US 2013/0296155 A1 · WHITE, OPAQUE, ß-SPODUMENE/RUTILE GLASS-CERAMICS; ARTICLES COMPRISING THE SAME; AND METHODS FOR MAKING THE SAME

Abstract

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: 62-75 SiO2; 10.5-17 Al2O3; 5-13 Li2O; 0-4 ZnO; 0-8 MgO; 2-5 TiO2; 0-4 B2O3; 0-5 Na2O; 0-4 K2O; 0-2 ZrO2; 0-7 P2O5; 0-0.3 Fe2O3; 0-2 MnOx; and 0.05-0.2 SnO2. Additionally, these glasses and glass-ceramics exhibit the following criteria: a. a ratio: [ Li 2  O + Na 2  O + K 2  O + MgO + ZnO _ ]  [ Al 2  O 3 + B 2  O 3 ] between 0.7 to 1.5; b. a ratio: [ TiO 2 + SnO 2 _ ]  [ SiO 2 + B 2  O 3 ] greater than 0.04. Furthermore, the glass-ceramics exhibit an opacity≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness and colors an observer angle of 10° and a CIE illuminant F02 determined with specular reflectance included of a* between −3 and +3, b* between −6 and +6, and L* between 88 and 97.

Claims24

Dependent claims

A glass-ceramic comprising:

a. a composition, in mole %, comprising:
i. 62-75 SiO2;
ii. 10.5-17 Al2O3;
iii. 5-13 Li2O;
iv. 0-4 ZnO;
v. 0-8 MgO;
vi. 2-5 TiO2;
vii. 0-4 B2O3;
viii. 0-5 Na2O;
ix. 0-4K2O;
x. 0-2 ZrO2;
xi. 0-7 P2O5
xii. 0-0.3 Fe2O3;
xiii. 0-2 MnOx;
and
xiv. 0.05-0.20 SnO2;
b. a ratio:
[
Li
2

O
+
Na
2

O
+
K
2

O
+
MgO
+
ZnO
]


[
Al
2

O
3
+
B
2

O
3
]
between 0.7 to 1.5;
c. a ratio:
[
TiO
2
+
SnO
2
]

[
SiO
2
+
B
2

O
3
]
greater than about 0.04;
d. one or more β-spodumene solid solutions comprising:
i. at least about 70 wt % of the crystalline phases of the glass-ceramic and
ii. one or more Li2O:Al2O3:SiO2 ratios between about 1:1:4.5-1:1:8;
e. at least one Ti-containing crystalline phase comprising:
i. about 2.5-8 wt % of the crystalline phases of the glass-ceramic,
ii. an acicular morphology exhibiting a length≧about 20 nm, and
iii. rutile;
f. an opacity comprising≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness;
and
g. optionally, one or more crystalline phase comprising:
i. up to about 10 wt % of the crystalline phases of the glass-ceramic;
and
ii. a spinel structure.

83 more elements

A process for making a crystallizable glass formulated to be crystallizable to glass-ceramics having β-spodumene as the predominant crystalline phase, the process comprising:

a. melting at a temperature below about 1600° C. a mixture of raw materials formulated to produce upon melting a crystallizable glass, in mole %, comprising:
i. 62-75 SiO2;
ii. 10.5-17 Al2O3;
iii. 5-13 Li2O;
iv. 0-4 ZnO;
v. 0-8 MgO;
vi. 2-5 TiO2;
vii. 0-4 B2O3;
viii. 0-5 Na2O;
ix. 0-4K2O;
x. 0-2 ZrO2;
xi. 0-7 P2O5
xii. 0-0.3 Fe2O3;
xiii. 0-2 MnOx;
and
xiv. 0.05-0.20 SnO2, wherein the mixture of raw materials is formulated to produce upon melting a crystallizable glass comprising:
(1.) a ratio:
[
Li
2

O
+
Na
2

O
+
K
2

O
+
MgO
+
ZnO
]


