阅读说明：本技术 具有优化的颜色包装的黑色β-锂辉石玻璃陶瓷 (Black beta-spodumene glass ceramic with optimized color packing ) 是由 A·V·德斯那 付强 A·M·维提尔 于 2018-11-30 设计创作，主要内容包括：提供了一种黑色β-锂辉石玻璃陶瓷。玻璃陶瓷包含β-锂辉石作为主晶相和锌尖晶石作为次晶相。玻璃陶瓷表征为如下色坐标：L*为20.0至40.0；a*为-1.0至0.5；以及b*为-5.0至1.0。玻璃陶瓷可以经过离子交换。还提供了玻璃陶瓷的生产方法。(A black beta-spodumene glass ceramic is provided. The glass ceramic comprises beta-spodumene as the primary crystalline phase and gahnite as the secondary crystalline phase. The glass-ceramic is characterized by the following color coordinates: l is 20.0 to 40.0; a is-1.0 to 0.5; and b is-5.0 to 1.0. The glass-ceramic may be ion exchanged. A method for producing the glass-ceramic is also provided.)

1. A glass-ceramic, comprising:

a β -spodumene crystal phase as a main crystal phase; and

the zinc spinel crystal phase is taken as a secondary crystal phase,

wherein the glass-ceramic is characterized by the following color coordinates:

l is 20.0 to 40.0;

a is-1.0 to 0.5; and

b is-5.0 to 1.0.

2. The glass ceramic of claim 1, further comprising pseudobrookite as a secondary crystalline phase.

3. The glass-ceramic of claim 1 or 2, further comprising ferrierite as a secondary crystalline phase.

4. The glass-ceramic of any of claims 1 through 3, wherein the glass-ceramic has a transmittance in the visible range of less than or equal to 1%.

5. The glass-ceramic of any one of claims 1 to 4, further comprising:

greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂；

Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃；

Greater than or equal to 3 wt% to less than or equal to 5 wt% Li₂O；

Greater than or equal to 0 wt% to less than or equal to 2 wt% Na₂O；

Greater than or equal to 0.5 wt% to less than or equal to 3 wt% MgO;

greater than or equal to 0.5 wt% to less than or equal to 4 wt% ZnO;

greater than or equal to 2% to less than or equal to 6% TiO by weight₂；

Greater than or equal to 0.1 wt.% to less than or equal to 1.0 wt.% SnO₂；

Greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

6. The glass-ceramic of any one of claims 1 to 5, further comprising greater than or equal to 65 wt.% to less than or equal to 67 wt.% SiO₂。

7. The glass-ceramic of any one of claims 1 to 6, further comprising less than or equal to 15 wt.% Li₂O。

8. The glass-ceramic of any one of claims 1 to 7, further comprising greater than or equal to 0 wt.% to less than or equal to 5 wt.% Na₂O。

9. The glass-ceramic of any one of claims 1 to 8, further comprising from greater than 0 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

10. The glass-ceramic of any one of claims 1 through 9, wherein the glass-ceramic has a crystallinity of greater than or equal to 50 wt.%.

11. The glass ceramic of any one of claims 1 to 10, wherein β -spodumene is the only predominant crystalline phase.

12. The glass ceramic of any one of claims 1 to 11, further comprising a grain size greater than or equal to 0.1 μ ι η to less than or equal to 1.0 μ ι η.

13. The glass-ceramic of any of claims 1 through 12, wherein the glass-ceramic is ion exchanged and comprises a compressive stress layer extending from a surface of the glass-ceramic into the glass-ceramic.

14. A consumer electronic product, comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic assembly at least partially located within the housing, the electronic assembly including at least a controller, a memory, and a display, the display located at or adjacent to a front surface of the housing; and

a cover glass disposed over the display,

wherein at least a portion of the housing comprises the glass-ceramic of any one of claims 1 to 12.

15. A consumer electronic product, comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic assembly at least partially located within the housing, the electronic assembly including at least a controller, a memory, and a display, the display located at or adjacent to a front surface of the housing; and

a cover glass disposed over the display,

wherein at least a portion of the housing comprises the glass-ceramic of claim 13.

