IP Library › Granted Patent US 11,351,756

Granted Patent B2

US 11,351,756 · App. 16/771,893 · Granted Jun 7, 2022

Laminate glass ceramic articles with UV-and NIR-blocking characteristics and methods of making the same

Inventors: Matthew John Dejneka (Corning, NY); Jesse Kohl (Horseheads, NY)

Assignee: CORNING INCORPORATED

B32B17/101 B32B7/027 B32B17/06 B32B17/10045 B32B17/10678 C03C3/091 C03C4/082 C03C4/085 B32B2250/03 B32B2250/40 B32B2307/42 B32B2307/71 B32B2315/08 C03C21/002

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Quick Facts

Patent No.: US 11,351,756
App. No.: 16/771,893
Granted: Jun 7, 2022
Kind: B2

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Abstract

A laminate glass-ceramic article is provided that includes: a core glass layer having a first coefficient of thermal expansion (CTE); and a plurality of clad glass-ceramic layers, each having a CTE that is lower than or equal to the first CTE of the core glass layer. A first of the clad glass-ceramic layers is laminated to a first surface of core glass layer and a second of the clad glass-ceramic layers is laminated to a second surface of the core glass layer. Further, a total thickness of the plurality of clad glass-ceramic layers is from about 0.05 mm to about 0.5 mm. In addition, each of the glass-ceramic layers includes: an alumino-boro-silicate glass, 0 mol %≤MoO3≤15 mol %, and 0 mol %≤WO3≤15 mol %, the WO3 (mol %) plus the MoO3 (mol %) is from 0.7 mol % to 19 mol %.

Claims (87)

1. A laminate glass-ceramic article, comprising:

a core glass layer having a first coefficient of thermal expansion (CTE); and

a plurality of clad glass-ceramic layers, each having a CTE that is lower than or equal to the first CTE of the core glass layer,

wherein a first of the clad glass-ceramic layers is laminated to a first surface of core glass layer and a second of the clad glass-ceramic layers is laminated to a second surface of the core glass layer,

wherein a total thickness of the plurality of clad glass-ceramic layers is from about 0.05 mm to about 0.5 mm,

wherein each of the clad glass-ceramic layers comprises:

an alumino-boro-silicate glass,

0 mol %≤MoO 3 ≤15 mol %,

0.1 mol %≤WO 3 15 mol %,

1 mol %≤Al 2 O 3 ≤20 mol %, and

0.1 mol %≤R 2 O≤15 mol %, R 2 O is one or more of Li 2 O, Na 2 O, K 2 O and Cs 2 O,

wherein the WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 19 mol %, and

wherein R 2 O (mol %) minus the Al 2 O 3 (mol %) is from −12 mol % to 4 mol %, and

wherein each of the glass-ceramic layers further comprises a glassy phase and at least one crystalline phase selected from the group consisting of a stoichiometric crystalline phase, a non-stoichiometric crystalline phase and a mixed stoichiometric and non-stoichiometric crystalline phase, and

wherein the at least one crystalline phase comprises a crystalline phase of M x WO 3 and/or M y MoO 3 , wherein M is at least one of H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Sn, P, S, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ga, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ta, Os, Ir, Pt, Au, TI, Pb, Bi, and U, and wherein 0≤x≤1 and 0≤y≤1.

2. The laminate article of claim 1 , wherein each of the glass-ceramic layers further comprises:

40 mol %≤SiO 2 ≤80 mol %;

3 mol %≤B 2 O 3 ≤50 mol %;

0 mol %≤RO≤2 mol %, RO is one or more of MgO, CaO, SrO and BaO;

0 mol %≤P 2 O 5 ≤3 mol %; and

0 mol %≤SnO 2 ≤0.5 mol %.

3. The laminate article of claim 2 , wherein each of the glass-ceramic layers further comprises: 0.7 mol %≤WO 3 ≤15 mol %, and 0 mol %≤MoO 3 ≤trace amounts, and further wherein the WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 15 mol %.

4. The laminate article of claim 2 , wherein each of the glass-ceramic layers further comprises: 0.1 mol %≤WO 3 ≤7 mol %, and 0.1 mol %≤MoO 3 ≤15 mol %.

