# US 10,501,364 B2 · Ion exchangeable glasses having high hardness and high modulus

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- Number: US 10,501,364 B2
- Document ID: US10501364B2
- Status: Granted
- Kind: B2
- Application number: 14/082,673
- Filed: 2013-11-18
- Published: 2014-05-22
- Granted: 2019-12-10
- Earliest claimed: 2012-11-21
- Assignees: Corning Incorporated
- Applicants: Corning Incorporated
- Inventors: Dana Craig Bookbinder; Timothy Michael Gross
- Web page: https://patentgrep.com/patent/US10501364B2

## CPC

- C03C 3/095: containing rare earths
- C03C 3/068: containing rare earths
- C03C 21/002: {to perform ion-exchange between alkali ions (C03C21/005 takes precedence)}
- C03C 2201/3411: Yttrium
- Y10T 428/315: Surface modified glass [e.g., tempered, strengthened, etc.]
- 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
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Ion-exchangeable glasses having high hardness and high elastic modulus. The base cover glass formulation includes Na2O, Y2O3, Al2O3, and SiO2. The glasses may further include P2O5, B2O3, and any of the alkali, alkaline earth, and rare earth oxides, as well as other divalent metal oxides. The ion-exchangeable glasses offer higher hardness, which provides more resistance to micro-ductile scratching damage. Ion-exchange of these glasses increases their resistance to cracking caused by frictive damage and increases retained strength following formation of surface damage.

## Claims

### Claim 1

A glass comprising SiO2, at least 18 mol % Al2O3, about 14 mol % Na2O, and from 2.5 mol % to about 6.5 mol % Y2O3, the glass having a molar ratio [Al2O3(mol %)/Y2O3(mol %)] of greater than 2.5, wherein the glass has a Young's modulus of at least 75 GPa and is ion exchangeable.

### Claim 2 (depends on 1)

The glass of claim 1, wherein the glass comprises: from about 40 mol % to about 82 mol % SiO2; from 18 mol % to about 40 mol % Al2O3; about 14 mol % Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 3 (depends on 1)

The glass of claim 1, wherein the glass comprises: from about 50 mol % to about 80 mol % SiO2; from 18 mol % to about 30 mol % Al2O3; about 14 mol % Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 4 (depends on 1)

The glass of claim 1, wherein Al2O3(mol %)/Na2O(mol %)>1.

### Claim 5 (depends on 1)

The glass of claim 1, further comprising at least one alkali metal oxide other than Na2O.

### Claim 6 (depends on 1)

The glass of claim 1, further comprising at least one divalent metal oxide.

### Claim 7 (depends on 6)

The glass of claim 6, wherein the at least one divalent metal oxide comprises at least one of ZnO and one or more alkaline earth oxide.

### Claim 8 (depends on 1)

The glass of claim 1, further comprising at least one rare earth oxide other than Y2O3.

### Claim 9 (depends on 1)

The glass of claim 1, further comprising at least one of B2O3, P2O5, and TiO2.

### Claim 10 (depends on 1)

The glass of claim 1, wherein the glass has a strain point of at least 700° C.

### Claim 11 (depends on 1)

The glass of claim 1, wherein the glass has a 200 gf Vickers hardness of at least 660 kgf/mm2.

### Claim 12 (depends on 1)

The glass of claim 1, wherein the glass is ion exchanged.

### Claim 13 (depends on 12)

The glass of claim 12, wherein the ion exchanged glass has a compressive layer extending from a surface of the glass to a depth of layer of at least 40 μm into the glass, wherein the compressive layer has a compressive stress of at least 800 MPa.

### Claim 14 (depends on 13)

The glass of claim 13, wherein the compressive layer comprises potassium ions.

### Claim 15 (depends on 12)

The glass of claim 12, wherein the ion exchanged glass has a 200 gf Vickers hardness of at least 750 kgf/mm2.

### Claim 16 (depends on 1)

The glass of claim 1, wherein the glass has a thickness in a range from about 0.1 mm up to about 1.5 mm.

### Claim 17 (depends on 1)

The glass of claim 1, wherein the glass is substantially free of Li2O.

### Claim 18

A glass comprising SiO2, at least 18 mol % Al2O3, about 14 mol % Na2O, and from 2.5 mol % to about 6.5 mol % Y2O3, the glass having a molar ratio [Al2O3(mol %)/Y2O3(mol %)] of greater than 2.5 and a Young's modulus of at least 75 GPa.

