Lithium silicate materials

• US 8,042,358 B2
• Filed: 11/05/2007
• Issued: 10/25/2011
• Est. Priority Date: 08/07/2003
• Status: Active Grant

• Current Assignee: Ivoclar Vivadent AG
• Original Assignee: Ivoclar Vivadent AG
• Inventors: Holand, Wolfram, Schweiger, Marcel, Burke, Harald, Rheinberger, Volker M.
• Primary Examiner(s): Lazorcik; Jason L.
• Application Number:
  US11/935,221
• Publication Number:
  US 20080120994A1
• Time in Patent Office: 1,450 Days
• Field of Search: 65/331
• US Class Current: 65/33.8
• CPC Class Codes: A61K 6/78 Pigments
• CPC Class Codes: A61K 6/807 comprising magnesium oxide
• CPC Class Codes: A61K 6/818 comprising zirconium oxide
• CPC Class Codes: A61K 6/833 Glass-ceramic composites
• CPC Class Codes: C03C 10/0027 containing SiO2, Al2O3, Li2O as main constituents
• CPC Class Codes: C03C 10/0036 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
• CPC Class Codes: C03C 3/097 containing phosphorus, niobium or tantalum
• CPC Class Codes: C03C 4/0021 for dental use

Abstract

Lithium silicate materials are described which can be easily processed by machining to dental products without undue wear of the tools and which subsequently can be converted into lithium silicate products showing high strength.

Claims

1. A process for manufacturing a lithium silicate restoration comprising preparing a lithium silicate blank which comprises:

(a) producing a melt of a starting glass containing the initial components SiO₂, Li₂O, and P₂O₅ or other nucleation agent as the main components;

(b) pouring the melt of the starting glass into a mould to form a starting glass blank and cooling the glass blank to room temperature;

(c) subjecting the starting glass blank to a first heat treatment at a first temperature to give a glass product which contains nuclei suitable for forming lithium metasilicate crystals;

or

(b′

) pouring the melt of the starting glass into a mould to form a starting glass blank and cooling the glass blank to a first temperature;

(c′

) holding the starting glass blank at the first temperature to give a glass product which contains nuclei suitable for forming lithium metasilicate crystals;

(d) subjecting the glass product of step (c) or (c′

) to a second heat treatment at a second temperature which is higher than the first temperature to obtain the lithium silicate blank with lithium metasilicate crystals as the main crystalline phase;

(e) cooling the lithium silicate blank having the lithium metasilicate crystals as the main crystalline phase; and

(f) shaping the cooled lithium silicate blank with lithium metasilicate crystals as the main crystalline phase into the shape of a dental restoration.

2. A process according to claim 1, wherein the shaping of the cooled lithium silicate blank into the shape of a dental restoration of step (f) comprises coating a dental framework with the lithium silicate blank.

3. A process according to claim 2 wherein the dental framework is coated by hot pressing the lithium silicate blank onto the dental framework.

4. A process according to claim 3, wherein the dental framework is a crown, a partial crown, a bridge, a coping, a veneer, a facing or an abutment.

5. A process according to claim 4, wherein the dental framework is made from a metal, an alloy, a ceramic or a glass ceramic.

6. A process according to claim 5, wherein the ceramic comprises zirconium oxide, aluminum oxide, a zirconium mix oxide, an aluminum mix oxide, or a combination thereof.

7. A process according to claim 3, wherein the lithium silicate blank which is coated onto the framework comprises lithium metasilicate crystals which are converted to lithium disilicate crystals during the hot pressing of the lithium silicate blank onto the dental framework.

8. A process according to claim 1, wherein the cooled lithium silicate blank with lithium metasilicate as the main crystalline phase of step (e) is shaped to a desired geometry by machining or by hot pressing to form a shaped lithium silicate product.

9. A process according to claim 8 wherein the dental restoration is an inlay, an onlay, a bridge, an abutment, a facing, a veneer, a facet, a crown, a partial crown, a framework or a coping.

10. A process according to claim 8 wherein the machining is performed by grinding or milling.

11. A process according to claim 10, wherein the machining is controlled by a computer.

12. A process according to claim 8, further comprising subjecting the shaped lithium silicate product to a third heat treatment at a third temperature of about 700 to 950°

C. for a period of about 5 to 30 minutes.

13. A process according to claim 12 wherein the third heat treatment converts the lithium metasilicate crystals to lithium disilicate crystals as the main crystalline phase.

