White, opaque,β-spodumene glass-ceramic articles with inherent damage resistance and methods for making the same
Crystallizable glasses, glass-ceramics, IXable glass-ceramics, and IX glass-ceramics are disclosed. The glass-ceramics exhibit β-spodumene ss as the predominant crystalline phase. These glasses and glass-ceramics, in mole %, include: 60-75 SiO 2 ; 10-18 Al 2 O 3 ; 5-14 Li 2 O; and 4.5 B 2 O 3 . The glass-ceramics also have a Vickers initiation crack threshold of at least about 25 kgf.
1. A glass-ceramic article comprising:
a) a composition, in mole %, comprising:
i) SiO 2 in a range from about 60 to about 75,
ii) Al 2 O 3 in a range from about 10 to about 18,
iii) Li 2 O in a range from about 5 to about 14, and
iv) B 2 O 3 in a range from about 10 to about 20,
wherein a ratio of the mole sum total [Li 2 O+Na 2 O+K 2 O+MgO+ZnO]/moles of [Al 2 O 3 ] is in a range from about 0.8 to about 1.5; and
b) a Vickers crack initiation threshold of a least about 25 kgf. wherein β-spodumene is the predominant crystalline phase.
2. The glass-ceramic article of claim 1 , wherein the Vickers crack initiation threshold is at least about 30 kgf.
3. The glass-ceramic article of claim 1 , wherein the Vickers crack initiation threshold is at least about 35 kgf.
4. The glass-ceramic article of claim 1 , wherein the Vickers crack initiation threshold is at least about 40 kgf.
5. The glass-ceramic article of claim 1 , wherein the Vickers crack initiation threshold is at least about 45 kgf.
6. The glass-ceramic article of claim 1 , wherein at least about 50% of the B 2 O 3 present in a residual glass comprises three-fold coordination boron cations.
7. The glass-ceramic article of claim 1 , wherein the composition further comprises:
v) MgO in a range from 0 to about 8,
vi) ZnO in a range from 0 to about 4,
vii) TiO 2 in a range from about 2 to about 5,
viii) Na 2 O in a range from 0 to about 5,
ix) K 2 O in a range from 0 to about 4, and
x) SnO 2 in a range from about 0.05 to about 0.5.
8. The glass-ceramic article of claim 1 , wherein the composition, in mole %, comprises:
i) SiO 2 in a range from about 60 to about 70,
ii) Al 2 O 3 in a range from about 10 to about 16,
iii) Li 2 O in a range from about 7 to about 10,
iv) B 2 O 3 in a range from about 6 to about 8,
v) MgO in a range from about 2 to about 5,
vi) ZnO in a range from about 1 to about 2,
vii) TiO 2 in a range from about 3 to about 4,
viii) Na 2 O in a range from about 0.4 to about 0.6, and
ix) SnO 2 in a range from about 0.2 to about 0.5.
9. The glass-ceramic article of claim 1 , wherein the composition comprises B 2 O 3 in a range from about 6 to about 10 mole %.
10. The glass-ceramic article of claim 1 , wherein the composition comprises B 2 O 3 in a range from about 6 to about 8 mole %.
11. The glass-ceramic article of claim 1 , wherein the composition comprises ZrO 2 in a range from 0 to about 3 mole %.
12. The glass-ceramic article of claim 1 , wherein the glass-ceramic article comprises a color presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02 determined from reflectance spectra measurements using a spectrophotometer with specular reflectance included comprising:
a) CIE a* in a range from about −2 to about 1;
b) CIE b* in a range from about −5 to about −2; and
c) CIE L* in a range from about 80 to about 98.
13. The glass-ceramic article of claim 1 , further comprising a compressive stress layer formed by ion-exchange.
14. The glass-ceramic article of claim 13 , wherein the compressive stress layer has a compressive stress of at least 80 MPa and a depth of layer (DOL) of at least about 2% of an overall thickness of the article.
15. An electronic device comprising the glass-ceramic article of claim 1 .
16. A glass-ceramic article comprising:
a) a composition, in mole %, comprising:
i) SiO 2 in a range from about 60 to about 75,
ii) Al 2 O 3 in a range from about 10 to about 18,
iii) Li 2 O in a range from about 5 to about 14,
iv) B 2 O 3 in a range from about 8 to about 20,
v) TiO 2 in a range from about 2 to about 5, and
vi) SnO 2 in a range from about 0.05 to about 0.5; and
b) a Vickers crack initiation threshold of a least about 25 kgf,
wherein β-spodumene is the predominant crystalline phase.
17. The glass-ceramic article of claim 16 , wherein the composition further comprises:
vii) MgO in a range from 0 to about 8,
viii) ZnO in a range from 0 to about 4,
ix) Na 2 O in a range from 0 to about 5, and
x) K 2 O in a range from 0 to about 4.
18. The glass-ceramic article of claim 16 , wherein the Vickers crack initiation threshold is at least about 30 kgf.
19. The glass-ceramic article of claim 16 , wherein the Vickers crack initiation threshold is at least about 35 kgf.
20. The glass-ceramic article of claim 16 , wherein the Vickers crack initiation threshold is at least about 40 kgf.
21. The glass-ceramic article of claim 16 , wherein the Vickers crack initiation threshold is at least about 45 kgf.
22. The glass-ceramic article of claim 16 , wherein at least about 50% of the B 2 O 3 present in a residual glass comprises three-fold coordination boron cations.
23. The glass-ceramic article of claim 16 , wherein the composition comprises ZrO 2 in a range from 0 to about 3 mole %.
24. The glass-ceramic article of claim 16 , wherein the glass-ceramic article comprises a color presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02 determined from reflectance spectra measurements using a spectrophotometer with specular reflectance included comprising:
a) CIE a* in a range from about −2 to about 1;
b) CIE b* in a range from about −5 to about −2; and
c) CIE L* in a range from about 80 to about 98.
25. The glass-ceramic article of claim 16 , further comprising a compressive stress layer formed by ion-exchange.
26. The glass-ceramic article of claim 25 , wherein the compressive stress layer has a compressive stress of at least 80 MPa and a depth of layer (DOL) of at least about 2% of an overall thickness of the article.
27. An electronic device comprising the glass-ceramic article of claim 16 .
28. The glass-ceramic article of claim 16 , wherein a ratio of the mole sum total [Li 2 O+Na 2 O+K 2 O+MgO+ZnO]/moles of [Al 2 O 3 ] is in a range from about 0.8 to about 1.5.