16. A glass-ceramic, comprising:

a β -spodumene crystal phase as a main crystal phase;

greater than or equal to 0.2 wt.% toLess than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄，

Wherein the glass-ceramic is characterized by the following color coordinates:

l is 20.0 to 40.0;

a is-1.0 to 0.5; and

b is-5.0 to 1.0.

17. The glass ceramic of claim 16, further comprising pseudobrookite as a secondary crystalline phase.

18. The glass ceramic of claim 16 or 17, further comprising maficite as a secondary crystalline phase.

19. The glass-ceramic of any one of claims 16 to 18, further comprising gahnite as a secondary crystalline phase.

20. The glass-ceramic of any of claims 16 through 19, wherein the glass-ceramic has a transmittance in the visible range of less than or equal to 1%.

21. The glass-ceramic of any one of claims 16 to 20, further comprising:

greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂；

Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃；

Greater than or equal to 3 wt% to less than or equal to 5 wt% Li₂O；

Greater than or equal to 0 wt% to less than or equal to 2 wt% Na₂O；

Greater than or equal to 0.5 wt% to less than or equal to 3 wt% MgO;

greater than or equal to 0.5 wt% to less than or equal to 4 wt% ZnO;

greater than or equal to 2 wt% to less than or equal toEqual to 6% by weight of TiO₂；

Greater than or equal to 0.1 wt.% to less than or equal to 1.0 wt.% SnO₂；

Greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

22. The glass ceramic of any one of claims 16 to 21, further comprising greater than or equal to 65 wt% to less than or equal to 67 wt% SiO₂。

23. The glass-ceramic of any one of claims 16 to 22, further comprising less than or equal to 15 wt.% Li₂O。

24. The glass-ceramic of any one of claims 16 to 23, further comprising greater than or equal to 0 wt.% to less than or equal to 5 wt.% Na₂O。

25. The glass ceramic of any one of claims 16 to 24, further comprising greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

26. The glass ceramic of any of claims 16 through 25, wherein the glass ceramic has a crystallinity of greater than or equal to 50 wt.%.

27. The glass ceramic of any one of claims 16 through 26, wherein β -spodumene is the only predominant crystalline phase.

28. The glass ceramic of any one of claims 16 to 27, further comprising a grain size greater than or equal to 0.1 μ ι η to less than or equal to 1.0 μ ι η.

29. The glass-ceramic of any of claims 16 through 28, wherein the glass-ceramic is ion exchanged and comprises a compressive stress layer extending from a surface of the glass-ceramic into the glass-ceramic.

30. A consumer electronic product, comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic assembly at least partially located within the housing, the electronic assembly including at least a controller, a memory, and a display, the display located at or adjacent to a front surface of the housing; and

a cover glass disposed over the display,

wherein at least a portion of the housing comprises the glass-ceramic of any of claims 16-28.

31. A consumer electronic product, comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic assembly at least partially located within the housing, the electronic assembly including at least a controller, a memory, and a display, the display located at or adjacent to a front surface of the housing; and

a cover glass disposed over the display,

wherein at least a portion of the housing comprises the glass-ceramic of claim 29.

32. A method, comprising:

nucleating a precursor glass-based article to form a nucleated glass-based article;

ceramming the nucleated glass-based article to form a glass-ceramic,

wherein the glass-ceramic comprises:

a β -spodumene crystal phase as a main crystal phase; and

a zinc spinel crystal phase as a secondary crystal phase, and

the glass-ceramic is characterized by the following color coordinates:

l is 20.0 to 40.0;

a is-1.0 to 1.0; and

b is-5.0 to 2.0.

33. The method of claim 32, wherein ceramming is performed at a temperature of greater than or equal to 900 ℃ to less than or equal to 1100 ℃.

34. The method of claim 32 or 33, wherein ceramming is performed for a period of time greater than or equal to 0.25 hours to less than or equal to 16 hours.

35. The method of any one of claims 32-34, wherein the temperature at which nucleation occurs is greater than or equal to 725 ℃ to less than or equal to 850 ℃.

36. The method of any of claims 32-35, wherein nucleation is performed for a period of time greater than or equal to 0.5 hours to less than or equal to 6 hours.

