Glass containers with delamination resistance and improved strength

• US 9,272,946 B2
• Filed: 11/08/2013
• Issued: 03/01/2016
• Est. Priority Date: 11/30/2012
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Chang, Theresa, Danielson, Paul Stephen, DeMartino, Steven Edward, Fadeev, Andrei Gennadyevich, Morena, Robert Michael, Pal, Santona, Peanasky, John Stephen, Schaut, Robert Anthony, Venkataraman, Natesan, Verkleeren, Ronald Luce
• Primary Examiner(s): Hicks, Robert J
• Assistant Examiner(s): Thomas, Kareen
• Application Number:
  US14/075,605
• Publication Number:
  US 20140151371A1
• Time in Patent Office: 844 Days
• Field of Search: 220/662, 220/657, 220/62.11, 220/62.15, 220/602, 220/663, 220/640, 220/643, 220/645, 220/659, 220/DIG.12, 501/53, 501/55, 501/68, 428/34.1, 428/34.4, 428/34.6, 428/410, 215/12.2, 215/12.1
• US Class Current: 1/1
• CPC Class Codes: A61J 1/065 Rigid ampoules, e.g. glass ampoules
• CPC Class Codes: A61J 1/1468 Containers characterised by specific material properties
• CPC Class Codes: B32B 17/06 comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• CPC Class Codes: B65D 1/0207 characterised by material, e.g. composition, physical features
• CPC Class Codes: B65D 1/0215 multilayered B65D81/3837 takes precedence
• CPC Class Codes: B65D 1/40 Details of walls other container details B65D23/00, B65D25/00
• CPC Class Codes: B65D 23/02 Linings or internal coatings
• CPC Class Codes: B65D 23/0814 characterised by the composition of the material
• CPC Class Codes: B65D 23/0821 consisting mainly of polymeric materials B65D23/0828 takes precedence
• CPC Class Codes: B65D 25/14 Linings or internal coatings of containers made by folding or erecting blanks made of paper B65D5/56 ; linings for domestic water storage heaters F24H1/183
• CPC Class Codes: B65D 25/34 Coverings or external coatings of containers made by folding or erecting blanks made of paper B65D5/62; for bottles or jars B65D23/08; wrappers B65D65/00
• CPC Class Codes: B65D 65/42 Applications of coated or impregnated materials
• CPC Class Codes: C03B 23/04 Re-forming tubes or rods
• CPC Class Codes: C03C 15/02 for making a smooth surface
• CPC Class Codes: C03C 17/005 Coating the outside
• CPC Class Codes: C03C 17/22 with other inorganic material C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/30 with silicon-containing compounds
• CPC Class Codes: C03C 17/32 with synthetic or natural resins C03C17/30 takes precedence
• CPC Class Codes: C03C 17/3405 with at least two coatings of organic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 21/002 : to perform ion-exchange between alkali ions C03C21/005 takes precedence
• CPC Class Codes: C03C 2217/78 : Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/111 : by dipping, immersion
• CPC Class Codes: C09D 179/08 : Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/13 : Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/131 : Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
• CPC Class Codes: Y10T 428/1317 : Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/24802 : Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/315 : Surface modified glass [e.g., tempered, strengthened, etc.]

Abstract

The glass containers described herein have at least two performance attributes selected from resistance to delamination, improved strength, and increased damage resistance. In one embodiment, a glass container with resistance to delamination and improved strength may include a body having an inner surface, an outer surface and a wall thickness extending between the outer surface and the inner surface. At least the inner surface of the body may have a delamination factor less than or equal to 10. The glass container may further include a compressively stressed layer extending from the outer surface of the body into the wall thickness. The compressively stressed layer may have a surface compressive stress greater than or equal to 150 MPa.

Claims

1. A glass container comprising:

a glass body having an inner surface, an outer surface and a wall thickness extending between the outer surface and the inner surface, wherein at least the inner surface of the glass body has a delamination factor less than or equal to 10; and

a compressively stressed layer extending from the outer surface of the glass body into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa.

2. The glass container of claim 1, wherein the surface compressive stress is greater than or equal to 200 MPa.

3. The glass container of claim 1, wherein the surface compressive stress is greater than or equal to 300 MPa.

4. The glass container of claim 1, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer greater than or equal to about 3 μ

m.

5. The glass container of claim 1, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer greater than or equal to about 25 μ

m.

