Strengthened glass containers resistant to delamination and damage

• US 10,117,806 B2
• Filed: 11/08/2013
• Issued: 11/06/2018
• 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, Timmons, Christopher Lee, Venkataraman, Natesan, Verkleeren, Ronald Luce, Bookbinder, Dana Craig
• Primary Examiner(s): Higgins, Gerard
• Application Number:
  US14/075,593
• Publication Number:
  US 20140151370A1
• Time in Patent Office: 1,824 Days
• Field of Search: 2065243, 215 122, 428 344, 428 346
• 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 1/0215 multilayered B65D81/3837 takes precedence
• CPC Class Codes: B65D 23/02 Linings or internal coatings
• CPC Class Codes: B65D 23/0821 consisting mainly of polymeric materials B65D23/0828 takes precedence
• CPC Class Codes: B65D 23/0835 consisting mainly of metallic compounds
• 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: C03B 27/0413 Stresses, e.g. patterns, values or formulae for flat or bent glass sheets
• CPC Class Codes: C03C 17/005 Coating the outside
• 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 17/42 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

Abstract

The glass containers described herein are resistant to delamination, have improved strength, and increased damage resistance. In one embodiment, a glass container 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 body may also have 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. A lubricous coating may be positioned around at least a portion of the outer surface of the body, such that the outer surface of the body with the lubricous coating has a coefficient of friction less than or equal to 0.7.

Claims

1. A glass container comprising:

a body comprising a borosilicate glass having a Type 1 chemical durability according to USP <

660>

, the body enclosing an interior volume and 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 has a delamination factor less than or equal to 10;

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; and

a lubricous coating positioned around at least a portion of the outer surface of the body, wherein the outer surface of the body with the lubricous coating has a coefficient of friction less than or equal to 0.7 and wherein the lubricous coating comprises at least one of a metal nitride, a metal sulfide, a metal oxide, a diamond-like carbon, a graphene, a carbide coating, an inorganic salt, or a polymer.

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 body is a glass body that is ion-exchange strengthened.

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

8. The glass container of claim 1, wherein the body is a glass body that 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 about 22% of the wall thickness.

10. The glass container of claim 1, wherein the 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 10, wherein the compressively stressed layer extends 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 10, wherein the compressively stressed layer extends 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 body.

17. The glass container of claim 1, wherein the body further comprises 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 borosilicate glass of the body.

18. The glass container of claim 1, wherein the body is a glass body and 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 such that an extrema in the concentration of each constituent component in the interior region is greater than or equal to about 80% and less than or equal to about 120% of a bulk concentration of the same constituent component at a mid-point of the thickness of the glass body when the glass container is in an as-formed condition exclusive of constituent components which are present in an amount less than 2 mol. %.

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 body is a glass body and the inner surface of the glass body has a persistent surface homogeneity such that for a discrete point on the interior surface of the glass container, an extrema of the concentration of each constituent component of the glass in the surface region at the discrete point is greater than or equal to about 70% and less than or equal to about 130% of the same constituent component in the surface region at any second discrete point on the interior surface of the glass container when the glass container is in an as-formed condition exclusive of constituent components which are present in an amount less than 2 mol. %.

21. The glass container of claim 20, wherein the persistent surface homogeneity extends into the wall thickness of the 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 body comprises glass and was etched.

23. The glass container of claim 1, wherein the inner surface of the body comprises glass was acid etched.

24. The glass container of claim 1, wherein the body further comprises a barrier coating positioned at the inner surface of the body.

25. The glass container of claim 24, 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.

26. The glass container of claim 24, wherein the barrier coating comprises at least one of Al₂O₃, TiO₂, ZrO₂, SnO, SnO₂ SiO₂, Ta₂O₅, Nb₂O₅, Cr₂O₃, V₂O₅, ZnO, HfO₂, or combinations thereof.

27. The glass container of claim 24, wherein the barrier coating comprises at least one of a polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenolics, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins, 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, substituted siloxanes, polyimides, polycarbonates, polyesters, parafins and waxes, or combinations thereof.

28. The glass container of claim 1, wherein the glass of the body has at least a class S3 acid resistance or better according to DIN 12116 dated March 2001.

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

1991.

30. The glass container of claim 1, wherein the glass of the body has at least a HgB2 hydrolytic resistance or better according to ISO 719:

1985.

31. The glass container of claim 1, wherein the glass of the body has at least a HgA2 hydrolytic resistance or better according to ISO 720:

1985.

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

660>

.

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

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

35. The glass container of claim 1, wherein the glass of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92 (2011).

36. The glass container of claim 35, wherein the Type I, Class B glass according to ASTM Standard E438-92 (2011) is free from zinc and compounds containing zinc.

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

38. The glass container of claim 1, wherein the lubricous coating is thermally stable at a temperature of at least about 250°

C. for 30 minutes.

39. The glass container of claim 1, wherein the lubricous coating is thermally stable at a temperature of at least about 260°

C. for 30 minutes.

40. The glass container of claim 1, wherein the lubricous coating is thermally stable at a temperature of at least about 280°

C. for 30 minutes.

41. The glass container of claim 1, wherein the lubricous coating is a tenacious inorganic coating.

42. The glass container of claim 41, wherein the tenacious inorganic coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO₂, diamond-like carbide, graphenes or a carbide coating.