37. The method of any one of claims 32-36, further comprising ion exchanging the glass-ceramic.

38. The method of any one of claims 32 to 37, wherein the precursor glass-based article comprises:

greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂；

Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃；

Greater than or equal to 3 wt% to less than or equal to 5 wt% Li₂O；

Greater than or equal to 0 wt% to less than or equal to 2 wt% Na₂O；

Greater than or equal to 0.5 wt% to less than or equal to 3 wt% MgO;

greater than or equal to 0.5 wt% to less than or equal to 4 wt% ZnO;

greater than or equal to 2% to less than or equal to 6% TiO by weight₂；

Greater than or equal to 0.1 wt.% to less than or equal to 1.0 wt.% SnO₂；

Greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

39. The method of any of claims 32 to 38, wherein the precursor glass-based article comprises greater than 0 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

40. A method, comprising:

nucleating a precursor glass-based article to form a nucleated glass-based article;

ceramming the nucleated glass-based article to form a glass-ceramic,

wherein the glass-ceramic comprises:

a β -spodumene crystal phase as a main crystal phase;

greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄，

The glass-ceramic is characterized by the following color coordinates:

l is 20.0 to 40.0;

a is-1.0 to 1.0; and

b is-5.0 to 2.0.

41. The method of claim 40, wherein ceramming is performed at a temperature of greater than or equal to 900 ℃ to less than or equal to 1100 ℃.

42. The method of claim 40 or 41, wherein ceramming is performed for a period of time greater than or equal to 0.25 hours to less than or equal to 16 hours.

43. The method of any one of claims 40 to 42, wherein nucleation is carried out at a temperature of greater than or equal to 725 ℃ to less than or equal to 850 ℃.

44. The method of any one of claims 40-43, wherein nucleation is performed for a period of time greater than or equal to 0.5 hours to less than or equal to 6 hours.

45. The method of any one of claims 40 to 44, further comprising ion exchanging the glass-ceramic.

46. The method of any one of claims 40 to 45, wherein the precursor glass-based article comprises:

greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂；

Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃；

Greater than or equal to 3 wt% to less than or equal to 5 wt% Li₂O；

Greater than or equal to 0 wt% to less than or equal to 2 wt% Na₂O；

Greater than or equal to 0.5 wt% to less than or equal to 3 wt% MgO;

greater than or equal to 0.5 wt% to less than or equal to 4 wt% ZnO;

greater than or equal to 2% to less than or equal to 6% TiO by weight₂；

Greater than or equal to 0.1 wt.% to less than or equal to 1.0 wt.% SnO₂；

Greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

47. The method of any of claims 40 to 46, wherein the precursor glass-based article comprises greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

48. A glass, comprising:

greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂；

Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃；

Greater than or equal to 3 wt% to less than or equal to 5 wt% Li₂O；

Greater than or equal to 0 wt% to less than or equal to 2 wt% Na₂O；

Greater than or equal to 0.5 wt% to less than or equal to 3 wt% MgO;

greater than or equal to 0.5 wt% to less than or equal to 4 wt% ZnO;

greater than or equal to 2% to less than or equal to 6% TiO by weight₂；

Greater than or equal to 0.1 wt.% to less than or equal to 1.0 wt.% SnO₂；

Greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And

greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

49. The glass of claim 48, comprising greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

Technical Field

The present description relates generally to glass-ceramic compositions. More particularly, the present description relates to black β -spodumene glass-ceramics that may form housings for electronic devices.

Background

Portable electronic devices, such as smartphones, tablets, and wearable devices (e.g., watches and fitness trackers), continue to become smaller and more complex. As such, the materials conventionally used on at least one exterior surface of such portable electronic devices continue to become more complex. For example, as portable electronic devices become smaller and thinner to meet consumer demand, the housings for these portable electronic devices also become smaller and thinner, resulting in higher performance requirements for the materials used to form these components.

Therefore, there is a need for materials exhibiting higher performance (e.g., damage resistance) and aesthetic appearance for use in portable electronic devices.

Disclosure of Invention

According to aspect (1), a glass-ceramic is provided. The glass-ceramic comprises: a β -spodumene crystal phase as a main crystal phase; and a gahnite crystal phase as a secondary crystal phase. The glass-ceramic is characterized by the following color coordinates: l is 20.0 to 40.0; a is-1.0 to 0.5; and b is-5.0 to 1.0.

According to aspect (2), there is provided the glass-ceramic of aspect (1), further comprising pseudobrookite as a secondary crystal phase.