14. A process according to claim 12, wherein the linear shrinkage that occurs during the third heat treatment is about 0.2 to 0.3%.

15. A process according to claim 12 which comprises an increasing of strength and fracture toughness of the lithium silicate blank.

16. A process according to claim 12, wherein the third heat treatment occurs during a firing of the layering materials or the hot pressing of the coating material onto the unfinished dental restoration.

17. A process according to claim 8 which comprises shaping of the lithium silicate blank to the desired geometry by hot pressing to produce the dental restoration.

18. A process for manufacturing a dental restoration according to claim 17 wherein the hot pressing comprises subjecting the lithium silicate blank to a heat treatment at a temperature of about 500 to 1200°

C. to convert the lithium silicate blank into a viscous state and pressing the viscous lithium silicate blank under a pressure of about 1 to 4 MPa into a mould or dye to obtain the dental restoration with a desired geometry.

19. A process according to claim 18 wherein the lithium silicate blank subjected to the heat treatment and pressing comprises lithium metasilicate crystals which are converted into lithium disilicate crystals during the heat treatment and pressing.

20. A process according to claim 18, which comprises an increasing of strength and fracture toughness of the lithium silicate blank.

21. A process according to claim 8, wherein the dental restoration has a biaxial strength of at least 250 MPa and a fracture toughness of at least 1.5 MPam^0.5.

22. A process according to claim 8, further comprising finishing the dental restoration to obtain an appearance that imitates the appearance of natural teeth.

23. A process according to claim 22, wherein the finishing step comprises applying a coating to the dental restoration by layering with powdered materials or by hot pressing a coating material onto the unfinished dental restoration.

24. The process according to claim 1 wherein the starting glass further comprises K₂O and Al₂O₃.

25. A process for fabricating a lithium silicate dental article making use of a machinable lithium metasilicate glass ceramic blank comprising:

(a) melting a starting glass composition comprising SiO₂, Li₂O, and P₂O₅ or other nucleation agent as the main components;

(b) forming the molten glass into shaped blanks;

(c) heat treating the glass blanks to convert the glass blanks into machinable glass-ceramic blanks comprising a lithium metasilicate phase as the main crystalline phase;

(d) cooling the lithium silicate blank having the lithium metasilicate crystals as the main crystalline phase;

(e) machining the cooled blanks into the shape of a dental article; and

(f) heat treating the shaped dental article comprising the lithium metasilicate phase to fully or partially convert the lithium metasilicate into lithium disilicate.

26. The process of claim 25 wherein the starting glass is melted at a temperature within the range of about 1300°

C. to about 1600°

C.

27. The process of claim 25 wherein the heat treating to convert the glass blanks into machinable glass-ceramic blanks is in the temperature range of from 450°

C. to 700°

C.

29. The process of claim 25 wherein the strength of the blank after step (c) increases by a factor of 1.7 to 4 after step (f).

30. The process of claim 29 wherein the factor is in the range of 2 to 4.

31. The process of claim 25 wherein the fracture toughness of the blank after step (c) increases by a factor of about of 1.5 to 3.0 after step (f).

32. The process of claim 31 wherein the factor is in the range of 1.6 to 2.6.

33. The process of claim 25 wherein the lithium silicate dental article comprises lithium disilicate as a main crystalline phase.

34. The process of claim 33 wherein the lithium silicate dental article further comprises minor crystalline phases comprising lithium phosphate and lithium metasilicate.

35. The process of claim 25 wherein the lithium metasilicate phase comprises lamellar or platelet crystals.

36. The process of claim 25 wherein the machinable glass-ceramic blank exhibits a biaxial strength of 80 to 180 MPa.

37. The process of claim 36 wherein the biaxial strength ranges from 90 to 150 MPa.

38. The process of claim 25 wherein the machinable glass-ceramic blank exhibits a fracture toughness of at least about 0.8 MPam^0.5.

39. The process of claim 25 wherein the lithium silicate dental article exhibits a biaxial strength of at least about 250 MPa after step (f).