6. The glass container of claim 1, wherein the glass body is ion-exchange strengthened.

7. The glass container of claim 1, wherein the glass body is high-temperature ion-exchange strengthened.

8. The glass container of claim 1, wherein the glass body is thermally tempered.

9. The glass container of claim 8, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer of up to 22% of the wall thickness.

10. The glass container of claim 1, wherein the glass body comprises laminated glass.

11. The glass container of claim 10, wherein the laminated glass comprises:

a core layer having a core coefficient of thermal expansion CTE_core; and

at least one cladding layer fused to the core layer and having a second coefficient of thermal expansion CTE_clad, wherein CTE_core is not equal to CTE_clad.

12. The glass container of claim 11, wherein:

the at least one cladding layer comprises a first cladding layer and a second cladding layer;

the first cladding layer is fused to a first surface of the core layer and the second cladding layer is fused to a second surface of the core layer; and

CTE_core is greater than CTE_clad.

13. The glass container of claim 11, wherein the compressively stressed layer extends from the outer surface of the glass body into the wall thickness to a depth of layer which is from about 1 μ

m to about 90% of the wall thickness.

14. The glass container of claim 11, wherein the compressively stressed layer extends from the outer surface of the glass body into the wall thickness to a depth of layer which is from about 1 μ

m to about 33% of the wall thickness.

15. The glass container of claim 11, wherein the at least one cladding layer has a delamination factor of less than or equal to 10 after the laminated glass is formed into the glass container.

16. The glass container of claim 11, wherein the at least one cladding layer forms the inner surface of the glass body.

17. The glass container of claim 1 further comprising an inorganic coating positioned on at least a portion of the outer surface of the glass body, wherein the inorganic coating has a coefficient of thermal expansion which is less than a coefficient of thermal expansion of the glass body.

18. The glass container of claim 1, wherein the glass body has an interior region extending between the inner surface of the glass body and the outer surface of the glass body, the interior region having a persistent layer homogeneity.

19. The glass container of claim 18, wherein the interior region has a thickness of at least 100 nm.

20. The glass container of claim 1, wherein the inner surface of the glass body has a persistent surface homogeneity.

21. The glass container of claim 20, wherein the persistent surface homogeneity extends into the wall thickness of the glass body to a depth D_SR of at least 10 nm from the inner surface of the glass body.

22. The glass container of claim 1, wherein the inner surface of the glass body is etched.

23. The glass container of claim 1, wherein the glass body has at least a class S3 acid resistance or better according to DIN 12116.

24. The glass container of claim 1, wherein the glass body has at least a class A2 base resistance or better according to ISO 695.

25. The glass container of claim 1, wherein the glass body has at least HGB2 hydrolytic resistance or better according to ISO 719.

26. The glass container of claim 1, wherein the glass body has at least HGA2 hydrolytic resistance or better according to ISO 720.

27. The glass container of claim 1, wherein the glass body has a Type 1 chemical durability according to USP <

660>

.

28. The glass container of claim 1, wherein the glass body is a mold-formed glass body.

29. The glass container of claim 1, wherein the glass body is formed with a glass forming process in which the glass body is monotonically cooled from a glass melt.

30. The glass container of claim 1, wherein the glass body is formed from an aluminosilicate glass composition.

31. The glass container of claim 1, wherein the glass body is formed from an alkali-aluminosilicate glass composition.

32. The glass container of claim 31, wherein the alkali-aluminosilicate glass composition is substantially free from boron and compounds containing boron.

33. The glass container of claim 31, wherein the alkali-aluminosilicate glass composition is substantially free from zinc and compounds containing zinc.

34. The glass container of claim 31, wherein the alkali-aluminosilicate glass composition is substantially free from phosphorous and compounds containing phosphorous.

35. The glass container of claim 1, wherein the glass body is formed from 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 from about 2.5 mol. % to about 10 mol % Na₂O and greater than about 0 mol. % to about 2.5 mol. % K₂O;

from about 9 mol. % to about 15 mol. % alkaline earth oxide; and

from about 0 mol. % to about 0.5 mol. % SnO₂.

36. The glass container of claim 35, wherein the glass composition is substantially free from boron and compounds containing boron.

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

38. The glass container of claim 35, wherein the glass composition is substantially free from phosphorous and compounds containing phosphorous.

39. The glass container of claim 1, wherein at least the inner surface of the glass body is formed from a Type I, Class B glass according to ASTM Standard E438-92.

