ALKALINE EARTH ALUMINO-SILICATE GLASS COMPOSITIONS WITH IMPROVED CHEMICAL AND MECHANICAL DURABILITY

• US 20130101853A1
• Filed: 10/25/2012
• Published: 04/25/2013
• Est. Priority Date: 10/25/2011
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Morena, Robert Michael, Drake, Melinda Ann
• Granted Patent: US 9,145,329 B2
• Time in Patent Office: Days
• US Class Current: 428/410
• CPC Class Codes: A61J 1/00 Containers specially adapted for medical or pharmaceutical purposes capsules or the like for oral use A61J3/07; specially adapted for surgical or diagnostic appliances or instruments A61B50/30; containers for radioactive substances G21F5/00
• CPC Class Codes: A61J 1/05 for collecting, storing or administering blood, plasma or medical fluids multiple bags systems for separating or storing blood components A61M1/0209; Infusion or perfusion containers
• CPC Class Codes: A61J 1/065 Rigid ampoules, e.g. glass ampoules
• CPC Class Codes: C03C 21/002 to perform ion-exchange between alkali ions C03C21/005 takes precedence
• CPC Class Codes: C03C 2204/00 Glasses, glazes or enamels with special properties
• CPC Class Codes: C03C 3/087 containing calcium oxide, e.g. common sheet or container glass
• CPC Class Codes: C03C 3/091 containing aluminium
• CPC Class Codes: C03C 3/093 containing zinc or zirconium
• CPC Class Codes: C03C 4/20 for chemical resistant glass
• CPC Class Codes: Y10T 428/315 Surface modified glass [e.g., tempered, strengthened, etc.]

Abstract

Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability and pharmaceutical packages comprising the same are disclosed herein. In one embodiment a glass composition may include from about 65 mol. % to about 75 mol. % SiO₂; from about 6 mol. % to about 12.5 mol. % Al₂O₃; and from about 5 mol. % to about 12 mol. % alkali oxide. The alkali oxide may include Na₂O and K₂O. The K₂O may be present in an amount less than or equal to 0.5 mol. %. The glass composition may also include from about 8.0 mol. % to about 15 mol. % of at least one alkaline earth oxide. The glass composition is susceptible to strengthening by ion-exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.

Claims

1. A glass composition comprising:

from about 65 mol. % to about 75 mol. % SiO₂;

from about 6 mol. % to about 12.5 mol. % Al₂O₃;

from about 5 mol. % to about 12 mol. % alkali oxide, wherein the alkali oxide comprises Na₂O and K₂O and the K₂O is present in an amount less than or equal to 0.5 mol. %; and

from about 8.0 mol. % to about 15 mol. % of at least one alkaline earth oxide, wherein the glass composition is susceptible to strengthening by ion-exchange.

2. The glass composition of claim 1 wherein SiO₂ is present in the glass composition in a concentration from about 67 mol. % to about 75 mol. %.

3. The glass composition of claim 1, wherein Al₂O₃ is present in the glass composition in a concentration from about 6 mol. % to about 10 mol. %.

4. The glass composition of claim 1, wherein the glass composition comprises less than about 1 mol. % B₂O₃.

5. The glass composition of claim 1, wherein the glass composition is free from boron and compounds of boron.

6. The glass composition of claim 1, wherein the alkaline earth oxide comprises at least one of SrO and BaO.

7. The glass composition of claim 6, wherein the alkaline earth oxide comprises SrO in an amount greater than or equal to about 1 mol. % and less than or equal to about 2 mol. %.

8. The glass composition of claim 6, wherein the alkaline earth oxide comprises SrO in an amount greater than 0 mol. % and less than or equal to about 6 mol. %.

9. The glass composition of claim 1, wherein the glass composition is free from barium and compounds of barium.

10. The glass composition of claim 1, wherein a concentration of Al₂O₃ is greater than about 7 mol. %.

11. The glass composition of claim 1, wherein the alkali metal oxide further comprises Li₂O in an amount from about 1 mol. % to about 3 mol. %.