According to aspect (3), there is provided the glass-ceramic of aspect (1) or (2), further comprising ferrierite (armalcolate) as a secondary crystal phase.

According to aspect (4), there is provided the glass-ceramic of any one of aspects (1) to (3), wherein the glass-ceramic has a transmittance in the visible light range of less than or equal to 1%.

According to aspect (5), there is provided the glass-ceramic of any one of aspects (1) to (4), further comprising: greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃Greater than or equal to 3% to less than or equal to 5% by weight Li₂O, greater than or equal to 0% by weight to less than or equal to 2% by weight Na₂O, from greater than or equal to 0.5% to less than or equal to 3% by weight MgO, from greater than or equal to 0.5% to less than or equal to 4% by weight ZnO, from greater than or equal to 2% to less than or equal to 6% by weight TiO₂From greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% SnO₂From greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

According to aspect (6), there is provided the glass-ceramic of any one of aspects (1) to (5), further comprising greater than or equal to 65% by weight to less than or equal to 67% by weight of SiO₂。

According to aspect (7), there is provided the glass-ceramic of any one of aspects (1) to (6), further comprising less than or equal to 15 wt% Li₂O。

According to aspect (8), there is provided the glass-ceramic of any one of aspects (1) to (7), further comprising greater than or equal to 0% by weight to less than or equal to 5% by weight of Na₂O。

According to aspect (9), there is provided the glass-ceramic of any one of aspects (1) to (6), further comprising from greater than 0 wt% to less than or equal to 1.5 wt% Fe₂O₃。

According to aspect (10), there is provided the glass-ceramic of any one of aspects (1) to (9), wherein the glass-ceramic has a crystallinity of 50 wt% or more.

According to aspect (11), there is provided the glass-ceramic of any one of aspects (1) to (10), wherein β -spodumene is the only predominant crystalline phase.

According to aspect (12), there is provided the glass-ceramic of any one of aspects (1) to (11), further comprising a grain size of greater than or equal to 0.1 μm to less than or equal to 1.0 μm.

According to aspect (13), there is provided the glass-ceramic of any one of aspects (1) to (12), wherein the glass-ceramic is ion exchanged and comprises a compressive stress layer extending from a surface of the glass-ceramic into the glass-ceramic.

According to an aspect (14), a consumer electronics product is provided. The consumer electronic product includes: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially within the housing, the electronic assembly including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass disposed over the display. At least a portion of the housing comprises the glass-ceramic of any one of aspects (1) to (12).

According to an aspect (15), a consumer electronics product is provided. The consumer electronic product includes: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially within the housing, the electronic assembly including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass disposed over the display. At least a portion of the housing comprises the glass-ceramic of aspect (13).

According to an aspect (16), there is provided a glass ceramic comprising β -spodumene as a predominant crystalline phase, greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄. The glass-ceramic is characterized by the following color coordinates: l is 20.0 to 40.0; a is-1.0 to 0.5; and b is-5.0 to 1.0.

According to the aspect (17), there is provided the glass-ceramic of the aspect (16), which further comprises pseudobrookite as a secondary crystal phase.

According to aspect (18), there is provided the glass-ceramic of aspect (16) or (17), further comprising ferrierite as a secondary crystal phase.

According to aspect (19), there is provided the glass-ceramic of any one of aspects (16) to (18), further comprising gahnite as a secondary crystal phase.

According to aspect (20), there is provided the glass-ceramic of any one of aspects (16) to (19), wherein a transmittance of the glass-ceramic in a visible light range is less than or equal to 1%.

According to aspect (21), there is provided the glass-ceramic of any one of aspects (16) to (20), further comprising: greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃Greater than or equal to 3% to less than or equal to 5% by weight Li₂O, greater than or equal to 0% by weight to less than or equal to 2% by weight Na₂O, from greater than or equal to 0.5% to less than or equal to 3% by weight MgO, from greater than or equal to 0.5% to less than or equal to 4% by weight ZnO, from greater than or equal to 2% to less than or equal to 6% by weight TiO₂From greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% SnO₂From greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

According to aspect (22), there is provided the glass-ceramic of any one of aspects (16) to (21), further comprising greater than or equal to 65 wt% to less than or equal to 67 wt% SiO₂。

According to aspect (23), there is provided the glass-ceramic of any one of aspects (16) to (22), further comprising less than or equal to 15 wt.% Li₂O。

According to aspect (24), there is provided the glass-ceramic of any one of aspects (16) to (23), further comprising greater than or equal to 0 wt% to less than or equal to 5 wt% Na₂O。

According to aspect (25), there is provided the glass-ceramic of any one of aspects (16) to (24), further comprising greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

According to aspect (26), there is provided the glass-ceramic of any one of aspects (16) to (25), wherein the glass-ceramic has a crystallinity of greater than or equal to 50 wt.%.

