Strengthened glass with ultra deep depth of compression

• US 10,640,420 B2
• Filed: 11/06/2018
• Issued: 05/05/2020
• Est. Priority Date: 10/31/2014
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Amin, Jaymin, Egboiyi, Benedict Osobomen, Pesansky, Jonathan David, Reiman, Kevin Barry, Roussev, Rostislav Vatchev, Strines, Brian Paul
• Primary Examiner(s): Fang, Shane
• Application Number:
  US16/182,004
• Publication Number:
  US 20190071350A1
• Time in Patent Office: 546 Days
• CPC Class Codes: C03C 21/002 to perform ion-exchange between alkali ions C03C21/005 takes precedence
• CPC Class Codes: C03C 3/097 containing phosphorus, niobium or tantalum

Abstract

Chemically strengthened glass articles having at least one deep compressive layer extending from a surface of the article to a depth of compression DOC of at least about 125 μm within the glass article. The compressive stress profile includes a single linear segment or portion extending from the surface to the depth of compression DOC. Alternatively, the compressive stress profile may include an additional portion extending from the surface to a relatively shallow depth and the linear portion extending from the shallow depth to the depth of compression.

Claims

1. A glass article, the glass article comprising a thickness tin a range from 0.1 mm to 1.0 mm, and a compressive region having a compressive stress CS_s, in a range from about 400 MPa to about 1200 MPa at a surface of the glass article, wherein the compressive region extends from the surface to a depth of compression DOC, wherein 0.12 ·

t ≤

DOC ≤

0.22·

t, and has a compressive stress profile, the compressive stress profile comprising;

a. a first portion b extending from the surface to a depth d_b below the surface and having a slope m_b; and

b. a second portion c extending from about d_c to the depth of compression DOC and having a slope m_c, wherein −

0.4 MPa/μ

m ≥

m_c≥

−

3.0 MPa/μ

m.

2. The glass article of claim 1, wherein the depth of compression DOC is in a range from about 95 μ

m to about 250 μ

m.

3. The glass article of claim 1, wherein the depth of compression DOC is in a range from about 100 μ

m to about 190 μ

m.

4. The glass article of claim 1, wherein the slope m_c is in a range from about −

0.7 MPa/μ

m to about −

2.7 MPa/μ

m.

6. The glass article of claim 1, wherein the glass article comprises an alkali aluminosilicate glass.

7. The glass article of claim 6, wherein the alkali aluminosilicate glass comprises up to about 10 mol % Li₂O.

8. The glass article of claim 6, wherein the alkali aluminosilicate glass comprises at least about 4 mol % P₂O₅ and from 0 mol % to about 4 mol % B₂O₃, wherein 1.3<

[(P₂O₅+R₂O)/M₂O₃]<

2.3, where M₂O₃=Al₂O₃+B₂O₃, and R₂O is the sum of monovalent cation oxides present in the alkali aluminosilicate glass.

9. The glass article of claim 6, wherein the glass is lithium-free.

10. The glass article of claim 6, wherein the glass consists essentially of from about 40 mol % to about 70 mol % SiO₂;

from about 11 mol % to about 25 mol % Al₂O₃;

from about 4 mol % to about 15 mol % P₂O₅;

from about 13 mol % to about 25 mol % Na₂O;

from about 13 to about 30 mol % R_x0, wherein R_xO is the sum of the alkali metal oxides, alkaline earth metal oxides, and transition metal monoxides present in the glass;

from about 11 to about 30 mol % M₂O₃,where M₂O₃=Al₂O₃+B₂O₃;

from 0 mol % to about 1 mol % K₂O;

from 0 mol % to about 4 mol % B₂O₃, and 3 mol % or less of one or more of TiO₂, MnO, Nb₂O₅, MoO₃, Ta₂O₅, WO₃, ZrO₂, Y₂O₃, La₂O₃, HfO₂, CdO, SnO₂, Fe₂O₃, CeO₂, As₂O₃, Sb₂O₃, Cl, and Br; and

1.3<

[(P₂O₅+R₂O)/M₂O₃]<

2.3, where R₂O is the sum of monovalent cation oxides present in the glass.

11. An electronic device comprising the glass article of claim 1.

5. A glass article, the glass article comprising a thickness t and a compressive region having a compressive stress CS_s, in a range from about 400 MPa to about 1200 MPa at a surface of the glass article, wherein the compressive region extends from the surface to a depth of compression DOC, wherein 0.1 ·

t≤

DOC≤

0.25·

t, and has a compressive stress profile, the compressive stress profile comprising;

a. a first portion b extending from the surface to a depth d_b below the surface and having a slope m_h; and

b. a second portion c extending from about d_c to the depth of compression DOC and having a slope m_c wherein the slope m_c is in a range from about −

1.5 MPa/μ

m to about −

2.7 MPa/μ

m.

12. The glass article of claim 5, wherein the depth of compression DOC is in a range from about 100 μ

m to about 190 μ

m.

13. The glass article of claim 5, wherein 0.12·

t DOCS ≤

0.224·

t “

and the thickness is in a range from 0.1 mm to about 1.0 mm”

.

14. The glass article of claim 5, wherein the glass article comprises an alkali aluminosilicate glass.

15. The glass article of claim 14, wherein the alkali aluminosilicate glass comprises up to about 10 mol % Li₂O.

16. The glass article of claim 14, wherein the alkali aluminosilicate glass comprises at least about 4 mol % P₂O₅ and from 0 mol % to about 4 mol % B₂O₃, wherein 1.3<

[(P₂O₅+R₂O)/M₂O₃]<

2.3, where M₂O₃=Al₂O₃+B₂O₃, and R₂O is the sum of monovalent cation oxides present in the alkali aluminosilicate glass.

17. The glass article of claim 14, wherein the glass consists essentially of from about 40 mol % to about 70 mol % SiO₂;

from about 11 mol % to about 25 mol % Al₂O₃;

from about 4 mol % to about 15 mol % P₂O₅;

from about 13 mol % to about 25 mol % Na₂O;

from about 13 to about 30 mol % R_xO is the sum of the alkali metal oxides, alkaline earth metal oxides, and transition metal monoxides present in the glass;

from about 11 to about 30 mol % M₂O₃,where M₂O₃=Al₂O₃+B₂O₃;

from 0 mol % to about 1 mol % K₂O;

from 0 mol % to about 4 mol % B₂O₃, and 3 mol % or less of one or more of TiO₂, MnO, Nb₂O₅, MoO₃, Ta₂O₅, WO₃, ZrO₂, Y₂O₃, La₂O₃, HfO₂, CdO, SnO₂, Fe₂O₃, CeO₂, As₂O₃, Sb₂O₃, Cl, and Br; and

1.3<

[(P₂O₅+R₂O)/M₂0₃]<

2.3, where R₂O is the sum of monovalent cation oxides present in the glass.

18. An electronic device comprising the glass article of claim 5.