Antimicrobial glass articles and methods of making and using same
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.
1. An antimicrobial glass article, comprising:
a glass substrate comprising a compressive stress layer that extends inward from a surface of the glass substrate to a first depth therein, and an antimicrobial silver-containing region that extends inward from the surface of the glass substrate to a second depth therein, wherein the glass article exhibits substantially no discoloration that is attributable to the presence of non-bridging oxygens upon exposure of the glass article to harsh conditions,
wherein the harsh conditions are a gas mix of argon and oxygen and plasma generation at 50 W for 3 minutes, followed by a thermal treatment of 120° C. for about 30 minutes, and
further wherein the glass substrate comprises a concentration of nonbridging oxygens of about 0.67 mol % to about 0.35 mol %.
2. The antimicrobial glass article of claim 1 , wherein the second depth is less than the first depth.
3. The antimicrobial glass article of claim 1 , wherein the antimicrobial silver-containing region comprises a silver concentration of about 5 weight percent or greater, based on a total weight of the antimicrobial silver-containing region.
4. The antimicrobial glass article of claim 1 , further comprising an additional layer disposed on the surface of the glass substrate.
5. The antimicrobial glass article of claim 4 , wherein the additional layer is selected from the group consisting of a reflection-resistant coating, a glare-resistant coating, fingerprint-resistant coating, smudge-resistant coating, a color-providing composition, an environmental barrier coating, and an electrically conductive coating.
6. The antimicrobial glass article of claim 1 , wherein a compressive stress of the compressive stress layer is about 200 megapascals to about 1.2 gigapascals and the depth of the compressive stress layer is less than about 100 micrometers (μm).
7. The antimicrobial glass article of claim 1 , wherein the antimicrobial silver-containing region has an average thickness of less than or equal to about 20 micrometers (μm).
8. The antimicrobial glass article of claim 7 , wherein a silver concentration at an outermost 50 nanometers (nm) of the antimicrobial silver-containing region is up to about 45 weight percent, based on a total weight of this outermost 50 nanometers (nm) of the antimicrobial silver-containing region.
9. The antimicrobial glass article of claim 1 , wherein the antimicrobial silver-containing region has an average thickness of up to about 150 micrometers (μm).
10. The antimicrobial glass article of claim 1 , wherein the antimicrobial silver-containing region has an average thickness in the range from about 20 micrometers (μm) to about 150 micrometers (μm).
11. The antimicrobial glass article of claim 9 , wherein a silver concentration at an outermost 50 nanometers of the antimicrobial silver-containing region is up to about 6 weight percent, based on a total weight of this outermost 50 nanometers of the antimicrobial silver-containing region.
12. The antimicrobial glass article of claim 1 , wherein the substantially no discoloration that is attributable to the presence of non-bridging oxygens upon exposure of the glass article to the harsh conditions comprises at least one of:
a change in optical transmittance of the glass article of less than or equal to about 3 percent relative to an optical transmittance before exposure to the harsh conditions,
a change in haze of the glass article of less than or equal to about 5 percent relative to a haze before exposure to the harsh conditions, and
a change in CIE 1976 color coordinates L*, a*, and b* of the glass article of less than or equal to about ±0.2, ±0.1, and ±0.1, respectively.
13. The antimicrobial glass article of claim 1 , wherein the antimicrobial glass article exhibits at least a 5 log reduction in a concentration of at least Staphylococcus aureus, Enterobacter aerogenes , and Pseudomonas aeruginosa bacteria under JIS Z 2801 (2000) testing conditions.
14. The antimicrobial glass article of claim 1 , wherein the antimicrobial glass article exhibits at least a 3 log reduction in a concentration of at least Staphylococcus aureus, Enterobacter aerogenes , and Pseudomonas aeruginosa bacteria under modified JIS Z 2801 (2000) testing conditions, wherein the modified conditions comprise heating the antimicrobial glass article to a temperature of about 23 degrees Celsius to about 37 degrees Celsius at a humidity of about 38 percent to about 42 percent for about 24 hours followed by drying for about 6 hours to about 24 hours.
15. The antimicrobial glass article of claim 1 , wherein the antimicrobial glass article exhibits at least a 2 log reduction in the concentration of at least Staphylococcus aureus, Enterobacter aerogenes , and Pseudomonas aeruginosa bacteria under a Dry Test.
16. The antimicrobial glass article of claim 1 , wherein the antimicrobial glass article is selected from the group consisting of a portion of a touch-sensitive display screen or cover plate for an electronic device, a non-touch-sensitive component of an electronic device, a surface of a household appliance, a surface of medical equipment, a biological or medical packaging vessel, and a surface of a vehicle component.
17. 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; and
forming an antimicrobial silver-containing region that extends inward from the surface of the glass substrate to a second depth, wherein the glass article undergoes substantially no discoloration that is attributable to the presence of non-bridging oxygens upon exposure of the glass article to harsh conditions,
wherein the harsh conditions are a gas mix of argon and oxygen and plasma generation at 50 W for 3 minutes, followed by a thermal treatment of 120° C. for about 30 minutes, and
further wherein the glass substrate comprises a concentration of nonbridging oxygens of about 0.67 mol % to about 0.35 mol %.
18. The method of claim 17 , wherein the second depth is less than the first depth.
19. The method of claim 17 , wherein the antimicrobial 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.
20. The method of claim 17 , further comprising forming an additional layer on at least a portion of the surface of the substrate, wherein the additional layer is selected from the group consisting of a reflection-resistant coating, a glare-resistant coating, fingerprint-resistant coating, smudge-resistant coating, a color-providing composition, an environmental barrier coating, and an electrically conductive coating.
21. The method of claim 17 , wherein a compressive stress of the compressive stress layer is about 200 megapascals to about 1.2 gigapascals and the depth of the compressive stress layer is less than about 100 micrometers (μm), and the antimicrobial silver-containing region has an average thickness of less than or equal to about 20 micrometers (/lm).
22. The method of claim 21 , wherein a silver concentration at an outermost 50 nanometers of the antimicrobial silver-containing region is up to about 45 weight percent, based on a total weight of this outermost 50 nanometers of the antimicrobial silver-containing region.
23. The method of claim 17 , wherein a compressive stress of the compressive stress layer is about 200 megapascals to about 1.2 gigapascals and the depth of the compressive stress layer is less than about 100 micrometers (μm), and the antimicrobial silver-containing region has an average thickness of up to about 150 micrometers (μm).
24. The method of claim 17 , wherein the antimicrobial silver-containing region has an average thickness in the range from about 20 micrometers (μm) to about 150 micrometers (μm).
25. The method of claim 23 , wherein a silver concentration at an outermost 50 nanometers of the antimicrobial silver-containing region is up to about 6 weight percent, based on a total weight of this outermost 50 nanometers of the antimicrobial silver-containing region.
26. The method of claim 17 , wherein the substantially no discoloration that is attributable to the presence of non-bridging oxygens upon exposure of the glass article to the harsh conditions comprises at least one of:
a change in optical transmittance of the glass article of less than or equal to about 3 percent relative to an optical transmittance before exposure to the harsh conditions,
a change in haze of the glass article of less than or equal to about 5 percent relative to a haze before exposure to the harsh conditions, and
a change in CIE 1976 color coordinates L*, a*, and b* of the glass article of less than or equal to about ±0.2, ±0.1, and ±0.1, respectively.
27. The method of claim 17 , wherein forming the compressive stress layer and forming the antimicrobial silver-containing region occur simultaneously.