomaterials and methods of making and using same

Inventors: Wei Xu (Basking Ridge, NJ); Yijun Wang (Basking Ridge, NJ); Dmitri Brodkin (Livingston, NJ)
Assignee: Ivoclar Vivadent AG
C04B35/486A61K6/17A61K6/818B01D61/002B01D61/005C01G25/02C02F1/445C04B35/488C04B35/4885C04B35/624C04B35/63416C04B35/63488C04B35/638C08K3/22C08L71/02B01D2311/02B01D2311/04C01P2004/64C02F2103/12C04B2235/3217C04B2235/5454C04B2235/5463C04B2235/602C04B2235/606C04B2235/608C04B2235/61C04B2235/612C04B2235/762C04B2235/765C04B2235/77C04B2235/781C04B2235/785C04B2235/96C04B2235/9653
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,441,661
App. No.
17/543,630
Granted
Oct 14, 2025
Kind
B2
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).

Claims (13)

1. 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.

2. A gel comprising a plurality of zirconia nanoparticles and water, wherein the zirconia nanoparticles have an average size of 10 to 30 nm, the zirconia nanoparticles are present at 70 to 85% by weight based on the total weight of the gel and the gel is free-standing and exhibits a viscosity at yield point of 1×10 9 to 50×10 9 mPa·s.

3. The gel of claim 2 , wherein the viscosity at yield point is 1×10 9 to 12×10 9 mPa·s and the gel is formable.

4. The gel of claim 3 , wherein the viscosity at yield point is 1×10 9 to 4×10 9 mPa·s and the gel is very soft.

5. The gel of claim 3 , wherein the viscosity at yield point is 4×10 9 to 8×10 9 mPa·s and the gel is soft.

6. The gel of claim 3 , wherein the viscosity at yield point is 8×10 9 to 12×10 9 mPa·s and the gel is semi-soft.

7. The gel of claim 2 , wherein the viscosity at yield point is 12×10 9 to 50×10 9 mPa·s and the gel is semi-rigid and not formable.

8. A gel comprising a plurality of zirconia nanoparticles and water, wherein 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 free-standing and exhibits a viscosity at yield point of 1×10 9 to 50×10 9 mPa·s.