40. The glass container of claim 1, wherein the glass container is a pharmaceutical package.

41. A glass container comprising:

a body having an inner surface, an outer surface and a wall thickness extending between the outer surface and the inner surface, wherein at least the inner surface of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92;

a compressively stressed layer extending into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa; and

a barrier coating positioned on the inner surface of the body such that a composition contained in the glass container contacts the barrier coating and not the inner surface of the body.

42. The glass container of claim 41, wherein the barrier coating has a delamination factor less than or equal to 10.

43. The glass container of claim 41, wherein the body comprises laminated glass.

44. The glass container of claim 43, wherein the laminated glass comprises:

a core layer having a core coefficient of thermal expansion CTE_core; and

at least one cladding layer fused to the core layer and having a second coefficient of thermal expansion CTE_clad, wherein CTE_core is not equal to CTE_clad.

45. The glass container of claim 44, wherein:

the at least one cladding layer comprises a first cladding layer and a second cladding layer;

the first cladding layer is fused to a first surface of the core layer and the second cladding layer is fused to a second surface of the core layer; and

CTE_core is greater than CTE_clad.

46. The glass container of claim 43, wherein the compressively stressed layer has a depth of layer which is from about 1 μ

m to about 90% of the wall thickness.

47. The glass container of claim 43, wherein the compressively stressed layer extends to a depth of layer which is from about 1 μ

m to about 33% of the wall thickness.

48. The glass container of claim 43 further comprising an inorganic coating positioned on at least a portion of the outer surface of the body, wherein the inorganic coating has a coefficient of thermal expansion which is less than a coefficient of thermal expansion of the body.

49. The glass container of claim 41, wherein the barrier coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, diamond-like carbide, graphenes or a carbide coating.

50. The glass container of claim 41, wherein the barrier coating comprises at least one of Al₂O₃, TiO₂, ZrO₂, SnO, SnO₂, Ta₂O₅, Nb₂O₅, Cr₂O₃, V₂O₅, ZnO, or HfO₂, or combinations thereof.

51. The glass container of claim 41, wherein the barrier coating comprises at least one of a polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins including polytetrafluorethylenes and other fluoro-substituted polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenolics, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins including polyethylenes, oxidized polyethylenes, polypropylenes, polyethylene/propylene copolymers, polyethylene/vinyl acetate copolymers, polyvinylchloride, polyacrylates, polymethacrylates, polystyrenes, polyterpenes, polyanhydrides, polymaleicanhydrides, polyformaldehydes, polyacetals and copolymers of polyacetals, polyimides, polycarbonates, polyesters, parafins and waxes, or various combinations thereof.

52. A glass container comprising:

a body having an inner surface, an outer surface and a wall thickness extending from the outer surface to the inner surface, wherein the body is formed from a glass composition which is free from constituent components which form species that volatilize significantly at temperatures corresponding to a viscosity in a range from about 200 poise to about 100 kilopoise; and

a compressively stressed layer extending from the outer surface of the body into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa.

53. The glass container of claim 52, wherein at least the inner surface of the body has a delamination factor less than or equal to 10.

54. The glass container of claim 53, further comprising a barrier coating positioned on the inner surface of the body.

55. The glass container of claim 54, wherein the barrier coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO₂, diamond-like carbide, graphenes or a carbide coating.

56. The glass container of claim 54, wherein the barrier coating comprises at least one of Al₂O₃, TiO₂, ZrO₂, SnO, SnO₂, SiO₂, Ta₂O₅, Nb₂O₅, Cr₂O₃, V₂O₅, ZnO, or HfO₂, or combinations thereof.

57. The glass container of claim 54, wherein the barrier coating comprises at least one of a polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins including polytetrafluorethylenes and other fluoro-substituted polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenolics, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins including polyethylenes, oxidized polyethylenes, polypropylenes, polyethylene/propylene copolymers, polyethylene/vinyl acetate copolymers, polyvinylchloride, polyacrylates, polymethacrylates, polystyrenes, polyterpenes, polyanhydrides, polymaleicanhydrides, polyformaldehydes, polyacetals and copolymers of polyacetals, polysiloxanes of dimethyl or diphenyl or methyl/phenyl mixtures, perfluorinated siloxanes and other substituted siloxanes, -polyimides, polycarbonates, polyesters, parafins and waxes, or various combinations thereof.