Coated, antimicrobial, chemically strengthened glass and method of making
The disclosure is directed to a chemically strengthened glass having antimicrobial properties and to a method of making such glass. In particular, the disclosure is directed to a chemically strengthened glass with antimicrobial properties and with a low surface energy coating on the glass that does not interfere with the antimicrobial properties of the glass. The antimicrobial has an Ag ion concentration on the surface in the range of greater than zero to 0.047 μg/cm 2 . The glass has particular applications as antimicrobial shelving, table tops and other applications in hospitals, laboratories and other institutions handling biological substances, where color in the glass is not a consideration.
1. A method of making an antimicrobial, chemically strengthened glass article, said method comprising:
providing a glass article having a first surface, and a plurality of ion exchangeable alkali metal ions;
providing a first ion-exchange bath comprising a plurality of first ion exchanging alkali metal ions, each having a larger size than the size of the ion exchangeable alkali metal ions, and ion exchanging a portion of the plurality of ion exchangeable alkali metal ions in the glass article for the first ion exchanging alkali metal ions in the first ion-exchange bath to impart a compressive stress greater than 250 MPa into the glass article;
providing a second ion-exchange bath comprising 0.005 wt % to 10 wt % silver nitrate having a plurality of silver ions and a plurality of the first ion exchanging alkali metal ions;
ion-exchanging the glass article with the compressive stress greater than 250 MPa in the second ion-exchange bath to ion exchange a portion of the silver ions and a portion of said first ion exchanging alkali metal ions into the first surface to form a glass article having a compressive stress of greater than 250 MPa and at least one antimicrobial surface; and
wherein the concentration of silver ions at the first surface of the glass article having a compressive stress greater than 250 MPa and at least one antimicrobial surface is in the range of greater than zero to less than 0.080 μg/cm 2 .
2. The method according to claim 1 , wherein the compressive stress is greater than 500 MPa.
3. The method according to claim 1 , wherein the second ion-exchange bath comprises silver nitrate in an amount in the range of 0.15 wt % to 5 wt %, and wherein the first ion exchanging metal ions comprise potassium metal ions.
4. The method according to claim 1 , wherein ion-exchanging the glass article with the compressive stress greater than 250 MPa in the second ion-exchange bath is conducted for less than or equal to 30 minutes.
5. The method according to claim 1 , wherein ion-exchanging the glass article with the compressive stress greater than 250 MPa in the second ion-exchange bath is conducted for less than or equal to 20 minutes.
6. The method according to claim 1 , wherein ion-exchanging the glass article with the compressive stress greater than 250 MPa in the second ion-exchange bath is conducted for less than or equal to 10 minutes.
7. The method according to claim 1 , wherein the glass article comprises a composition selected from a group consisting of soda lime glass, alkali aluminosilicate glass and alkali aluminoborosilicate glass.
8. The method according to claim 7 , wherein the provided glass article exhibits a composition selected from a group consisting of:
(a) 60-70 mol % SiO 2 ; 6-14 mol % Al 2 O 3 ; 0-15 mol % B 2 O 3 ; 0-20 mol % Na 2 O; 0-10 mol % K 2 O; 0-8 mol % MgO; 0-10 mol % CaO; 0-5 mol % ZrO 2 ; 0-1 mol % SnO 2 ; 0-1 mol % CeO 2 ; less than 50 ppm As 2 O 3 ; and less than 50 ppm Sb 2 O 3 ; wherein 12 mol %≦Na 2 O+K 2 O≦20 mol % and 0 mol %≦MgO+CaO≦10 mol %; and
(b) 64 mol %≦SiO 2 ≦68 mol %; 12 mol %≦Na 2 O≦16 mol %; 8 mol %≦Al 2 O 3 ≦12 mol %; 0 mol %≦B 2 O 3 ≦3 mol %; 2 mol %≦K 2 O≦5 mol %; 4 mol %≦MgO≦6 mol %; and 0 mol %≦CaO≦5 mol %, and wherein 66 mol %≦SiO 2 +B 2 O 3 +CaO≦69 mol %; Na 2 O+K 2 O+B 2 O 3 +MgO+CaO+SrO≧10 mol %; 5 mol %≦MgO+CaO+SrO≦8 mol %; (Na 2 O+B 2 O 3 )−Al 2 O 3 ≦2 mol %; 2 mol %≦Na 2 O−Al 2 O 3 ≦6 mol %; and 4 mol %≦(Na 2 O+K 2 O)−Al 2 O 3 ≦10 mol %;
(c) 61 mol %≦SiO 2 ≦75 mol %; 9 mol %≦Na 2 O≦21 mol %; 7 mol %≦Al 2 O 3 ≦15 mol %; 0 mol %≦B 2 O 3 ≦12 mol %; 0 mol %≦K 2 O≦4 mol %; 0 mol %≦MgO≦7 mol %; and 0 mol %≦CaO≦mol %;
(d) 50 mol %≦SiO 2 ≦70 mol %; 8 mol %≦Na 2 O≦16 mol %; 9 mol %≦Al 2 O 3 ≦17 mol %; 2 mol %≦B 2 O 3 ≦12 mol %; 0 mol %≦K 2 O≦4 mol %; 0 mol %≦MgO≦4 mol %; and 0 mol %≦CaO≦0.2 mol %, wherein the alkali metal oxides and the alkaline earth metal oxides are modifiers and the ratio:
[(mol % Al 2 O 3 +mol % B 2 O 3 )÷Σ mol % modifiers] is greater than 1; and
(e) SiO 2 >50 mol %; 11 mol %≦Na 2 O≦25 mol %; 7 mol %≦Al 2 O 3 ≦26 mol %; o mol %≦B 2 O 3 ≦9 mol %; 0 mol %≦K 2 O≦2.5 mol %; 0 mol %≦MgO≦8.5 mol %; and 0 mol %≦CaO≦1.52 mol %.
9. The method according to claim 1 , further comprising:
applying a low surface energy coating to the first surface of the glass article, the low surface energy coating being selected from the group consisting of fluoroalkylsilanes, perfluoropolyether alkoxy silanes, perfluoroalkyl alkoxy silanes, fluoroalkylsilane-(non-fluoroalkylsilane) copolymers, and mixtures of fluoroalkylsilanes and hydrophilic silanes; and
curing the low surface energy coating to form a Si—O bond between the low surface energy coating and the first surface of the glass article;
wherein the low surface energy coating has a thickness in the range of 0.5 nm to 20 nm.
10. The method according to claim 9 , wherein the low surface energy coating is a perfluoroalkyl alkoxy silane of formula (R F1 ) x —Si(OR) 4-x , where x=1 or 2, R F1 moiety is a perfluoroalkyl group having a carbon chain length in the range of 16-30 carbon atoms and OR is acetoxy, —OCH 3 or OCH 2 H 3 .
11. The method according to claim 9 , wherein the low surface energy coating is a perfluoropolyether alkoxy silane of formula [CF 3 —(CF 2 CF 2 O) a ] x —Si(OR) 4-x where a is in the range of 5-10, x=1, and OR is acetoxy, —OCH 3 or OCH 2 H 3 , and further wherein a total perfluoroether chain is defined from the silicon atom in the alkoxy silane to the end of the alkoxy silane having a length in the range of 1 nm to 10 nm.
12. The method according to claim 9 , wherein the low surface energy coating is a perfluoroalkyl alkyl alkoxy silane of formula [R F2 —(CH 2 ) b ] x —Si(OR) 4-x where R F2 is a perfluoroalkyl group having a carbon chain length in the range of 10-16 carbon atoms, b is in the range of 14-20, x=2 or 3 and OR is acetoxy, —OCH 3 or OCH 2 H 3 .
13. The method according to claim 9 , wherein applying the low surface energy coating comprises applying said low surface energy coating to form coating domains and a non-coating domain area on the first surface of the glass article.
14. The method according to claim 9 , wherein applying the low surface energy coating comprises applying said low surface energy coating uniformly across the first surface of the glass article, and further wherein the low surface energy coating has a thickness in the range of 0.5 nm to 10 nm.
15. The method according to claim 9 , wherein the low surface energy coating has a thickness in the range of 1 nm to 3 nm.