9. The gel of claim 8 , wherein the viscosity at yield point is 1×10 9 to 12×10 9 mPa·s and the gel is formable.

10. The gel of claim 9 , wherein the viscosity at yield point is 1×10 9 to 4×10 9 mPa·s and the gel is very soft.

11. The gel of claim 9 , wherein the viscosity at yield point is 4×10 9 to 8×10 9 mPa·s and the gel is soft.

12. The gel of claim 9 , wherein the viscosity at yield point is 8×10 9 to 12×10 9 mPa·s and the gel is semi-soft.

13. The gel of claim 8 , wherein the viscosity at yield point is 12×10 9 to 50×10 9 mPa's and the gel is semi-rigid and not formable.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 6, 2021
From: XU, WEI; WANG, YIJUN; BRODKIN, DMITRI
To: IVOCLAR VIVADENT AG
Reel/Frame 058313/0039 →
Continuity (4)
Continuation 15817994 · Nov 20, 2017
Continuation 15388165 · Dec 22, 2016
Division 15240673 · Aug 18, 2016
Related Publication 20220089502A1 · Mar 24, 2022
References Cited (80)
US 2467089A · Griest · 1949 [cited by applicant]
US 4758541A · Tsukuma · 1988 [cited by applicant]
US 4963264A · Davis · 1990 [cited by applicant]
US 5553630A · Dupuis · 1996 [cited by applicant]
US 6232367B1 · Kobashigawa · 2001 [cited by applicant]
US 6376590B2 · Kolb et al. · 2002 [cited by applicant]
US 6787080B1 · Lange et al. · 2004 [cited by applicant]
US 6869501B2 · Davidson et al. · 2005 [cited by applicant]
US 7241437B2 · Davidson et al. · 2007 [cited by applicant]
US 7429422B2 · Davidson et al. · 2008 [cited by applicant]
US 7538055B2 · Tsukuma et al. · 2009 [cited by applicant]
US 7655586B1 · Brodkin et al. · 2010 [cited by applicant]
US 7674523B2 · Davidson et al. · 2010 [cited by applicant]
US 7806694B2 · Brodkin et al. · 2010 [cited by applicant]
US 7833621B2 · Jones et al. · 2010 [cited by applicant]
US 7989504B2 · Adam et al. · 2011 [cited by applicant]
US 8216439B2 · Olevsky et al. · 2012 [cited by applicant]
US 8298329B2 · Knapp et al. · 2012 [cited by applicant]
US 8309015B2 · Rolf et al. · 2012 [cited by applicant]
US 8425809B2 · Ketharam et al. · 2013 [cited by applicant]
US 8598058B2 · Mathers et al. · 2013 [cited by applicant]
US 8969227B2 · Mathers et al. · 2015 [cited by applicant]
US 9120200B2 · Haerle · 2015 [cited by applicant]
US 9657152B2 · Kolb et al. · 2017 [cited by applicant]
US 9820917B1 · Xu · 2017 [cited by examiner]
US 9822039B1 · Xu et al. · 2017 [cited by applicant]
US 11208355B2 · Xu · 2021 [cited by examiner]
US 20040222098A1 · Clasen et al. · 2004 [cited by applicant]
US 20080242746A1 · Morimura et al. · 2008 [cited by applicant]
US 20090004098A1 · Schmidt et al. · 2009 [cited by applicant]
US 20090074655A1 · Suciu · 2009 [cited by applicant]
US 20090115084A1 · Moon · 2009 [cited by applicant]
US 20090189115A1 · Suciu · 2009 [cited by applicant]
US 20090208746A1 · Suciu · 2009 [cited by applicant]
US 20090274993A1 · Bergstrom et al. · 2009 [cited by applicant]
US 20090294357A1 · Binner et al. · 2009 [cited by applicant]
US 20100003630A1 · Yamashita et al. · 2010 [cited by applicant]
US 20100075170A1 · Adair et al. · 2010 [cited by applicant]
US 20110027742A1 · Fujisaki et al. · 2011 [cited by applicant]
US 20110230340A1 · Binner et al. · 2011 [cited by applicant]
US 20120058883A1 · Yamashita et al. · 2012 [cited by applicant]
US 20120264588A1 · Kolb et al. · 2012 [cited by applicant]
US 20120277088A1 · Mathers et al. · 2012 [cited by applicant]
US 20130313738A1 · Carden · 2013 [cited by applicant]
US 20140057774A1 · Mathers et al. · 2014 [cited by applicant]
US 20140147387A1 · Butts et al. · 2014 [cited by applicant]
US 20150238291A1 · Hauptmann et al. · 2015 [cited by applicant]
US 20150328613A1 · Shi et al. · 2015 [cited by applicant]
US 20160095798A1 · Brodkin et al. · 2016 [cited by applicant]
US 20170231730A1 · Shen et al. · 2017 [cited by applicant]
US 20180170812A1 · Xu et al. · 2018 [cited by applicant]
US 20220089501A1 · Xu · 2022 [cited by examiner]
EP 2692311 · 2014 [cited by applicant]
WO 2014209626 · 2014 [cited by applicant]
Adam, et al., “Milling of Zirconia Nanoparticles in a Stirred Media Mill,” J. Am. Ceram. Soc., 2008, vol. 91 , No. 9, pp. 2836-2843. Jan. 1, 2008. [cited by applicant]
Alaniz, J.E., et al., “Optical Properties of Transparent Nanocrystalline Yttria Stabilized Zirconia,” Optical Materials, Jul. 16, 2009, vol. 32, pp. 62-68. Jul. 16, 2009. [cited by applicant]