43. The glass container of claim 41, wherein the tenacious inorganic coating comprises at least one of TiN, BN, HBN TiO₂, Ta₂O₅, HfO₂, Nb₂O₅, V₂O₅, SiO₂, MoS₂, SiC, SnO, SnO₂, ZrO₂, Al₂O₃, BN, ZnO, and BC.

44. The glass container of claim 1, wherein the lubricous coating comprises a tenacious organic coating and the tenacious organic coating has a mass loss of less than about 5% of its mass when heated from a temperature of 150°

C. to 350°

C. at a ramp rate of about 10°

C./minute.

45. The glass container of claim 44, wherein the tenacious organic coating comprises a polymer.

46. The glass container of claim 45, wherein the tenacious organic coating further comprises a coupling agent.

47. The glass container of claim 1, wherein the lubricous coating is a transient coating.

48. The glass container of claim 47, wherein the transient coating pyrolizes at temperatures less than or equal to 300°

C. in less than or equal to 1 hour.

49. The glass container of claim 47, wherein the transient coating comprises a mixture of polyoxyethylene glycol, methacrylate resin, melamine formaldehyde resin, and polyvinyl alcohol.

50. The glass container of claim 47, wherein the transient coating comprises one or more polysaccharides.

51. The glass container of claim 47, wherein the transient coating comprises polyacrylic acid or a derivative of polyacrylic acid.

52. The glass container of claim 47, wherein the transient coating comprises an inorganic salt.

53. The glass container of claim 47, wherein the transient coating comprises at least one of:

poly(ethylene oxides), poly (propylene oxides), ethylene oxide-propylene oxide copolymers, polyvinyl-pyrrolidinones, polyethyleneimines, poly(methyl vinyl ethers), polyacrylamides, polymethacrylamides, polyurethanes, poly(vinylacetates), polyvinyl formal, polyformaldehydes, poly(alkyl methacrylates), methyl celluloses, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl celluloses, sodium carboxymethyl celluloses, methyl hydroxypropyl celluloses, poly (acrylic acids) and salts thereof, poly(methacrylic acids) and salts thereof, ethylene-maleic anhydride copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, vinyl acetate-vinyl alcohol copolymers, methyl vinyl ether-maleic anhydride copolymers, emulsifiable polyurethanes, polyoxyethylene stearates, and polyolefins, polypropylenes and copolymers thereof, starches and modified starches, hydrocolloids, polyacryloamide, vegetable and animal fats, wax, tallow, soap, stearine-paraffin emulsions, polysiloxanes of dimethyl or diphenyl or methyl/phenyl mixtures, siloxanes, alkylsilanes, aromatic silanes, and oxidized polyethylene.

54. The glass container of claim 1, wherein a light transmission through the glass container with the lubricous coating is greater than or equal to about 55% of a light transmission through an uncoated glass container for wavelengths of light from about 400 nm to about 700 nm.

55. 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 the glass body is formed from a Type I, Class B glass according to ASTM Standard E438-92 (2011);

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;

a barrier layer positioned on the inner surface of the glass body such that a composition contained in the glass container does not contact the inner surface of the glass body; and

a lubricous coating positioned around at least a portion of the outer surface of the glass body, wherein the outer surface of the glass body with the lubricous coating has a coefficient of friction less than or equal to 0.7 and wherein the lubricous coating comprises at least one of a metal nitride, a metal sulfide, a metal oxide, a diamond-like carbon, a graphene, a carbide coating, an inorganic salt, or a polymer.

56. The glass container of claim 55, wherein the glass body with the barrier layer has a delamination factor less than or equal to 10.

57. The glass container of claim 55, wherein the glass container is thermally stable at a temperature of at least about 250°

C. for 30 minutes.

58. The glass container of claim 55, wherein the glass container is thermally stable at a temperature of at least about 260°

C. for 30 minutes.

59. The glass container of claim 55, the glass container is thermally stable at a temperature of at least about 280°

C. for 30 minutes.

60. The glass container of claim 55 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.

61. A glass container comprising:

a body comprising borosilicate glass, the 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 has a delamination factor less than or equal to 10 and the glass of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92 (2011), wherein the glass of the body was formed under processing conditions which mitigate the vaporization of volatile species in the glass;

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; and

a lubricous coating around at least a portion of the outer surface of the body, wherein the outer surface of the body with the lubricous coating has a coefficient of friction less than or equal to 0.7 and wherein the lubricous coating comprises at least one of a metal nitride, a metal sulfide, a metal oxide, a diamond-like carbon, a graphene, a carbide coating, an inorganic salt, or a polymer.

62. The glass container of claim 61, wherein the glass of the body was formed at forming temperatures which are less than a lowest vaporization temperature of the volatile species in the glass.

63. The glass container of claim 61, wherein the glass of the body was formed at forming speeds which are less than forming speeds at which volatile species in the glass composition vaporize.

64. The glass container of claim 61, wherein the lubricous coating is thermally stable at temperatures greater than or equal to 250°

C.

65. The glass container of claim 64, wherein the lubricous coating is thermally stable at temperatures less than or equal to 400°

C.