[
Al
2

O
3
+
B
2

O
3
]
comprises between 0.7 to 1.5;
(2.) a ratio:
[
TiO
2
+
SnO
2
]

[
SiO
2
+
B
2

O
3
]
comprises greater than 0.04;
and
(3.) wherein upon first heating at between about 700° C.-810° C. for between about 15-120 minutes and then heating between about 850° C.-1250° C. for between about 15-240 minutes, the crystallizable glass is capable of transforming to a glass-ceramic comprising:
(a.)β-spodumene solid solutions comprising:
(i.) at least about 70 wt % of the crystalline phases of the glass-ceramic and
(ii.) a Li2O:Al2O3:SiO2 ratio between about 1:1:4.5-1:1:8;
(b.) a Ti-containing crystalline phase comprising:
(i.) about 2.5-8 wt % the crystalline phases of the glass-ceramic and
(ii.) an acicular morphology exhibiting a length≧about 20 nm, and
(iii.) rutile;
(c.) an opacity comprising ≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness;
and
(d.) optionally, one or more crystalline phase comprising:
(i.) about 1-10 wt % of the crystalline phases of the glass-ceramic and
(ii.) a spinel structure.

84 more elements

A process for making a glass-ceramics having β-spodumene as the predominant crystalline phase, the process comprising:

a. heating a crystallizable glass at a rate of about 1-10° C./min to a nucleation temperature (Tn) between about 700° C.-810° C.;
b. maintaining the crystallizable glass at the nucleation temperature (Tn) for between about 15-120 minutes to produce a nucleated crystallizable glass;
c. heating the nucleated crystallizable glass at a rate of about 1° C.-10° C./min to a crystallization temperature (Tc) between about 850° C.-1250° C.;
d. maintaining the nucleated crystallizable glass at the crystallization temperature (Tc) for between about 15-240 minutes to produce a glass-ceramic having one or more β-spodumene solid solutions as the predominant crystalline phase;
and
e. cooling the glass-ceramic to about room temperature,
i. wherein, in mole percent (mole %), the crystallizable glass comprises:
(1.) 62-75 SiO2;
(2.) 10.5-17 Al2O3;
(3.) 5-13 Li2O;
(4.) 0-4 ZnO;
(5.) 0-8 MgO;
(6.) 2-5 TiO2;
(7.) 0-4 B2O3;
(8.) 0-5 Na2O;
(9.) 0-4K2O;
(10.) 0-2 ZrO2;
(11.) 0-7 P2O5
(12.) 0-0.3 Fe2O3;
(13.) 0-2 MnOx;
and
(14.) 0.05-0.20 SnO2;
(15.) a ratio:
[
Li
2

O
+
Na
2

O
+
K
2

O
+
MgO
+
ZnO
]


[
Al
2

O
3
+
B
2

O
3
]
comprises between 0.7 to 1.5;
(16.) a ratio:
[
TiO
2
+
SnO
2
]

[
SiO
2
+
B
2

O
3
]
comprises greater than 0.04;
and
ii. wherein the glass-ceramic comprising:
(1.) β-spodumene solid solutions comprising:
(a.) at least about 70 wt % of the crystalline phases of the glass-ceramic and
(b.) a Li2O:Al2O3:SiO2 ratio between about 1:1:4.5-1:1:8;
(2.) a Ti-containing crystalline phase comprising about 2.5-8 wt % the crystalline phases of the glass-ceramic and rutile;
(3.) an opacity comprising≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness;
and
(4.) optionally, one or more crystalline phase comprising:
(a.) about 1-10 wt % of the crystalline phases of the glass-ceramic and
(b.) a spinel structure.

87 more elements

Dependencies are inferred from the claim text.

White, opaque, ß-spodumene/rutile glass-ceramics; articles comprising the same; and methods for making the same

Life of this patent

White, opaque, ß-spodumene/rutile glass-ceramics; articles comprising the same; and methods for making the same

Life of this patent

Abstract

Claims24