According to aspect (27), there is provided the glass-ceramic of any one of aspects (16) to (26), wherein β -spodumene is the only predominant crystalline phase.

According to aspect (28), there is provided the glass-ceramic of any one of aspects (16) to (27), further comprising a grain size of greater than or equal to 0.1 μm to less than or equal to 1.0 μm.

According to aspect (29), there is provided the glass-ceramic of any of aspects (16) to (28), wherein the glass-ceramic is ion exchanged and comprises a compressive stress layer extending from a surface of the glass-ceramic into the glass-ceramic.

According to an aspect (30), a consumer electronics product is provided. The consumer electronic product includes: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially within the housing, the electronic assembly including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass disposed over the display. At least a portion of the housing comprises the glass-ceramic of any of aspects (16) to (28).

According to an aspect (31), a consumer electronics product is provided. The consumer electronic product includes: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially within the housing, the electronic assembly including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass disposed over the display. At least a portion of the housing comprises the glass-ceramic of aspect (29).

According to aspect (32), a method is provided. The method comprises the following steps: nucleating the precursor glass-based article to form a nucleated glass-based article; ceramming the nucleated glass-based article to form a glass-ceramic. The glass-ceramic comprises: a β -spodumene crystal phase as a main crystal phase; and a gahnite crystal phase as a secondary crystal phase. The glass-ceramic is characterized by the following color coordinates: l is 20.0 to 40.0; a is-1.0 to 1.0; and b is-5.0 to 2.0.

According to aspect (33), there is provided the method of aspect (32), wherein the ceramization is performed at a temperature of greater than or equal to 900 ℃ to less than or equal to 1100 ℃.

According to aspect (34), there is provided the method of aspect (32) or (33), wherein the ceramming is performed for a period of time greater than or equal to 0.25 hours to less than or equal to 16 hours.

According to aspect (35), there is provided the method of any one of aspects (32) to (34), wherein the nucleation is performed at a temperature of greater than or equal to 725 ℃ to less than or equal to 850 ℃.

According to aspect (36), there is provided the method of any one of aspects (32) to (35), wherein the nucleation is performed for a period of time greater than or equal to 0.5 hours to less than or equal to 6 hours.

According to aspect (37), there is provided the method of any one of aspects (32) to (36), further comprising ion exchanging the glass-ceramic.

According to aspect (38), there is provided the method of any one of aspects (32) to (37), wherein the precursor glass-based article comprises: greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃Greater than or equal to 3% to less than or equal to 5% by weight Li₂O, greater than or equal to 0% by weight to less than or equal to 2% by weight Na₂O, from greater than or equal to 0.5% to less than or equal to 3% by weight MgO, from greater than or equal to 0.5% to less than or equal to 4% by weight ZnO, from greater than or equal to 2% to less than or equal to 6% by weight TiO₂From greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% SnO₂From greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄.。

According to aspect (39), there is provided the method of any one of aspects (32) to (38), wherein the precursor glass-based article comprises from greater than 0 wt% to less thanOr equal to 1.5 wt% Fe₂O₃。

According to an aspect (40), a method is provided that includes nucleating a precursor glass-based article to form a nucleated glass-based article, ceramming the nucleated glass-based article to form a glass ceramic, the glass ceramic including β -spodumene as a predominant crystalline phase, greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃(ii) a And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄. The glass-ceramic is characterized by the following color coordinates: l is 20.0 to 40.0; a is-1.0 to 1.0; and b is-5.0 to 2.0.

According to aspect (41), there is provided the method of aspect (40), wherein the ceramizing is performed at a temperature of greater than or equal to 900 ℃ to less than or equal to 1100 ℃.