5. The laminate article of claim 1 , wherein a thickness of the core glass layer is from about 0.2 mm to about 2.8 mm.

6. The laminate article of claim 1 , wherein the laminate glass-ceramic article further comprises a total transmittance of less than or equal to 5% at ultraviolet (UV) wavelengths below 390 nm and a total transmittance from about 1% to about 15% in the near infrared (NIR) spectrum from 700 nm to 1500 nm.

7. The laminate article of claim 6 , wherein the laminate glass-ceramic article further comprises a total transmittance from about 1% to about 30% in the visible spectrum from 400 nm to 700 nm.

8. The laminate article of claim 6 , wherein the laminate glass-ceramic article further comprises a total transmittance of greater than or equal to about 70% in the visible spectrum from 400 nm to 700 nm.

9. The laminate article of claim 1 , wherein 0.1 mol %≤WO 3 ≤10 mol %.

10. The laminate article of claim 9 , wherein each of the glass-ceramic layers further comprises:

40 mol %≤SiO 2 ≤80 mol %;

3 mol %≤B 2 O 3 ≤50 mol %;

0 mol %≤RO≤2 mol %, RO is one or more of MgO, CaO, SrO and BaO;

0 mol %≤P 2 O 5 ≤3 mol %; and

0 mol %≤SnO 2 ≤0.5 mol %.

11. The laminate article of claim 9 , wherein a thickness of the core glass layer is from about 0.2 mm to about 2.8 mm.

12. The laminate article of claim 11 , wherein each of the glass-ceramic layers further comprises: 0.7 mol %≤WO 3 ≤15 mol %, and 0 mol %≤MoO 3 ≤trace amounts, and further wherein the WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 15 mol %.

13. The laminate article of claim 11 , wherein each of the glass-ceramic layers further comprises: 0.1 mol %≤WO 3 ≤7 mol %, and 0.1 mol %≤MoO 3 ≤15 mol %.

14. The laminate article of claim 9 , wherein the laminate glass-ceramic article further comprises a total transmittance of less than or equal to 5% at ultraviolet (UV) wavelengths below 390 nm and a total transmittance from about 1% to about 15% in the near infrared (NIR) spectrum from 700 nm to 1500 nm.

15. The laminate article of claim 14 , wherein the laminate glass-ceramic article further comprises a total transmittance from about 1% to about 30% in the visible spectrum from 400 nm to 700 nm.

16. The laminate article of claim 14 , wherein the laminate glass-ceramic article further comprises a total transmittance of greater than or equal to about 70% in the visible spectrum from 400 nm to 700 nm.

17. The laminate article of claim 9 , wherein the at least one crystalline phase comprises ternary metal oxides of the general formula M′ x M″ y O z , where M″ is a transition metal or a combination of transition metals, M′ is a metal or a combination of metals that differ from M″, 2≤z≤5, and x and y are based on z and the valence of M′ and M″.

18. A laminate glass-ceramic article, comprising:

a core glass-ceramic layer having a first coefficient of thermal expansion (CTE); and

a plurality of clad glass layers, each having a CTE that is lower than or equal to the first CTE of the core glass-ceramic layer,

wherein a first of the clad glass layers is laminated to a first surface of core glass-ceramic layer and a second of the clad glass layers is laminated to a second surface of the core glass-ceramic layer,

wherein a total thickness of the plurality of clad glass layers is from about 0.05 mm to about 0.5 mm, and

wherein the core glass-ceramic layer comprises:

an alumino-boro-silicate glass,

0 mol %≤MoO 3 ≤15 mol %,

0.1 mol %≤WO 3 ≤15 mol %,

1 mol %≤Al 2 O 3 ≤20 mol %, and

0.1 mol %≤R 2 O≤15 mol %, R 2 O is one or more of Li 2 O, Na 2 O, K 2 O and Cs 2 O,

wherein the WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 19 mol %, and

wherein R 2 O (mol %) minus the Al 2 O 3 (mol %) is from −12 mol % to 4 mol %,

wherein the glass-ceramic layer further comprises a glassy phase and at least one crystalline phase selected from the group consisting of a stoichiometric crystalline phase, a non-stoichiometric crystalline phase and a mixed stoichiometric and non-stoichiometric crystalline phase, and

19. The laminate article of claim 18 , wherein the core glass-ceramic layer further comprises:

40 mol %≤SiO 2 ≤80 mol %;

3 mol %≤B 2 O 3 ≤50 mol %;

0 mol %≤RO≤2 mol %, RO is one or more of MgO, CaO, SrO and BaO;

0 mol %≤P 2 O 5 ≤3 mol %; and

0 mol %≤SnO 2 ≤0.5 mol %.