40. The process of claim 25 wherein the lithium silicate dental article exhibits a biaxial strength of greater than about 400 MPa after step (f).

41. The process of claim 25 wherein the lithium silicate dental article exhibits a fracture toughness of at least about 1.5 MPam^0.5 after step (f).

42. The process of claim 25 wherein the lithium silicate dental article exhibits a fracture toughness of greater than about 2 MPam^0.5 after step (f).

43. The process of claim 25 wherein the lithium silicate dental article exhibits a chemical solubility below about 100 μ

g/cm².

44. The process of claim 25 wherein the starting glass further comprises one or more of K₂O, Al₂O₃, ZnO, Na₂O, ZrO₂, Me^IIO, and a coloring/fluorescent metal oxide.

45. The process of claim 44 wherein the Me^IIO comprises CaO, BaO, SrO, MgO or a mixture thereof.

46. The process of claim 45 wherein the coloring/fluorescent metal oxide comprises an oxide of Ta, Tb, Y, La, Er, Pr, Ce, Ti, V, Fe, Mn or a mixture thereof.

47. The process of claim 25 further comprising coating the dental article with a coating.

48. The process of claim 25 wherein the dental article comprises an inlay, an onlay, a bridge, an abutment, a facing, a veneer, a facet, a crown, a partial crown, a framework or a coping.

49. The process of claim 25 wherein machining comprises milling, trimming and/or grinding.

28. The process of 25 wherein the heat treating to fully or partially convert the lithium metasilicate into lithium disilicate is in the temperature range of from about 700°

C. to about 950°

C.

50. A process for fabricating a lithium silicate glass-ceramic dental article making use of a machinable glass ceramic blank comprising:

(a) melting a starting glass composition comprising SiO₂, Li₂O, P₂O₅ or other nucleation agent;

(b) forming the molten glass into shaped blanks;

(c) heat treating the glass blanks to convert the glass blanks into machinable glass-ceramic blanks comprising a metastable lithium metasilicate phase as the main crystalline phase and having a strength of 80 to 180 MPa and a fracture toughness of at least about 0.8 MPam^0.5;

(d) cooling the lithium silicate blank having the lithium metasilicate phase as the main crystalline phase;

(e) machining the cooled blanks into the shape of a dental article; and

(f) heat treating the shaped dental article comprising the metastable lithium silicate phase to fully or partially convert the metastable phase into a final phase to provide a glass-ceramic dental article with a strength of at least about 250 MPa and a fracture toughness of at least about 1.5 MPam^0.5.

51. The process of claim 50 wherein negligible linear shrinkage occurs during the conversion from the metastable phase into a final phase.

52. The process of claim 51 wherein the linear shrinkage is less than about 0.3%.

53. The process of claim 50 wherein the final phase comprises lithium disilicate as a main crystalline phase.

54. The process of claim 53 wherein the final phase further comprises lithium metasilicate and lithium phosphate as minor crystalline phases.

55. The process of claim 50 wherein the starting glass is melted at a temperature within the range of about 1300°

C. to about 1600°

C.

56. The process of claim 50 wherein the heat treating to convert the glass blanks into machinable glass-ceramic blanks is in the temperature range of from 450°

C. to 700°

C.

57. The process of claim 50 wherein the heat treating to fully or partially convert the metastable phase into a final phase is in the temperature range of from about 700°

C. to about 950°

C.

58. The process of claim 50 wherein the starting glass further comprises one or more of K₂O, Al₂O₃, ZnO, Na₂O, ZrO₂, Me^IIO, and a coloring/fluorescent metal oxide.

59. The process of claim 50 wherein the Me^IIO comprises CaO, BaO, SrO, MgO or a mixture thereof.

60. The process of claim 56 wherein the coloring/fluorescent metal oxide comprises an oxide of Ta, Tb, Y, La, Er, Pr, Ce, Ti, V, Fe, Mn or a mixture thereof.

61. The process of claim 50 further comprising coating the dental article with a coating.

62. The process of claim 50 wherein the metastable lithium metasilicate phase comprises lamellar or platelet crystals.

63. The process of claim 50 wherein the dental article comprises an inlay, an onlay, a bridge, an abutment, a facing, a veneer, a facet, a crown, a partial crown, a framework or a coping.