Strengthened glass substrates with glass frits and methods for making the same
Strengthened glass substrates with glass fits and methods for forming the same are disclosed. According to one embodiment, a method for forming a glass frit on a glass substrate may include providing a glass substrate comprising a compressive stress layer extending from a surface of the glass substrate into a thickness of the glass substrate, the compressive stress having a depth of layer DOL and an initial compressive stress CS i . A glass frit composition may be deposited on at least a portion of the surface of the glass substrate. Thereafter, the glass substrate and the glass frit composition are heated in a furnace to sinter the glass fit composition and bond the glass frit composition to the glass substrate, wherein, after heating, the glass substrate has a fired compressive stress CS f which is greater than or equal to 0.70*CS i .
1. A method for forming a glass frit on a glass substrate, the method comprising:
providing a glass substrate comprising a compressive stress layer extending from a surface of the glass substrate into a thickness of the glass substrate, the compressive stress layer having a depth of layer DOL and an initial compressive stress CS i , wherein the glass substrate is an ion-exchanged glass substrate comprising aluminosilicate or alkali borosilicate glass;
depositing a lead free glass frit composition on at least a portion of the surface of the glass substrate to form a glass assembly;
heating the entire glass assembly in a furnace to sinter the lead free glass frit composition and bond the lead free glass frit composition to the glass substrate, wherein, after heating, the lead free glass frit composition is fully vitrified and the glass substrate has a fired compressive stress CS f which is greater than or equal to 0.70*CS i ,
wherein the entire glass assembly is heated by:
heating the glass assembly to a first temperature T 1 ;
holding the glass assembly at the first temperature T 1 for a first holding time HT 1 ;
heating the glass assembly to a second temperature T 2 ; and
holding the glass assembly at the second temperature T 2 for a second holding time HT 2 , wherein the second temperature T 2 is less than or equal to about 450° C. and the first temperature T 1 is less than or equal to the second temperature T 2 .
2. The method of claim 1 , wherein:
the glass assembly is heated from room temperature to the first temperature T 1 at a first ramp rate R 1 ; and
the glass assembly is heated from the first temperature T 1 to the second temperature T 2 at a second ramp rate R 2 .
3. The method of claim 1 , wherein the initial compressive stress CS; is greater than or equal to about 600 MPa and the depth of layer DOL is greater than or equal to about 30 μm.
4. The method of claim 1 , wherein the lead free glass frit composition has a softening point which is less than or equal to 400° C.
5. The method of claim 1 , wherein the lead free glass frit composition has a glass transition temperature which is less than or equal to 375° C.
6. The method of claim 1 , wherein the glass substrate has a substrate coefficient of thermal expansion CTE s , the lead free glass frit composition has a frit coefficient of thermal expansion CTE F , and the frit coefficient of thermal expansion CTE F is within +/−10×10 −7 /° C. of the substrate coefficient of thermal expansion CTE s .
7. The method of claim 1 , wherein the substrate coefficient of thermal expansion CTE s is in a range from about 80×10 −7 /° C. to about 95×10 −7 /° C. over a temperature range from 0° C. to 300° C.
8. The method of claim 1 , wherein the lead free glass frit composition comprises:
from about 50 mol. % to about 75 mol. % SnO;
from about 28 mol. % to about 35 mol. % P 2 O 5 ;
from about 2 mol. % to about 10 mol. % ZnO; and
from about 1 mol. % to about 5 mol. % B 2 O 3 .
9. The method of claim 1 , wherein the lead free glass frit composition comprises:
from about 40 mol. % to about 60 mol. % V 2 O 5 ;
from about 15 mol. % to about 30 mol. % P 2 O 5 ;
from about 20 mol. % to about 35 mol. % Sb 2 O 3 ;
from about 0 mol. % to about 2 mol. % AlO 3 ;
from about 0 mol. % to about 5 mol. % Fe 2 O 3 ; and
from about 0 mol. % to about 2 mol. % TiO 2 .
10. The method of claim 1 , wherein the lead free glass frit composition comprises:
from about 30 mol. % to about 50 mol. % V 2 O 5 ;
from about 10 mol. % to about 30 mol. % P 2 O 5 ;
from about 0 mol. % to about 10 mol. % ZnO;
from about 10 mol. % to about 30 mol. % Fe 2 O 3 ; and
from about 10 mol. % to about 30 mol. % TiO 2 ; and
the glass frit composition is free from antimony and compounds containing antimony.
11. The method of claim 1 , wherein the lead free glass frit composition comprises:
from about 50 mol. % to about 60 mol. % V 2 O 5 ;
from about 25 mol. % to about 30 mol. % P 2 O 5 ;
from about 10 mol. % to about 20 mol. % Sb 2 O 3 ;
from about 0 mol. % to about 2 mol. % AlO 3 ;
from about 0 mol. % to about 2.5 mol. % Fe 2 O 3 ; and
from about 0 mol. % to about 2 mol. % TiO 2 .
12. The method of claim 1 , wherein the second temperature T 2 ranges from 400° C. to 500° C. and the second hold time HT 2 ranges from 5 to 30 minutes.
13. A method for forming a glass frit on a glass substrate, the method comprising:
providing a glass substrate comprising a compressive stress layer extending from a surface of the glass substrate into a thickness of the glass substrate, the compressive stress layer having a depth of layer DOL and an initial compressive stress CS i , wherein the glass substrate is an ion-exchanged glass substrate comprising aluminosilicate or alkali borosilicate glass;
depositing a lead free glass frit composition on at least a portion of the surface of the glass substrate to form a glass assembly, the lead free glass frit composition having a softening point which is less than or equal to 400° C.; and
heating the entire glass assembly in a furnace to a temperature less than or equal to 450° C. such that, after heating, the lead free glass frit composition is fully vitrified and sintered and bonded to the glass substrate,
wherein the entire glass assembly is heated by:
heating the glass assembly to a first temperature T 1 ;
holding the glass assembly at the first temperature T 1 for a first holding time HT 1 ;
heating the glass assembly to a second temperature T 2 ; and
holding the glass assembly at the second temperature T 2 for a second holding time HT 2 , wherein the second temperature T 2 is less than or equal to about 450° C. and the first temperature T 1 is less than or equal to the second temperature T 2 .
14. The method of claim 13 , wherein the lead free glass frit composition has a glass transition temperature which is less than or equal to 375° C.
15. The method of claim 13 , wherein the glass substrate has a substrate coefficient of thermal expansion CTEs, the lead free glass frit composition has a frit coefficient of thermal expansion CTE F , and the frit coefficient of thermal expansion CTE F is within +/−10×10 −7 /° C. of the substrate coefficient of thermal expansion CTE s .
16. The method of claim 13 , wherein the substrate coefficient of thermal expansion CTE is in a range from about 80×10 −7 /° C. to about 95×10 −7 /° C. over a temperature range from 0° C. to 300° C.
17. The method of claim 13 , wherein the second temperature T 2 ranges from 400° C. to 500° C. and the second hold time HT 2 ranges from 5 to 30 minutes.