Antimicrobial glass articles and methods of making and using same

Patent metadata

Field	Value
Publication number	US-10131574-B2
Application number	US-201414306317-A
Country	US
Kind code	B2
Filing date	Jun 17, 2014
Priority date	Jun 17, 2013
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

Described herein are various antimicrobial glass articles that have improved resistance to discoloration when exposed to harsh conditions. The improved antimicrobial glass articles described herein generally include a glass substrate that has a low concentration of nonbridging oxygen atoms, a compressive stress layer and an antimicrobial silver-containing region that each extend inward from a surface of the glass substrate to a specific depth, such that the glass article experiences little-to-no discoloration when exposed to harsh conditions. Methods of making and using the glass articles are also described.

First claim

What is claimed is:

1. A method of making an antimicrobial glass article, the method comprising:
providing a glass substrate;
forming a compressive stress layer that extends inward from a surface of the glass substrate to a first depth;
forming an antimicrobial ionic silver-containing region that extends inward from the surface of the glass substrate to a second depth, the surface of the glass substrate containing a haze-inducing residue containing ionic silver; and
chemically cleaning the glass substrate after the forming steps by contacting the glass substrate with a cleaning solution at an ambient temperature for less than or equal to about 15 minutes to remove the haze-inducing residue containing ionic silver from the surface of the glass substrate, wherein the cleaning solution comprises any one of:
ammonium hydroxide and hydrogen peroxide in water;
about 0.01 wt % to about 5 wt % sodium chloride in water, and
about 0.01 wt % to about 5 wt % citric acid in water.

2. The method of claim 1 , further comprising:
contacting the glass substrate with a rinsing agent after the step of chemically cleaning the glass substrate.

3. The method of claim 2 , wherein the step of contacting the glass substrate with a rinsing agent comprises:
immersing the glass substrate in the rinsing agent; and
spraying the glass substrate with the rinsing agent after the immersing.

4. The method of claim 1 , wherein the second depth is less than the first depth, and the glass substrate comprises a low concentration of nonbridging oxygens.

5. The method of claim 1 , wherein the antimicrobial ionic silver-containing region comprises a silver concentration of about 5 weight percent or greater, based on the total weight of the antimicrobial silver-containing region.

6. The method of claim 1 , further comprising:
forming an additional layer on at least a portion of the surface of the substrate, wherein the additional layer comprises a reflection-resistant coating, a glare-resistant coating, fingerprint-resistant coating, smudge-resistant coating, a color-providing composition, an environmental barrier coating, or an electrically conductive coating.

7. The method of claim 4 , wherein the concentration of nonbridging oxygens in the glass substrate is in the range from about −1 mol % to about 20 mol %.

8. The method of claim 1 , wherein a compressive stress of the compressive stress layer is about 200 megapascals to about 1.2 gigapascals and the first depth is less than about 100 micrometers (μm), and the antimicrobial ionic silver-containing region has an average thickness of less than or equal to about 20 micrometers (μm).

9. The method of claim 8 , wherein a silver concentration at an outermost 50 nanometers (nm) of the antimicrobial ionic silver-containing region is up to about 45 weight percent, based on a total weight of the outermost 50 nanometers (nm) of the antimicrobial ionic silver-containing region.

10. The method of claim 1 , wherein a compressive stress of the compressive stress layer is about 200 megapascals to about 1.2 gigapascals and the first depth is less than about 100 micrometers (μm), and the antimicrobial ionic silver-containing region has an average thickness of up to about 150 micrometers (μm).

11. The method of claim 1 , wherein ammonium hydroxide and hydrogen peroxide in water are each present in an amount of less than 2 volume percent.

12. The method of claim 1 , wherein contacting the glass substrate with a cleaning solution includes using ultrasonic agitation while the glass substrate is contacted with the cleaning solution.

13. The method of claim 1 , wherein the cleaning solution comprises any one of:
about 0.01 wt % to about 5 wt % sodium chloride in water; and
about 0.01 wt % to about 5 wt % citric acid in water.

14. The method of claim 1 , wherein the cleaning solution comprises about 0.01 wt % to about 5 wt % sodium chloride in water.

15. The method of claim 1 , wherein the cleaning solution comprises about 0.01 wt % to about 5 wt % citric acid in water.

16. A method of making an antimicrobial glass article, the method comprising:
providing a glass substrate;
forming a compressive stress layer that extends inward from a surface of the glass substrate to a first depth;
forming an antimicrobial ionic silver-containing region that extends inward from the surface of the glass substrate to a second depth, the surface of the glass substrate containing a haze-inducing residue containing ionic silver; and
chemically cleaning the glass substrate after the forming steps by contacting the glass substrate with a chemical cleaning solution to remove the haze-inducing residue containing ionic silver from the surface of the glass substrate and to form an antimicrobial glass article exhibiting an average haze of about 0.1% or less.

17. The method of claim 16 , wherein the chemical cleaning solution comprises any one of:
ammonium hydroxide and hydrogen peroxide in water;
about 0.01 wt % to about 5 wt % sodium chloride in water, and
about 0.01 wt % to about 5 wt % citric acid in water.

18. The method of claim 17 , wherein ammonium hydroxide and hydrogen peroxide in water are each present in an amount of less than 2 volume percent.

19. The method of claim 16 , further comprising:
contacting the glass substrate with a rinsing agent after the step of chemically cleaning the glass substrate.

20. The method of claim 19 , wherein the step of contacting the glass substrate with a rinsing agent comprises:
immersing the glass substrate in the rinsing agent; and
spraying the glass substrate with the rinsing agent after the immersing.

21. The method of claim 16 , wherein contacting the glass substrate with a chemical cleaning solution comprises a contact time of less than or equal to about 15 minutes.

22. The method of claim 16 , wherein contacting the glass substrate with a cleaning solution includes using ultrasonic agitation while the glass substrate is contacted with the cleaning solution.

23. The method of claim 16 , wherein the cleaning solution comprises any one of:
about 0.01 wt % to about 5 wt % sodium chloride in water; and
about 0.01 wt % to about 5 wt % citric acid in water.

24. The method of claim 16 , wherein the cleaning solution comprises about 0.01 wt % to about 5 wt % sodium chloride in water.

25. The method of claim 16 , wherein the cleaning solution comprises about 0.01 wt % to about 5 wt % citric acid in water.

Assignees

• Corning Inc

Inventors

• Jin Yuhui
• Milia Charlotte Diane
• Wolcott Christine Coulter

Classifications

• C03C21/002

  to perform ion-exchange between alkali ions (C03C21/005 takes precedence) · CPC title

• Y10T428/315

  Surface modified glass [e.g., tempered, strengthened, etc.] · CPC title

• A01N59/16

  Heavy metals; Compounds thereof · CPC title

• A01N25/08

  containing solids as carriers or diluents · CPC title

• C03C2204/02

  Antibacterial glass, glaze or enamel · CPC title