IP Library Granted Patent US 11,267,747
Granted Patent B2
US 11,267,747 · App. 15/077,036 · Granted Mar 8, 2022

High strength, scratch resistant and transparent glass-based materials

Inventors: George Halsey Beall (Big Flats, NY); Marie Jacqueline Monique Comte (Fontenay aux Roses, FR); Paulo Jorge Gaspar Marques (Le Chatelet en Brie, FR)
Assignee: CORNING INCORPORATED
C03C10/0009C03C3/085C03C3/091C03C3/093C03C4/0092C03C10/0045C03C10/0054C03C21/002
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Quick Facts
Patent No.
US 11,267,747
App. No.
15/077,036
Granted
Mar 8, 2022
Kind
B2
Abstract

Embodiments of a transparent glass-based material comprising a glass phase and a second phase that is different from and is dispersed in the glass phase are provided. The second phase may comprise a crystalline or a nanocrystalline phase, a fiber, and/or glass particles. In some embodiments, the second phase is crystalline. In one or more embodiments, the glass-based material has a transmittance of at least about 88% over a visible spectrum ranging from about 400 nm to about 700 nm and a fracture toughness of at least about 0.9 MPa·m 1/2 , and wherein a surface of the glass-based material, when scratched with a Knoop diamond at a load of at least 5 N to form a scratch having a width w, is free of chips having a size of greater than 3w.

Claims (69)

1. A glass-based material, the glass-based material comprising a glass phase and a second phase that is different than the glass phase and dispersed within the glass phase, wherein the glass-based material has a transmittance of at least about 88%/mm over a visible spectrum ranging from about 400 nm to about 700 nm and a fracture toughness of at least about 0.9 MPa·m 1/2 , and wherein a surface of the glass-based material, when scratched with a Knoop diamond at a load of at least 5 N to form a scratch having a width w, is free of chips having a size of greater than 3w, wherein the second phase is a crystalline ceramic phase comprising at least one of mullite, spinel, β-quartz, petalite, lithium disilicate, β-spodumene, nepheline, and alumina, and wherein the glass phase comprises at least one of a soda lime glass, an alkali aluminosilicate glass, and a lithium alumina silicate glass.

2. The glass-based material of claim 1 , wherein the crystalline ceramic phase comprises any one or more of:

crystals having a mean crystalline size in a range from 5 nm to 200 nm, as determined from x-ray diffraction/Rietveld analysis; and

up to 98 volume % of the glass-based materials.

3. The glass-based material of claim 2 , further comprising a second crystalline phase, the second crystalline phase comprising nepheline or anorthite.

4. The glass-based material of claim 1 , wherein a difference in refractive index between the glass phase and the second phase is less than about 0.025.

5. The glass-based material of claim 1 , wherein the glass-based material is ion exchanged and has a retained strength after abrasion of at least about 250 MPa as measured by abraded ring-on-ring testing.

6. The glass-based material of claim 1 , wherein the glass-based material has a coefficient of thermal expansion of less than about 45×10 −7 K −1 .

7. The glass-based material of claim 1 , wherein the glass-based material has a Young's modulus in a range from about 80 GPa to about 100 GPa.

8. The glass-based material of claim 1 , wherein the glass-based material has a thickness in a range from about 0.1 mm to about 2 mm, and wherein the glass-based material has at least about a 60% survival rate when dropped in an inverted ball on sandpaper test with a 4.2 g stainless steel ball having a diameter of 10 mm from a drop height of 80 cm onto a 30 grit sandpaper positioned above the surface of the glass-based material so there is a 100 μm air gap, wherein the survival rate is based on testing at least 5 samples.

9. The glass-based material of claim 1 , having a fracture toughness of greater than 1.2 MPa·m 1/2 .

10. A consumer electronic product comprising the glass-based material of claim 1 .

11. The glass-based material of claim 1 , wherein the glass comprises:

55 to 75 mol % SiO 2 ;

10 to 20 mol % Al 2 O 3 ;

0 to 16 mol % B 2 O 3 ;

0 to 4 mol % Na 2 O;

0 to 4 mol % K 2 O;

0 to 8 mol % Li 2 O;

0 to 12 mol % MgO;

0 to 10 mol % ZnO;

0 to 5 mol % ZrO 2 ; and

0 to 0.5 mol % SnO 2 .

12. The glass-based material of claim 11 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

13. The glass-based material of claim 1 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

14. A glass-based material comprising a glass phase and a second phase that is different than the glass phase and dispersed within the glass phase, the glass-based material having a transmission of at least 88%/mm over a visible spectrum ranging from about 400 nm to about 700 nm and a fracture toughness of at least about 0.9 MPa·m 1/2 , wherein:

a. the second phase comprises particles having a mean size in a range from 5 nm to 200 nm;

b. the glass phase has a first index of refraction and the second phase has a second index of refraction, wherein the difference between the first index of refraction and the second index of refraction is less than about 0.025;

c. a volume fraction of the second phase in the glass-based material is in a range from 10 to about 98%;

d. the second phase is a crystalline ceramic phase comprising at least one of mullite, spinel, β-quartz, petalite, lithium disilicate, β-spodumene, nepheline, and alumina; and

e. the glass phase comprises at least one of a soda lime glass, an alkali aluminosilicate glass, and a lithium alumina silicate glass.

