Strengthened glass and compositions therefor

• US 10,144,198 B2
• Filed: 04/29/2015
• Issued: 12/04/2018
• Est. Priority Date: 05/02/2014
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Cites, Jeffrey Scott, Cleary, Thomas Michael, Couillard, James Gregory, Gomez, Sinue, Moore, Michael John, Morena, Robert Michael, Price, James Joseph, Sorensen, Jr., Charles Mitchel, Walter, Jonathan Earl
• Primary Examiner(s): Khan, Tahseen
• Application Number:
  US14/699,263
• Publication Number:
  US 20150314571A1
• Time in Patent Office: 1,315 Days
• Field of Search: 428215
• CPC Class Codes: B32B 17/06 comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10137 Chemical strengthening
• CPC Class Codes: B32B 2307/102 Insulating
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/56 Damping, energy absorption
• CPC Class Codes: B32B 2605/006 Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
• CPC Class Codes: C03C 2204/00 Glasses, glazes or enamels with special properties
• CPC Class Codes: C03C 27/10 with the aid of adhesive specially adapted for that purpose
• CPC Class Codes: C03C 3/091 containing aluminium
• CPC Class Codes: C03C 3/093 containing zinc or zirconium
• CPC Class Codes: C03C 3/097 containing phosphorus, niobium or tantalum
• CPC Class Codes: C03C 4/18 for ion-sensitive glass
• CPC Class Codes: Y10T 428/24967 Absolute thicknesses specified
• CPC Class Codes: Y10T 428/24983 Hardness
• CPC Class Codes: Y10T 428/315 Surface modified glass [e.g., tempered, strengthened, etc.]

Abstract

A glass laminate structure comprising an external glass sheet and an internal glass sheet wherein one or both of the glass sheets comprises SiO₂+B₂O₃+Al₂O₃≥86.5 mol. %. and R₂O—RO—Al₂O₃<about 5 mol. %. Exemplary glass sheet can comprise between about 69-80 mol. % SiO₂, between about 6-12 mol. % Al₂O₃, between about 2-10 mol. % B₂O₃, between about 0-5 mol. % ZrO₂, Li₂O, MgO, ZnO and P₂O₅, between about 6-15 mol. % Na₂O, between about 0-3 mol. % K₂O and CaO, and between about 0-2 mol. % SnO₂ to provide a mechanically robust and environmentally durable structure.

Claims

1. A glass laminate structure comprising:

an external glass sheet;

an internal glass sheet; and

wherein one or both of the glass sheets comprises SiO₂+B₂O₃+Al₂O₃≥

86.5 mol. %, B₂O₃(mol. %)≤

Al₂O₃(mol. %), and R₂O—

RO—

Al₂O₃<

about 5 mol. %, and wherein one or both of the glass sheets is ion-exchanged to a compressive stress of at least about 300 MPa and a depth of layer of compressive stress of at least about 15 microns with a Knoop Scratch Threshold>

about 12 N and a hardness to modulus ratio greater than about 0.112, or a Vickers indentation threshold in a range from about 10 to about 15 Kg.

2. The glass laminate structure of claim 1, wherein one or both of the glass sheets comprises either one or both of the following:

SiO₂+B₂O₃+Al₂O₃≥

about 88 mol. %, and R₂O—

RO—

Al₂O₃<

about 3 mol. %.

3. The glass laminate structure of claim 1, wherein either the external glass sheet or the internal glass sheet is a chemically strengthened glass sheet and comprises SiO₂+B₂O₃+Al₂O₃≥

86.5 mol. %. and R₂O—

RO—

Al₂O₃<

about 5 mol. %, and wherein the other of the external glass sheet or the internal glass sheet comprises a material selected from the group consisting of soda-lime glass and annealed glass.

4. The glass laminate structure of claim 1, wherein one or both of the glass sheets further comprises:

between about 69-80 mol. % SiO₂;

between about 6-12 mol. % Al₂O₃;

between about 2-10 mol. % B₂O₃;

between about 0-5 mol. % ZrO₂, Li₂O, MgO, ZnO and P₂O₅;

between about 6-15 mol. % Na₂O;

between about 0-3 mol. % K₂O and CaO; and

between about 0-2 mol. % SnO₂.

5. The glass laminate structure of claim 1, wherein one or both of the glass sheets further comprises:

between about 72-80 mol. % SiO₂;

between about 8-12 mol. % Al₂O₃;

between about 4-10 mol. % B₂O₃;

between about 0-4 mol. % ZrO₂, MgO, and ZnO;

between about 0-2 mol. % Li₂O, CaO, and P₂O₅;

between about 7-14 mol. % Na₂O;

between about 0.1-2.5 mol. % K₂O; and

between about 0.1-1.5 mol. % SnO₂.

