# US 11,993,539 B2 · Chemically strengthenable lithium aluminosilicate glasses with inherent damage resistance

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- Number: US 11,993,539 B2
- Document ID: US11993539B2
- Status: Granted
- Kind: B2
- Application number: 18/195,880
- Filed: 2023-05-10
- Published: 2023-09-07
- Granted: 2024-05-28
- Earliest claimed: 2016-01-08
- Assignees: Corning Incorporated
- Applicants: Corning Incorporated
- Inventors: George Halsey Beall; Matthew John Dejneka; Qiang Fu; Sinue Gomez; Robert Michael Morena; Charlene Marie Smith
- Web page: https://patentgrep.com/patent/US11993539B2

## CPC

- C03C 3/097: containing phosphorus, niobium or tantalum
- B32B 17/06: comprising glass as the main or only constituent of a layer, next to another layer of a specific {material}
- C03C 3/085: containing an oxide of a divalent metal
- C03C 3/087: containing calcium oxide, e.g. common sheet or container glass
- C03C 3/091: containing aluminium
- C03C 3/093: containing zinc or zirconium
- C03C 21/002: {to perform ion-exchange between alkali ions (C03C21/005 takes precedence)}
- H05K 5/03: Covers
- B32B 2307/50: having particular mechanical properties
- C03C 4/18: for ion-sensitive glass
- C03C 2204/00: Glasses, glazes or enamels with special properties
- H05K 5/0017: {with operator interface units}
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS

## Abstract

A group of glass compositions in the Li2O—Al2O3—SiO2—B2O3 family that can be chemically strengthened in single or multiple ion exchange baths containing at least one of NaNO3 and KNO3 for a short time (2-4 hours) to develop a deep depth of layer (DOL). In some instances, the DOL is at least 70 μm; in others, at least about 100 μm. The ion exchanged glasses have a high damage resistance (indentation fracture toughness ranging form greater than 10 kgf to greater than 50 kgf) that is better than or at least comparable to that of sodium aluminosilicate glasses.

## Claims

### Claim 1

A lithium aluminosilicate glass article, wherein the lithium aluminosilicate glass article is formed from a glass comprising:
from 55 mol % to 75 mol % SiO2;
from 10 mol % to 18 mol % Al2O3;
from 7 mol % to 14 mol % Li2O;
from 0.2 mol% to 5 mol% Na2O;
from 0 mol % to 1 mol % K2O;
from 3 mol % to 7 mol % B2O3; and
from 0 mol % to 1 mol % P2O5, wherein R2O—Al2O3 is from −0.5 to 0, where R2O=Li2O+Na2O+K2O+Rb2O+Cs2O.

### Claim 2 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass comprises:
from 57 mol % to 67 mol % SiO2.

### Claim 3 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass comprises:
from 12 mol % to 18 mol % Al2O3.

### Claim 4 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass comprises:
from 7 mol % to 10 mol % Li2O.

### Claim 5 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass comprises:
from 7 mol % to 12.6 mol %.

### Claim 6 (depends on 4)

The lithium aluminosilicate glass article of claim 4, wherein the glass comprises:
from 57 mol % to 67 mol % SiO2; and
from 12 mol % to 18 mol % Al2O3.

### Claim 7 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass comprises:
from 3.5 mol % to 7 mol % B2O3.

### Claim 8 (depends on 1)

The lithium aluminosilicate glass of claim 1, wherein the glass comprises:
from 0 mol % to 1 mol % TiO2.

### Claim 9 (depends on 1)

The lithium aluminosilicate glass of claim 1, wherein the glass comprises:
from 0 mol % to 2 mol % ZnO.

### Claim 10 (depends on 1)

The lithium aluminosilicate glass of claim 1, wherein the glass is free of As2O3 and Sb2O3.

### Claim 11 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass from which the lithium aluminosilicate glass article is formed is characterized by
(Al2O3 (mol %)+B2O3 (mol %))/R2O (mol %) is in a range from 0.9 to 1.9,
where R2O=Li2O+Na2O+K2O+Rb2O+Cs2O.

### Claim 12 (depends on 4)

The lithium aluminosilicate glass article of claim 4, wherein the glass from which the lithium aluminosilicate glass article is formed is characterized by
(Al2O3 (mol %)+B2O3 (mol %))/R2O (mol %) is in a range from 0.9 to 1.9,
where R2O=Li2O+Na2O+K2O+Rb2O+Cs2O.

### Claim 13 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass is characterized by
Al2O3 (mol %)>B2O3 (mol %).

### Claim 14 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass from which the lithium aluminosilicate glass article is formed has a liquidus viscosity of at least 10 kP.

### Claim 15 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the lithium aluminosilicate glass has a softening point of 840° C. or less.

### Claim 16 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass from which the lithium aluminosilicate glass article is formed has an anneal point of at least 510° C.

### Claim 17 (depends on 1)

The lithium aluminosilicate glass article of claim 1, wherein the glass from which the lithium aluminosilicate glass article is formed has an elastic modulus of at least 68 GPa.

### Claim 18 (depends on 1)

A consumer electronic product, comprising:
a housing having a front surface, a back surface and side surfaces;
electrical components provided at least partially within the housing, the electrical components including at least a controller, a memory, and a display, the display being provided at or adjacent the front surface of the housing; and
a cover glass disposed over the display,
wherein at least one of a portion of the housing or the cover glass comprises the lithium aluminosilicate glass article of claim 1.