12. The glass composition of claim 1, wherein the Na₂O is present in an amount from about 3.5 mol. % to about 8 mol. %.

13. The glass composition of claim 1, wherein the alkaline earth oxide is present in an amount from about 10 mol. % to about 14 mol. %.

14. The glass composition of claim 1, wherein the alkaline earth oxide comprises MgO and CaO.

15. The glass composition of claim 14, wherein MgO is present in an amount greater than 0 mol. % and less than or equal to 3.5 mol. %.

16. The glass composition of claim 1 further comprising ZrO₂ in an amount less than or equal to about 1.5 mol. %.

17. The glass composition of claim 1, further comprising ZnO in an amount less than or equal to about 2.0 mol. %.

18. The glass composition of claim 1 further comprising SnO₂ in an amount less than or equal to about 0.3 mol. %.

19. The glass composition of claim 1, wherein the glass composition is substantially free from phosphorous and compounds of phosphorous.

20. The glass composition of claim 1, wherein the glass composition has a liquidus viscosity greater than or equal to 85 kP.

21. The glass composition of claim 1, wherein a ratio MgO:

Σ

RO is less than 0.3.

22. The glass composition of claim 1, wherein the glass composition has at least a class S3 acid resistance according to DIN 12116 both before and after ion-exchange strengthening.

23. The glass composition of claim 1, wherein the glass composition has a class A1 base resistance according to ISO 695 both before and after ion-exchange strengthening.

24. The glass composition of claim 1, wherein the glass composition has a type HGA1 hydrolytic resistance according to ISO 720 after ion exchange strengthening.

25. The glass composition of claim 1, wherein the glass composition has a Type HGA1 hydrolytic resistance according to ISO 720 before strengthening by ion exchange and after strengthening by ion exchange.

55. The glass composition of claim 20, wherein a ratio MgO:

Σ

RO is less than 0.3.

26. A glass composition comprising:

from about 67 mol. % to about 75 mol. % SiO₂;

from about 6 mol. % to about 10 mol. % Al₂O₃;

from about 5 mol. % to about 12 mol. % alkali oxide, wherein the alkali oxide comprises K₂O in an amount less than or equal to about 0.5 mol. %;

from about 8 mol. % to about 15 mol. % of alkaline earth oxide, wherein the at least one alkaline earth oxide comprises at least one of SrO and BaO, wherein;

the glass composition is free from boron and compounds of boron;

the glass composition is free from phosphorous and compounds of phosphorous; and

the glass composition is ion exchangeable to a depth of layer greater than or equal to about 15 μ

m with a corresponding compressive stress greater than or equal to about 250 MPa.

27. The glass composition of claim 26, wherein the alkali oxide comprises Na₂O in an amount from about 3.5 mol. % to about 8 mol. %.

28. The glass composition of claim 26, wherein the alkaline earth oxide comprises SrO in an amount greater than or equal to about 1 mol. % and less than or equal to about 2 mol. %.

29. The glass composition of claim 26, wherein the alkaline earth oxide comprises SrO in an amount greater than 0 mol. % and less than or equal to about 6 mol. %.

30. The glass composition of claim 26, wherein the glass composition is free from barium and compounds of barium.

31. The glass composition of claim 26, wherein a concentration of Al₂O₃ is greater than about 7 mol. %.

32. The glass composition of claim 26, wherein the alkali metal oxide further comprises Li₂O in an amount from about 1 mol. % to about 3 mol. %.

33. The glass composition of claim 26, wherein the alkaline earth oxide is present in an amount from about 10 mol. % to about 14 mol. %.

34. The glass composition of claim 26, wherein the alkaline earth oxide further comprises MgO and CaO.

35. The glass composition of claim 34, wherein MgO is present in an amount greater than 0 mol. % and less than or equal to 3.5 mol. %.

36. The glass composition of claim 35, wherein the glass composition further comprises ZnO in an amount less than or equal to 2.0 mol. %.