20. The laminate article of claim 19 , wherein the core glass-ceramic layer further comprises: 0.7 mol %≤WO 3 ≤15 mol %, and 0 mol %≤MoO 3 ≤trace amounts, and further wherein the WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 15 mol %.

21. The laminate article of claim 19 , wherein the core glass-ceramic layer further comprises: 0.1 mol %≤WO 3 ≤7 mol %, and 0.1 mol %≤MoO 3 ≤15 mol %.

22. The laminate article of claim 18 , wherein a thickness of the core glass-ceramic layer is from about 0.2 mm to about 2.8 mm.

23. The laminate article of claim 18 , wherein the laminate article further comprises a total transmittance of less than or equal to 5% at ultraviolet (UV) wavelengths below 390 nm and a total transmittance from about 1% to about 15% in the near infrared (NIR) spectrum from 700 nm to 1500 nm.

24. The laminate article of claim 23 , wherein the laminate glass-ceramic article further comprises a total transmittance from about 1% to about 30% in the visible spectrum from 400 nm to 700 nm.

25. A window, comprising:

a laminate glass-ceramic article, comprising:

a core glass layer having a first coefficient of thermal expansion (CTE); and

a plurality of clad glass-ceramic layers, each having a CTE that is lower than or equal to the first CTE of the core glass layer,

wherein a total thickness of the plurality of clad glass-ceramic layers is from about 0.05 mm to about 0.5 mm,

wherein each of the clad glass-ceramic layers comprises: an alumino-boro-silicate glass, 0 mol %≤MoO 3 ≤15 mol %, 0.1 mol %≤WO 3 ≤15 mol %, 1 mol %≤Al 2 O 3 ≤20 mol %, and 0.1 mol %≤R 2 O≤15 mol %, R 2 O is one or more of Li 2 O, Na 2 O, K 2 O and Cs 2 O, wherein WO 3 (mol %) plus the MoO 3 (mol %) is from 0.7 mol % to 19 mol %, and wherein R 2 O (mol %) minus the Al 2 O 3 (mol %) is from −12 mol % to 4 mol %,

wherein the laminate glass-ceramic article further comprises: (a) a total transmittance of less than or equal to 5% at ultraviolet (UV) wavelengths below 390 nm, (b) a total transmittance from about 1% to about 15% in the near infrared (NIR) spectrum from 700 nm to 1500 nm, and (c) a total transmittance from about 1% to about 30% in the visible spectrum from 400 nm to 700 nm.

26. A window, comprising:

a laminate glass-ceramic article, comprising:

a core glass layer having a first coefficient of thermal expansion (CTE); and

a plurality of clad glass-ceramic layers, each having a CTE that is lower than or equal to the first CTE of the core glass layer,

wherein a total thickness of the plurality of clad glass-ceramic layers is from about 0.05 mm to about 0.5 mm, and

wherein the laminate glass-ceramic article further comprises: (a) a total transmittance of less than or equal to 5% at ultraviolet (UV) wavelengths below 390 nm, (b) a total transmittance from about 1% to about 15% in the near infrared (NIR) spectrum from 700 nm to 1500 nm, and (c) a total transmittance of greater than or equal to about 70% in the visible spectrum from 400 nm to 700 nm.

Assignments (1)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 23, 2021

From: DEJNEKA, MATTHEW JOHN; KOHL, JESSE

To: CORNING INCORPORATED

Reel/Frame 055363/0249 →

Continuity (2)

Provisional Application 62599517 · Dec 15, 2017

Related Publication 20210070018A1 · Mar 11, 2021

Cited By (2)

US 12,252,437 US 12,637,388