6. The glass laminate structure of claim 1, wherein one or both of the glass sheets further comprises:

between about 74-80 mol. % SiO₂;

between about 8-11 mol. % Al₂O₃;

between about 4-9 mol. % B₂O₃;

between about 0-2 mol. % ZrO₂;

between about 0-3 mol. % MgO and ZnO;

between about 0-1 mol. % Li₂O and P₂O₅;

between about 7-12 mol. % Na₂O;

between about 0.1-2.2 mol. % K₂O;

between about 0-1.5 mol. % CaO; and

between about 0.1-0.5 mol. % SnO₂.

7. The glass laminate structure of claim 1, wherein (R₂O+RO)/(P₂O₅+B₂O₃+Al₂O₃) is between about 0.5-1.2, between about 0.6-0.9, or between about 0.65-0.85.

8. The glass laminate structure of claim 1 wherein one or both of the glass sheets is ion-exchanged to a compressive stress of at least about 300 MPa and a depth of layer of compressive stress of at least about 15 microns with a Knoop Scratch Threshold >

about 16 N and a hardness to modulus ratio>

about 0.116.

9. The glass laminate structure of claim 1, wherein the internal glass sheet has a thickness ranging from about 0.3 mm to about 1.5 mm, and wherein the external glass sheet has a thickness ranging from about 1.5 mm to about 3.0 mm.

10. The glass laminate structure of claim 1, wherein the external glass sheet has a thickness ranging from about 0.3 mm to about 1.5 mm, and wherein the internal glass sheet has a thickness ranging from about 1.5 mm to about 3.0 mm.

11. The glass laminate structure of claim 1, further comprising a polymer interlayer between the external and internal glass sheets, wherein the polymer interlayer comprises a single polymer sheet, a multilayer polymer sheet, or a composite polymer sheet.

12. The glass laminate structure of claim 1, wherein the structure is selected from the group consisting of an automotive side-window, automotive sunroof, automotive windshield, architectural window, and a display.

13. A glass sheet comprising SiO₂+B₂O₃+Al₂O₃≥

86.5 mol. %, B₂O₃(mol. %)≤

Al₂O₃(mol. %), and R₂O—

RO—

Al₂O₃<

about 5 mol. %, wherein the glass sheet, when ion-exchanged to a compressive stress of at least about 300 MPa and a depth of layer of compressive stress of at least about 15 microns, has a Knoop Scratch Threshold >

about 12 N and a hardness to modulus ratio greater than about 0.112, or a Vickers indentation threshold in a range from about 10 to about 15 Kg.

14. The glass sheet of claim 13, further comprising either one or both SiO₂+B₂O₃+Al₂O₃≥

about 88 mol. %, and R₂O—

RO—

Al₂O₃<

about 3 mol. %.

15. The glass sheet of claim 13 further comprising:

between about 69-80 mol. % SiO₂;

between about 6-12 mol. % Al₂O₃;

between about 2-10 mol. % B₂O₃;

between about 0-5 mol. % ZrO₂, Li₂O, MgO, ZnO and P₂O₅;

between about 6-15 mol. % Na₂O;

between about 0-3 mol. % K₂O and CaO; and

between about 0-2 mol. % SnO₂.

16. The glass sheet of claim 13 further comprising:

between about 72-80 mol. % SiO₂;

between about 8-12 mol. % Al₂O₃;

between about 4-10 mol. % B₂O₃;

between about 0-4 mol. % ZrO₂, MgO, and ZnO;

between about 0-2 mol. % Li₂O, CaO, and P₂O₅;

between about 7-14 mol. % Na₂O;

between about 0.1-2.5 mol. % K₂O; and

between about 0.1-1.5 mol. % SnO₂.

17. The glass sheet of claim 13 further comprising:

between about 74-80 mol. % SiO₂;

between about 8-11 mol. % Al₂O₃;

between about 4-9 mol. % B₂O₃;

between about 0-2 mol. % ZrO₂;

between about 0-3 mol. % MgO and ZnO;

between about 0-1 mol. % Li₂O and P₂O₅;

between about 7-12 mol. % Na₂O;

between about 0.1-2.2 mol. % K₂O;

between about 0-1.5 mol. % CaO; and

between about 0.1-0.5 mol. % SnO₂.

18. The glass sheet of claim 13, wherein (R₂O+RO)/(P₂O₅+B₂O₃+Al₂O₃) is between about 0.5-1.2, between about 0.6-0.9, or between about 0.65-0.85.