37. The glass composition of claim 35, wherein the glass composition is free from zinc and compounds containing zinc.

38. The glass composition of claim 35, wherein the glass composition further comprises Li₂O in an amount greater than or equal to 1 mol. % and less than or equal to 3 mol. %.

39. The glass composition of claim 35, wherein the glass composition is free from lithium and compounds containing lithium.

40. The glass composition of claim 35, wherein the glass composition comprises:

from about 5 mol. % to about 6 mol. % CaO; and

from about 2 mol. % to about 4 mol. % SrO.

41. The glass composition of claim 26, wherein the glass composition comprises:

from about 2 mol. % to about 5 mol. % CaO; and

from about 3 mol. % to about 6 mol. % SrO.

42. The glass composition of claim 26 further comprising ZrO₂ in an amount less than or equal to about 1.5 mol. %.

43. The glass composition of claim 26, further comprising ZnO in an amount less than or equal to about 2.0 mol. %.

44. The glass composition of claim 26, wherein the glass composition has a liquidus viscosity greater than or equal to 85 kP.

45. The glass composition of claim 26, wherein a ratio MgO:

Σ

RO is less than 0.3.

46. The glass composition of claim 26, wherein the glass composition has at least a class S3 acid resistance according to DIN 2116 both before and after ion-exchange strengthening.

47. The glass composition of claim 26, wherein the glass composition has a class S1 base resistance according to ISO 695 both before and after ion-exchange strengthening.

48. The glass composition of claim 26, wherein the glass composition has a type HGA1 hydrolytic resistance according to ISO 720 after ion-exchange strengthening.

49. The glass composition of claim 26, wherein the glass composition has a Type HGA1 hydrolytic resistance according to ISO 720 before strengthening by ion exchange and after strengthening by ion exchange.

50. A glass article formed from glass having a composition comprising:

from about 67 mol. % to about 75 mol. % SiO₂;

from about 6 mol. % to about 10 mol. % Al₂O₃;

from about 5 mol. % to about 12 mol. % alkali oxide, wherein the alkali oxide comprises Na₂O and K₂O and the K₂O is present in an amount less than or equal to 0.5 mol. %;

from about 8 mol. % to about 15 mol. % of the at least one alkaline earth oxide, wherein the composition is free from boron and compounds of boron and the glass article has;

at least a class S3 acid resistance according to DIN 12116;

a class A1 base resistance according to ISO 695; and

a type HGA1 hydrolytic resistance according to ISO 720.

51. The glass article of claim 50, wherein the glass article has a compressive stress greater than or equal to about 250 MPa.

52. The glass article of claim 50, wherein the glass article has a depth of layer greater than or equal to about 15 μ

m.

53. The glass article of claim 50, wherein the glass article has a coefficient of thermal expansion less than or equal to 70×

10<sup>−

7</sup>K<sup>−

1</sup>.

54. The glass composition of claim 50, wherein the glass composition is substantially free from phosphorous and compounds of phosphorous.

56. A glass article comprising:

a compressive stress layer with a compressive stress greater than or equal to about 250 MPa and depth of layer greater than or equal to about 15 μ

m; and

a type HGA1 hydrolytic resistance according to ISO 720, wherein the glass article is formed from a glass composition which is free of boron and compounds of boron and free from phosphorous and compounds of phosphorous.

57. The glass article of claim 56, wherein the glass composition has a class S1 base resistance according to ISO 695.

58. The glass composition of claim 56, the glass composition has at least a class S3 acid resistance according to DIN 2116.

59. The glass article of claim 56, wherein the glass composition comprises:

from about 67 mol. % to about 75 mol. % SiO₂;

from about 6 mol. % to about 10 mol. % Al₂O₃;

from about 5 mol. % to about 12 mol. % alkali oxide, wherein the alkali oxide comprises Na₂O and K₂O and the K₂O is present in an amount less than or equal to 0.5 mol. %; and

from about 8.0 mol. % to about 15 mol. % of at least one alkaline earth oxide.

60. The glass composition of claim 59, wherein a ratio MgO:

Σ

RO is less than 0.3.