US 11,926,555 B2
Crack-resistant glass-ceramic articles and methods for making the same
Lionel Joel Mary Beunet, Montigny Loing (FR); Marie Jacqueline Monique Comte, Fontenay aux Roses (FR); Allan Mark Fredholm, Vulaines sur Seine (FR); Qiang Fu, Painted Post, NY (US); Anne Paris, Thomery (FR); Sophie Peschiera, Veneux les Sablons (FR); and Charlene Marie Smith, Corning, NY (US)
Assigned to CORNING INCORPORATED, Corning, NY (US)
Filed by CORNING INCORPORATED, Corning, NY (US)
Filed on Oct. 30, 2020, as Appl. No. 17/085,115.
Application 15/641,875 is a division of application No. 14/505,763, filed on Oct. 3, 2014, granted, now 9,701,574, issued on Jul. 11, 2017.
Application 17/085,115 is a continuation of application No. 15/641,875, filed on Jul. 5, 2017, granted, now 10,822,267.
Claims priority of provisional application 61/888,617, filed on Oct. 9, 2013.
Prior Publication US 2021/0047234 A1, Feb. 18, 2021
This patent is subject to a terminal disclaimer.
Int. Cl. C03C 10/00 (2006.01); C03B 32/02 (2006.01); C03C 3/093 (2006.01); C03C 10/02 (2006.01); C03C 10/08 (2006.01); C03C 10/12 (2006.01); C03C 21/00 (2006.01)
CPC C03C 10/0027 (2013.01) [C03B 32/02 (2013.01); C03C 3/093 (2013.01); C03C 10/0018 (2013.01); C03C 10/0045 (2013.01); C03C 10/0054 (2013.01); C03C 21/002 (2013.01); Y10T 428/315 (2015.01)] 20 Claims
OG exemplary drawing
 
1. A glass-ceramic article comprising:
a composition, in mole %, comprising:
SiO2 in the range from 62 to 75;
Al2O3 in the range from 10.5 to 17;
Li2O in the range from 5 to 13;
ZnO in the range from 0 to 4;
MgO in the range from 0 to 8;
B2O3 in the range from 0 to 4;
Na2O in the range from 0 to 5;
K2O in the range from 0 to 4;
ZrO2 in the range from 0 to 2;
P2O5 in the range from 0 to 7;
Fe2O3 in the range from 0 to 0.3;
MnOx in the range from 0 to 2;
SnO2 in the range from 0.05 mole % to 0.2 mole %;
a ratio [Li2O+Na2O+K2O+MgO+ZnO]/[Al2O3+B2O3]
in the range from 0.7 to 1.5;
a crystalline phase, wherein the crystalline phase comprises β-spodumene; and
a Vickers crack initiation threshold of at least 12 kgf.
 
12. A glass-ceramic article comprising:
a composition, in mole %; comprising:
SiO2 in the range from 62 to 75;
Al2O3 in the range from 10.5 to 17;
Li2O in the range from 5 to 13;
ZnO in the range from 0 to 4;
MgO n the range from 0 to 8;
B2O3 in the range from 0 to 4;
Na2O in the range from 0 to 5;
K2O in the range from 0 to 4;
ZrO2 in the range from 0 to 2;
P2O5 in the range from 0 to 7;
Fe2O3 in the range from 0 to 0.3;
MnOx in the range from 0 to 2;
a ratio [Li2O+Na2O+K2O+MgO+ZnO]/[Al2O3+B2O3]
in the range from 0.7 to 1.5;
a crystalline phase; wherein the crystalline phase comprises β-spodumene and cordierite; and
a Vickers crack initiation threshold of at least 12 kgf,
wherein the glass-ceramic article further comprises a compressive stress of at least 300 MPa.
 
16. A method of making a glass-ceramic article comprising:
ceramming a precursor glass article having a thickness of less than 5 mm by
a) heating the at a rate in the range from 1° C./minute to 10° C./minute to a nucleating temperature (Tn) in the range from 700° C. to 810° C.,
b) maintaining the precursor glass article at the Tn to produce a nucleated crystallizable glass article,
c) heating the nucleated precursor glass article at a rate in the range from 1° C./minute to 10° C./minute to a crystallization temperature (Tc) in the range from 850° to 1250° C.,
d) maintaining the nucleated precursor glass article at the Tc to produce a glass-ceramic article having a crystalline phase, and
e) cooling the glass-ceramic article to room temperature at an average rate in the range from 10° C./minute to 25° C./minute,
wherein the glass-ceramic article comprises a composition, in mole %, comprising:
SiO2 in the range from 62 to 75;
Al2O3 in the range from 10.5 to 17;
Li2O in the range from 5 to 13;
ZnO in the range from 0 to 4;
MgO in the range from 0 to 8;
B2O3 in the range from 0 to 4;
Na2O in the range from 0 to 5;
K2O in the range from 0 to 4;
ZrO2 in the range from 0 to 2;
P2O5 in the range from 0 to 7;
Fe2O3 in the range from 0 to 0.3;
MnOx in the range from 0 to 2;
SnO2 in the range from 0.05 mole % to 0.2 mole %;
a ratio [Li2O+Na2O+K2O+MgO+ZnO]/[Al2O3+B2O3]in the range from 0.7 to 1.5;
the crystalline phase comprises β-spodumene; and
the glass-ceramic article exhibits a Vickers crack initiation threshold of at least 12 kgf.