### Claim 19 (depends on 18)

The glass of claim 18, wherein the glass comprises: from about 40 mol % to about 82 mol % SiO2; from 18 mol % to about 40 mol % Al2O3; about 14 mol % Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 20 (depends on 18)

The glass of claim 18, wherein the glass comprises: from about 50 mol % to about 80 mol % SiO2; from 18 mol % to about 30 mol % Al2O3; about 14 mol % Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 21 (depends on 18)

The glass of claim 18, wherein Al2O3(mol %)/Na2O(mol %)>1.

### Claim 22 (depends on 18)

The glass of claim 18, further comprising at least one alkali metal oxide other than Na2O.

### Claim 23 (depends on 18)

The glass of claim 18, further comprising at least one divalent metal oxide.

### Claim 24 (depends on 18)

The glass of claim 18, wherein the at least one divalent oxide comprises at least one of ZnO and one or more alkaline earth oxide.

### Claim 25 (depends on 18)

The glass of claim 18, further comprising at least one rare earth oxide other than Y2O3.

### Claim 26 (depends on 18)

The glass of claim 18, further comprising at least one of B2O3, P2O5, and TiO2.

### Claim 27 (depends on 18)

The glass of claim 18, wherein the glass has a strain point of at least 700° C.

### Claim 28 (depends on 18)

The glass of claim 18, wherein the glass has a 200 gf Vickers hardness of at least 660 kgf/mm2.

### Claim 29 (depends on 18)

The glass of claim 18, wherein the glass has a Young's modulus of at least 80 GPa.

### Claim 30 (depends on 29)

The glass of claim 29, wherein the glass is ion exchanged and has a compressive layer extending from a surface of the glass to a depth of layer of at least 40 μm into the glass, wherein the compressive layer has a compressive stress of at least 800 MPa.

### Claim 31 (depends on 30)

The glass of claim 30, wherein the compressive layer comprises potassium ions.

### Claim 32 (depends on 29)

The glass of claim 29, wherein the glass is ion exchanged and has a 200 gf Vickers hardness of at least 750 kgf/mm2.

### Claim 33 (depends on 18)

The glass of claim 18, wherein the glass has a thickness in a range from about 0.1 mm up to about 1.5 mm.

### Claim 34 (depends on 18)

The glass of claim 18, wherein the glass is substantially free of Li2O.

### Claim 35

A glass comprising SiO2, at least 18 mol % Al2O3, from about 14 mol % Na2O, and from 2.5 mol % to about 6.5 mol % Y2O3, the glass having a molar ratio [Al2O3(mol %)/(Y2O3(mol %))] of greater than 2.5 and a 200 gf Vickers hardness of at least 660 kgf/mm2 and a Young's modulus of at least 75 GPa.

### Claim 36 (depends on 35)

The glass of claim 35, wherein the glass comprises: from about 40 mol % to about 82 mol % SiO2; from 18 mol % to about 40 mol % Al2O3; about 14 mol Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 37 (depends on 35)

The glass of claim 35, wherein the glass comprises: from about 50 mol % to about 80 mol % SiO2; from 18 mol % to about 30 mol % Al2O3; about 14 mol % Na2O; and from 2.5 mol % to about 6.5 mol % Y2O3.

### Claim 38 (depends on 35)

The glass of claim 35, wherein Al2O3(mol %)/Na2O(mol %)>1.

### Claim 39 (depends on 35)

The glass of claim 35, further comprising at least one alkali metal oxide other than Na2O.

### Claim 40 (depends on 35)

The glass of claim 35, further comprising at least one divalent metal oxide.

### Claim 41 (depends on 40)

The glass of claim 40, wherein the at least one divalent metal oxide comprises at least one of ZnO and one or more alkaline earth oxide.

### Claim 42 (depends on 35)

The glass of claim 35, further comprising at least one rare earth oxide other than Y2O3.

### Claim 43 (depends on 35)

The glass of claim 35, further comprising at least one of B2O3, P2O5, and TiO2.

### Claim 44 (depends on 35)

The glass of claim 35, wherein the glass has a strain point of at least 700° C.

### Claim 45 (depends on 35)

The glass of claim 35, wherein the glass is ion exchanged.

### Claim 46 (depends on 45)

The glass of claim 45, wherein the ion exchanged glass has a compressive layer extending from a surface of the glass to a depth of layer of at least 40 μm into the glass, wherein the compressive layer has a compressive stress of at least 800 MPa.

### Claim 47 (depends on 45)

The glass of claim 45, wherein the ion exchanged glass has a 200 gf Vickers hardness of at least 750 kgf/mm2.

### Claim 48 (depends on 46)

The glass of claim 46, wherein the compressive layer comprises potassium ions.

### Claim 49 (depends on 35)

The glass of claim 35, wherein the glass has a thickness in a range from about 0.1 mm up to about 1.5 mm.

### Claim 50 (depends on 35)

The glass of claim 35, wherein the glass is substantially free of Li2O.