According to aspect (42), there is provided the method of aspect (40) or (41), wherein the ceramming is performed for a period of time greater than or equal to 0.25 hours to less than or equal to 16 hours.

According to aspect (43), there is provided the method of any one of aspects (40) to (42), wherein the nucleation is performed at a temperature of greater than or equal to 725 ℃ to less than or equal to 850 ℃.

According to aspect (44), there is provided the method of any one of aspects (40) to (43), wherein the nucleation is performed for a period of time greater than or equal to 0.5 hours to less than or equal to 6 hours.

According to aspect (45), there is provided the method of any one of aspects (40) to (44), further comprising ion exchanging the glass-ceramic.

According to aspect (46), there is provided the method of any one of aspects (40) to (45), wherein the precursor glass-based article comprises: greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃Greater than or equal to 3% to less than or equal to 5% by weight Li₂O, greater than or equal to 0% by weight to less than or equal to 2% by weight Na₂O, from greater than or equal to 0.5% to less than or equal to 3% by weight MgO, greater than or equal to 05 to less than or equal to 4 wt% ZnO, greater than or equal to 2 to less than or equal to 6 wt% TiO₂From greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% SnO₂From greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄.。

According to aspect (47), there is provided the method of any one of aspects (40) to (45), wherein the precursor glass-based article comprises greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

According to aspect (48), a glass is provided. The glass comprises: greater than or equal to 60 wt% to less than or equal to 70 wt% SiO₂Greater than or equal to 15 wt% to less than or equal to 25 wt% Al₂O₃Greater than or equal to 3% to less than or equal to 5% by weight Li₂O, greater than or equal to 0% by weight to less than or equal to 2% by weight Na₂O, from greater than or equal to 0.5% to less than or equal to 3% by weight MgO, from greater than or equal to 0.5% to less than or equal to 4% by weight ZnO, from greater than or equal to 2% to less than or equal to 6% by weight TiO₂From greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% SnO₂From greater than or equal to 0.2 wt% to less than or equal to 3.0 wt% Fe₂O₃And greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% Co₃O₄。

According to aspect (49), there is provided the glass of aspect (48), comprising greater than or equal to 0.2 wt.% to less than or equal to 1.5 wt.% Fe₂O₃。

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.

Drawings

FIG. 1 schematically shows a cross-section of a glass-ceramic having a compressive stress layer on a surface thereof according to embodiments disclosed and described herein;

FIG. 2A is a plan view of an exemplary electronic device incorporating any of the glass-ceramics disclosed herein;

FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A;

FIG. 3 is an X-ray diffraction pattern of a glass-ceramic according to an embodiment;

FIG. 4 is a Scanning Electron Microscope (SEM) image of a glass-ceramic according to an embodiment at a first magnification;

FIG. 5 is a Scanning Electron Microscope (SEM) image of the glass-ceramic of FIG. 5 at a second magnification;

FIG. 6 is a thermal map of a glass composition from 30 ℃ to 1100 ℃ using a differential scanning calorimetry scan;

FIG. 7 is a graph of a and b color coordinates of precursor glass compositions, comparative example glass-ceramics, and glass-ceramics produced according to an embodiment in various ceramming cycles;

FIG. 8 is a plot of Lx color coordinates of the precursor glass composition of FIG. 7, a comparative example glass-ceramic, and glass-ceramics produced at various ceramming cycles according to an embodiment;

FIG. 9 is a transmission spectrum of a glass-ceramic according to an embodiment having a thickness of 0.8 mm;

fig. 10 is a graph of the change in L and b color coordinates as a result of ion exchange of the glass ceramic according to the embodiment and the glass ceramic of the comparative example.

Detailed Description

Reference will now be made in detail to black β -spodumene glass-ceramics according to various embodiments. In particular, black β -spodumene glass ceramics have an aesthetic appearance and can undergo ion exchange without significant color change. Accordingly, the black β -spodumene glass-ceramic is suitable for use as a housing for portable electronic devices.

In the description below, like reference numerals designate similar or corresponding parts throughout the several views shown in the drawings. It is also to be understood that, unless otherwise indicated, terms such as "top," "bottom," "outward," "inward," and the like are words of convenience and are not to be construed as limiting terms. Whenever a group is described as consisting of at least one of a group of elements or a combination thereof, it is understood that the group may consist of any number of those listed elements, either individually or in combination with each other. Unless otherwise indicated, a range of numerical values set forth includes both the upper and lower limits of the range, as well as any range between the stated ranges. As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean "at least one" or "one or more", unless otherwise indicated. It is also to be understood that the various features disclosed in the specification and in the drawings may be used in any and all combinations.