Anselmi-Tamburini, U. et al., “Transparent Nanometric Cubic and Tetragonal Zirconia Obtained by High-Pressure Pulsed Electric Current Sintering,” Adv. Funct. Mater., 2007, vol. 17, pp. 3267-3273. Jan. 1, 2007. [cited by applicant]
Apetz, R., et al., “Transparent Alumina: A Light Scattering Model,” J. Am. Ceram. Soc., 2003, vol. 86, No. 3, pp. 480-786. Jan. 1, 2003. [cited by applicant]
Binner, J., et al., “Compositional Effects in Nanostructured Yttria Partially Stabilized Zirconia,” Int. J. Appl. Ceram. Tec., 2011, vol. 8, pp. 766-782. Jan. 1, 2011. [cited by applicant]
Binner, J., et al., “Processing of Bulk Nanostructured Ceramics,” J. Eur. Ceram. Soc., 2008, vol. 28, pp. 1329-1339. Jan. 1, 2008. [cited by applicant]
Casolco, S.R. et al., “Transparent/translucent polycrystalline nanostructured yttria stabilized zirconia with varying colors,” Scripta Mater., 2007, vol. 58, No. 6, pp. 516-519. Jan. 1, 2007. [cited by applicant]
Cho, M.-S., et al., “Opalescence of all-ceramic core and veneer materials,” Dental Materials, 2009, vol. 25, pp. 695-702. Jan. 1, 2009. [cited by applicant]
Dialysis, Obtained from https://www.merriam-webster.com/dictionary/dialysis on Jan. 8, 2017. Jan. 8, 2017. [cited by applicant]
Egen, M., et al., “Artificial Opals as Effect Pigments in Clear-Coatings,” Macromol. Mater. Eng., 2004, vol. 289, pp. 158-163. Jan. 1, 2004. [cited by applicant]
Garcia, J.C., et al., “Structural, Electronic, and Optical Properties of ZrO2 from Ab Initio Calculations,” J. Appl. Phys., 2006, vol. 100, No. 1, 104103, 10 pages. Jan. 1, 2006. [cited by applicant]
Klimke, J. , et al., “Transparent Tetragonal Yttria-Stabilized Zirconia Ceramics,” J. Am. Ceram. Soc., 2011, vol. 94, No. 6, pp. 1850-1858. Jan. 1, 2011. [cited by applicant]
Knapp, K., “Understanding Zirconia Crown Esthetics and Optical Properties,” Inclusive Magazine, 2011, 6 pages. Jan. 1, 2011. [cited by applicant]
Lee, Y-K., et al., “Measurement of Opalescence of Tooth Enamel,” Journal of Dentistry, 2007, vol. 35, pp. 690-694. Jan. 1, 2007. [cited by applicant]
Lee, Y-K., “Influence of Scattering/Absorption Characteristics on the Color of Resin Composites,” Dental Materials, 2007, vol. 23, pp. 124-131. Jan. 1, 2007. [cited by applicant]
Lee, Y-K., et al., “Changes in Opalescence and Fluorescence Properties of Resin Composites after Accelerated Aging,” Dental Materials, 2006, vol. 22, pp. 653-660. Jan. 1, 2006. [cited by applicant]
Lee, Y-K., et al., “Measurement of Opalescence of Resin Composites,” Dental Materials, 2005, vol. 21, pp. 1068-1074. Jan. 1, 2005. [cited by applicant]
Peelen. J.G.J., et al., “Light Scattering by Pores in Polycrystalline Materials: Transmission Properties of Alumina,” Journal of Applied Physics, 1974, vol. 45, pp. 216-220. Jan. 1, 1974. [cited by applicant]
Primus, C.M., et al., “Opalescence of Dental Porcelain Enamels,” Quintessence International, 2002, vol. 33, pp. 439-449. Jan. 1, 2002. [cited by applicant]
Rignanese, G.M., et al., “First-principles Study of the Dynamical and Dielectric Properties of Tetragonal Zirconia,” Phys. Rev. B,, Aug. 31, 2001, vol. 64, No. 13, 134301, 7 pages. Jan. 1, 2001. [cited by applicant]
Schwartz, L., et al., “Introduction to Tangential Flow Filtration for Laboratory and Process Development Applications,” Obtained from http://www.pall.com/main/laboratory/literature-library-details.page?id=34212 on Jan. … [cited by applicant]
Srdic, V.V., et al., “Sintering Behavior of Nanocrystalline Zirconia Prepared by Chemical Vapor Synthesis,” J. Am. Ceram. Soc., 2000, vol. 83, No. 4, pp. 729-736. Jan. 1, 2000. [cited by applicant]
Srdic, V.V., et al., “Sintering Behavior of Nanocrystalline Zirconia Doped with Alumina Prepared by Chemical Vapor Synthesis,” J. Am. Ceram. Soc., 2000, vol. 83, No. 8, pp. 1853-1860. Jan. 1, 2000. [cited by applicant]
Trunec, M., et al., “Compaction and Presureless Sintering of Zirconia Nanoparticles,” J. Am. Ceram. Soc., 2007, vol. 90, No. 9, pp. 2735-2740. Jan. 1, 2007. [cited by applicant]
White, S.N., et al., “Biological Organization of Hydroxyapatite Crystallites into a Fibrous Continuum Toughens and Controls Anisotropy in Human Enamel,” J.Dent. Res, Jan. 1, 2001, vol. 80, No. 1, pp. 321-326. Jan. 1, 20… [cited by applicant]
Yu, B., et al., “Difference in Opalescence of Restorative Materials by the Illuminant,” Dental Materials, 2009, vol. 25, pp. 1014-1021. Jan. 1, 2009. [cited by applicant]