15. The glass-based material of claim 14 , wherein the crystalline ceramic phase comprises crystals having a mean crystalline size in a range from 5 nm to 200 nm, as determined from x-ray diffraction/Rietveld analysis.

16. The glass-based material of claim 14 , further comprising a second crystalline phase, the second crystalline phase comprising nepheline or anorthite.

17. The glass-based material of claim 14 , having a fracture toughness of greater than 1.2 MPa·m 1/2 .

18. A consumer electronic product comprising the glass-based material of claim 14 .

19. The glass-based material of claim 14 , wherein the glass comprises:

55 to 75 mol % SiO 2 ;

10 to 20 mol % Al 2 O 3 ;

0 to 16 mol % B 2 O 3 ;

0 to 4 mol % Na 2 O;

0 to 4 mol % K 2 O;

0 to 8 mol % Li 2 O;

0 to 12 mol % MgO;

0 to 10 mol % ZnO;

0 to 5 mol % ZrO 2 ; and

0 to 0.5 mol % SnO 2 .

20. The glass-based material of claim 19 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

21. The glass-based material of claim 14 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

22. A glass-based material comprising a glass phase and a second phase that is different than the glass phase and dispersed within the glass phase, the glass-based material having a transmission of at least 88%/mm over a visible spectrum ranging from about 400 nm to about 700 nm, a fracture toughness of at least about 0.9 MPa·m 1/2 a coefficient of thermal expansion of less than about 45×10 −7 K −1 , and a Young's modulus in a range from about 80 GPa to about 100 GPa, wherein the second phase is a crystalline ceramic phase comprising at least one of mullite, spinel, β-quartz, petalite, lithium disilicate, β-spodumene, nepheline, and alumina, and wherein the glass phase comprises at least one of a soda lime glass, an alkali aluminosilicate glass, and a lithium alumina silicate glass.

23. The glass-based material of claim 22 , wherein a difference in refractive index between the glass phase and the second phase is less than about 0.025.

24. The glass-based material of claim 22 , wherein the glass-based material is ion exchanged and has a retained strength after abrasion of at least about 250 MPa as measured by abraded ring-on-ring testing.

25. The glass-based material of claim 22 , wherein the glass-based material has a thickness in a range from about 0.1 mm to about 2 mm, and wherein the glass-based material has at least about a 60% survival rate when dropped in an inverted ball on sandpaper test with a 4.2 g stainless steel ball having a diameter of 10 mm from a drop height of 80 cm onto a 30 grit sandpaper positioned above the surface of the glass-based material so there is a 100 μm air gap, wherein the survival rate is based on testing at least 5 samples.

26. The glass-based material of claim 22 , wherein a surface of the glass-based material, when scratched with a Knoop diamond at a load of at least 5 N to form a scratch having a width w, is free of chips having a size of greater than 3w.

27. The glass-based material of claim 22 , having a fracture toughness of greater than 1.2 MPa·m 1/2 .

28. A consumer electronic product comprising the glass-based material of claim 22 .

29. The glass-based material of claim 22 , wherein the glass comprises:

55 to 75 mol % SiO 2 ;

10 to 20 mol % Al 2 O 3 ;

0 to 16 mol % B 2 O 3 ;

0 to 4 mol % Na 2 O;

0 to 4 mol % K 2 O;

0 to 8 mol % Li 2 O;

0 to 12 mol % MgO;

0 to 10 mol % ZnO;

0 to 5 mol % ZrO 2 ; and

0 to 0.5 mol % SnO 2 .

30. The glass-based material of claim 29 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

31. The glass-based material of claim 22 , wherein the crystalline ceramic phase comprises at least one of mullite and β-quartz.

32. The glass-based material of claim 22 , wherein the crystalline ceramic phase comprises at least one of mullite, spinel, petalite, lithium disilicate, β-spodumene, nepheline, and alumina.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 4, 2016
From: BEALL, GEORGE HALSEY; COMTE, MARIE JACQUELINE MONIQUE; MARQUES, PAULO GASPAR JORGE
To: CORNING INCORPORATED
Reel/Frame 038456/0336 →
Continuity (3)
Provisional Application 62186547 · Jun 30, 2015
Provisional Application 62137345 · Mar 24, 2015
Related Publication 20160280589A1 · Sep 29, 2016
Cited By (1)
US 12,391,604