SCRATCH-RESISTANT LIQUID BASED COATINGS FOR GLASS

• US 20150132563A1
• Filed: 11/08/2013
• Published: 05/14/2015
• Est. Priority Date: 11/08/2013
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: O'Malley, Shawn Michael, Schneider, Vitor Marino
• Granted Patent: US 9,663,400 B2
• Time in Patent Office: Days
• US Class Current: 428/312.8
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 17/256 Coating containing TiO2
• CPC Class Codes: C03C 2217/22 ZrO2
• CPC Class Codes: C03C 2217/425 consisting of a porous layer
• CPC Class Codes: C03C 2217/45 Inorganic continuous phases
• CPC Class Codes: C03C 2217/475 Inorganic materials
• CPC Class Codes: C03C 2217/76 Hydrophobic and oleophobic coatings
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: C03C 2218/32 After-treatment
• CPC Class Codes: C23C 18/06 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 18/1216 Metal oxides C23C18/1212 takes precedence
• CPC Class Codes: C23C 18/1245 Inorganic substrates other than metallic
• CPC Class Codes: C23C 18/1254 Sol or sol-gel processing
• CPC Class Codes: C23C 18/127 Preformed particles
• CPC Class Codes: C23C 18/1283 Control of temperature, e.g. gradual temperature increase, modulation of temperature
• CPC Class Codes: Y10T 428/24997 Of metal-containing material

Abstract

A sol-gel method for forming durable, scratch-resistant coatings on glass substrates. Zirconia coatings, for example, are formed from a solution of zirconium oxychloride octahydrate in an organic, polar, aprotic solvent such as dimethylformamide. Annealed coatings, which optionally include an additive such as graphene, have a low coefficient of friction and can exhibit high hardness and hydrophobicity.

Claims

1. A method comprising:

providing a solution comprising a metal salt, an organo-metallic compound, or combinations thereof in a polar aprotic solvent;

depositing the solution onto a glass substrate to form a coating on the substrate; and

annealing the coating.

2. The method according to claim 1, wherein the metal salt comprises aluminum, zirconium, titanium, nickel, zinc, yttrium, scandium or combinations thereof.

3. The method according to claim 1, wherein the organo-metallic compound comprises aluminum, zirconium, titanium, nickel, zinc, yttrium, scandium or combinations thereof.

4. The method according to claim 1, wherein the solvent is selected from the group consisting of dimethylformamide, tetrahydrofuran, ethyl acetate, acetone, dichloromethane, acetonitrile, dimethyl sulfoxide and n-methyl pyrrolidone.

5. The method according to claim 1, wherein the metal salt comprises zirconium oxychloride.

6. The method according to claim 1, wherein the metal salt comprises zirconium oxychloride and the solvent comprises dimethylformamide.

7. The method according to claim 1, wherein the solution has a concentration of 0.05 to 2 M.

8. The method according to claim 1, further comprising adding semiconductor nanoparticles, metal nanoparticles, graphene, or a combination thereof dispersed in a polar aprotic solvent to the solution prior to the depositing.

9. The method according to claim 8, wherein the nanoparticles are in the form of nanotubes, nanowires, nanodots, or combinations thereof.

10. The method according to claim 1, wherein the depositing comprises spin-coating, dip-coating, spray-coating, tape-casting, ink jet, slot dye coating, misting, stamping, or washing the substrate in the solution.

11. The method according to claim 1, wherein the depositing comprises forming a patterned coating.

12. The method according to claim 1, wherein the annealing comprises heating the coating at 150°

C. to 450°

C.

13. The method according to claim 1, wherein the annealing comprises first heating the coating at 150°

C. to 450°

C., and then heating the coating at 90°

C. to 120°

C.

14. The method according to claim 1, further comprising crystallizing the coating after the annealing.

15. The method according to claim 1, further comprising crystallizing the coating during the annealing.

16. The method according to claim 1, wherein the providing comprises mixing at least one of zirconium oxychloride octahydrate or zirconium acetylacetonate in dimethylformamide to form a first solution, separately mixing titanium isopropoxide in dimethylformamide to form a second solution, and combining the first and second solutions to a desired atom concentration of zirconium and titanium.

17. The method according to claim 1, wherein the glass substrate comprises chemically-strengthened glass.

18. A method comprising:

providing a solution comprising zirconium oxychloride and titanium isopropoxide in a polar aprotic solvent;

depositing the solution onto a substrate to form a coating on the substrate; and

annealing the coating.

19. A glass article comprising

a glass substrate;

an inorganic coating selected from the group consisting of a zirconia coating, a titania coating and a zirconia-titania coating disposed over at least a portion of a major surface of the glass substrate; and

particles of an additive dispersed throughout the coating.

20. The glass article according to claim 19, wherein the additive particles are selected from the group consisting of nanotubes, nanowires, nanodots, semiconductor nanoparticles, metal nanoparticles, graphene, and combinations thereof.

21. The glass article according to claim 19, wherein the inorganic coating is porous.

22. The glass article according to claim 19, further comprising carbon and/or chlorine localized within pores of the inorganic coating.

23. The glass article according to claim 19, wherein the inorganic coating is hydrophobic.

24. The glass article according to claim 19, wherein the glass substrate comprises ion-exchanged glass.