All components of the glasses described herein are expressed in weight percent (wt%), and the compositions are on an oxide basis, unless otherwise specified. All temperatures are expressed in degrees Celsius (. degree. C.) unless otherwise noted.

It is noted that the terms "substantially" and "about" may be used herein to represent the degree of inherent uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms "comprises," "comprising," and any other variation thereof, are intended to cover a non-exclusive inclusion, such that a non-exclusive inclusion does not imply that all of the features and functions of the subject matter claimed herein are in fact, or even wholly, essential to the subject matter. For example, "substantially free of K₂The glass of O' is one in which K is not actively driven₂O is added or dosed to the glass, but may be present in very small amounts as a contaminantIn, for example, its amount is less than about 0.01 wt%. As used herein, when the term "about" is used to modify a numerical value, the particular numerical value is also disclosed.

The glass-ceramics described herein contain a primary crystalline phase, a secondary crystalline phase, and a residual glass phase. The primary crystalline phase is the predominant crystalline phase, defined herein as the crystalline phase that occupies the largest portion of the glass-ceramic by weight. Thus, the secondary crystalline phase is present in less than the weight percent of the primary crystalline phase, based on the weight percent of the glass-ceramic.

In an embodiment, the primary crystalline phase comprises β -spodumene β -spodumene characterized by the formula LiAl (SiO)₃)₂And has a tetragonal crystal structure in embodiments, β -spodumene is the only predominant crystalline phase.

In some embodiments, the glass-ceramic comprises a secondary crystalline phase comprising at least one of gahnite, pseudobrookite, and magnesioptite. In an embodiment, the secondary crystalline phase comprises gahnite. Gahnite is characterized by the chemical formula ZnAl₂O₄And has an octahedral crystal structure. In some embodiments, additional secondary crystalline phases may be present in the glass-ceramic. The additional secondary crystalline phases may include pseudobrookite and/or magnesioptite, and may be present in addition to gahnite.

In embodiments, the total crystallinity of the glass-ceramic is sufficiently high to provide enhanced mechanical properties, such as: hardness, young's modulus and scratch resistance. As used herein, the units of total crystallinity provided are weight% and refer to the sum of the weight% of all crystalline phases present in the glass-ceramic. In embodiments, the total crystallinity is greater than or equal to 50 weight percent, for example: greater than or equal to 55 wt%, greater than or equal to 60 wt%, greater than or equal to 65 wt%, greater than or equal to 70 wt%, greater than or equal to 75 wt%, or greater. It should be understood that any of the above ranges may be combined with any other ranges in an embodiment. In embodiments, the total crystallinity of the glass-ceramic is greater than or equal to 50 weight percent to less than or equal to 75 weight percent, for example: greater than or equal to 55 wt% to less than or equal to 70 wt%, or greater than or equal to 60 wt% to less than or equal to 65 wt%, and all ranges and subranges between the foregoing values. The total crystallinity of the glass-ceramic is determined by Rittwald's quantitative analysis of the X-ray diffraction (XRD) results.

The crystalline phases in the glass-ceramic have small grain sizes. In some embodiments, the grain size of the crystalline phases in the glass-ceramic may have a size greater than or equal to 0.1 μm to less than or equal to 1.0 μm, for example: greater than or equal to 0.2 μm to less than or equal to 0.9 μm, greater than or equal to 0.3 μm to less than or equal to 0.8 μm, greater than or equal to 0.4 μm to less than or equal to 0.7 μm, or greater than or equal to 0.5 μm to less than or equal to 0.6 μm, and all ranges and subranges therebetween.

The glass-ceramics disclosed herein are opaque. In embodiments, the glass-ceramic exhibits a transmittance in the visible range (380nm to 760nm) of less than or equal to 10%, for example: less than or equal to 9%, less than or equal to 8%, less than or equal to 7%, less than or equal to 6%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.75%, less than or equal to 0.5%, or less. As used herein, transmittance refers to total transmittance, and is measured using a Perkin Elmer Lambda (Perkin Elmer Lambda)950UV/Vis/NIR spectrophotometer with a 150mm integrating sphere. The sample was mounted at the entrance end of the ball, which allowed collection of the wide angle scattered light, and a reference Spectralon reflector dish was located above the exit end of the ball. The total transmission is generated relative to the open beam baseline measurement.

In an embodiment, the glass-ceramic is black. Glass-ceramics can be characterized by the following color coordinates: l is from 20.0 to 40.0, a is from-1.0 to 0.5, and b is from-5.0 to 1.0. In some embodiments, the glass-ceramic may have a value of L x of 20.0 to 40.0, for example: 21.0 to 39.0, 22.0 to 38.0, 23.0 to 37.0, 24.0 to 36.0, 23.0 to 35.0, 25.0 to 34.0, 26.0 to 33.0, 27.0 to 32.0, 28.0 to 31.0, or 29.0 to 30.0%, and all ranges and subranges therebetween. In some embodiments, the glass-ceramic may have a value of-1.0 to 0.5, for example: -0.9 to 0.4, -0.8 to 0.3, -0.7 to 0.2, -0.6 to 0.1, -0.5 to 0.0, or-0.4 to-0.1, -0.3 to-0.2, and all ranges and subranges between the foregoing values. In some embodiments, the glass-ceramic may have a b value of-5.0 to 1.0, for example: -4.5 to 0.5, -4.0 to 0.0, -3.5 to-0.5, -3.0 to-1.0, -2.5 to-1.5, or-2.0, and all ranges and subranges between the foregoing values. As used herein, color coordinates were measured under SCI UVC conditions using an X-rite Ci 7F 02 light source.

The composition of β -spodumene glass-ceramics will now be described in the embodiments of glass-ceramics described herein, unless otherwise indicated, the constituent components (e.g., SiO)₂、Al₂O₃、LiO₂And Na₂O, etc.) is based on the weight percent (wt%) of the oxide. The components of the glass-ceramic according to embodiments are discussed independently below. It is to be understood that any of the various stated ranges for one component may be combined individually with any of the various stated ranges for any of the other components.

In embodiments of the glass-ceramics disclosed herein, SiO₂Is the largest component. SiO 2₂As the main network former and stabilizes the network structure. If SiO₂Too low, the desired β -spodumene crystalline phase may not be successfully formed₂Has a low CTE and is alkali free. However, pure SiO₂Has a high melting point. Thus, if SiO is present in the glass-ceramic₂Too high a concentration of (b) may result in a decrease in formability of the precursor glass composition used to form the glass-ceramic due to the higher SiO₂The concentration increases the difficulty of melting the glass, which in turn negatively affects the formability of the precursor glass. In embodiments, the glass composition comprises SiO₂The amount of (a) is generally greater than or equal to 60.0% by weight, for example: greater than or equal to 61.0 wt%, greater than or equal to 62.0 wt%, greater than or equal to 63.0 wt%, greater than or equal to 64.0 wt%, greater than or equal to 65.0 wt%, greater than or equal to 66.0 wt%, greater than or equal to 67.0 wt%, greater than or equal to 68.0 wt%, or greater than or equal to 69.0 wt%% of the total weight of the composition. In embodiments, the glass composition comprises SiO₂In an amount less than or equal to 70.0 wt%, for example: less than or equal to 69.0 wt%, less than or equal to 68.0 wt%, less than or equal to 67.0 wt%, less than or equal to 66.0 wt%, less than or equal to 65.0 wt%, less than or equal to 64.0 wt%, less than or equal to 63.0 wt%, less than or equal to 62.0 wt%, or less than or equal to 61.0 wt%. It should be understood that any of the above ranges may be combined with any other ranges in an embodiment. In embodiments, the glass composition comprises SiO₂The amount of (a) is greater than or equal to 60.0 wt% to less than or equal to 70.0 wt%, for example: greater than or equal to 61.0 wt% to less than or equal to 69.0 wt%, greater than or equal to 62.0 wt% to less than or equal to 68.0 wt%, greater than or equal to 63.0 wt% to less than or equal to 67.0 wt%, greater than or equal to 64.0 wt% to less than or equal to 66.0 wt%, or greater than or equal to 65.0 wt% to less than or equal to 67.0 wt%, and all ranges and subranges between the foregoing values.