Glass containers with delamination resistance and improved damage tolerance

• US 10,307,333 B2
• Filed: 11/08/2013
• Issued: 06/04/2019
• 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:
  US14/075,620
• Publication Number:
  US 20140151320A1
• Time in Patent Office: 2,034 Days
• Field of Search: 501 67, 501 66, 501 68, 501 69, 501 70, 428 347
• 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 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. A tenacious inorganic coating may be positioned around at least a portion of the outer surface of the body. The outer surface of the body with the tenacious inorganic coating may have a coefficient of friction less than or equal to 0.7.

Claims

1. A glass container comprising:

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

660>

, the 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 wherein the glass container does not include a coating on the inner surface of the glass body; and

a tenacious inorganic coating positioned around at least a portion of the outer surface of the glass body, wherein the tenacious inorganic coating is an outermost coating on the outer surface of the glass body and the outer surface of the glass body with the tenacious inorganic coating has a coefficient of friction less than or equal to 0.7, and wherein the tenacious inorganic coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO₂ diamond-like carbon, graphenes, or a carbide coating.

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

C. for 30 minutes.

3. The glass container of claim 2, wherein the tenacious inorganic coating is thermally stable at a temperature of at least about 280°

C. for 30 minutes.

4. The glass container of claim 1, 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, or BC.

5. 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 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. %.

6. The glass container of claim 5, wherein the interior region has a thickness of at least 100 nm.

7. The glass container of claim 5, 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, or BC.

8. The glass container of claim 1, wherein 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. %.

9. The glass container of claim 8, 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.

10. The glass container of claim 1, wherein the inner surface of the glass body was etched.

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

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

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

1991.

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

1985.

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

1985.

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

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

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

19. The glass container of claim 18, wherein the Type I, Class B glass according to ASTM Standard E438-92 (2011) is substantially free from zinc and compounds containing zinc.

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

21. A glass container comprising:

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

660>

, 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 wherein the glass container does not include a coating on the inner surface of the body; and

a transient coating positioned around at least a portion of the outer surface of the body, wherein the outer surface of the body with the transient coating has a coefficient of friction less than or equal to 0.7;

wherein the transient coating comprises one or more of;

one or more polysaccharides;

polyacrylic acid or a derivative of polyacrylic acid;

an inorganic salt;

or

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, 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, 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, substituted siloxanes, alkylsilanes, aromatic silanes, and oxidized polyethylene.

22. The glass container of claim 21, wherein the transient coating pyrolizes at temperatures less than or equal to 300°

C. in less than or equal to 1 hour.

23. The glass container of claim 21, wherein the transient coating comprises one or more polysaccharides.

24. The glass container of claim 21, wherein the transient coating comprises polyacrylic acid or a derivative of polyacrylic acid.

25. The glass container of claim 23, wherein the transient coating comprises an inorganic salt.

26. The glass container of claim 21, 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, 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, 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, substituted siloxanes, alkylsilanes, aromatic silanes, and oxidized polyethylene.

27. The glass container of claim 21, 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. %.

28. The glass container of claim 27, wherein the interior region has a thickness of at least 100 nm.

29. The glass container of claim 21, 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. %.

30. The glass container of claim 29, 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 body.

31. The glass container of claim 21, wherein the inner surface of the body comprises glass and was etched.

32. The glass container of claim 21, wherein the inner surface of the body comprises glass and was acid etched.

33. The glass container of claim 21, wherein the glass of the body has at least a class S3 acid resistance or better according to DIN 12116 dated March 2001.

34. The glass container of claim 21, wherein the glass of the body has at least a class A2 base resistance or better according to ISO 695:

1991.

35. The glass container of claim 21, wherein the glass of the body has at least a type HgB2 hydrolytic resistance or better according to ISO 719:

1985.

36. The glass container of claim 21, wherein the glass of the body has at least a type HgA2 hydrolytic resistance or better according to ISO 720:

1985.

37. The glass container of claim 21, wherein the body is a glass body and was formed with a glass forming process in which the glass body was monotonically cooled from a glass melt.

38. The glass container of claim 21, wherein the glass of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92 (2011).

39. The glass container of claim 38, wherein the Type I, Class B glass according to ASTM Standard E438-92 (2011) is free from zinc and compounds containing zinc.

40. The glass container of claim 21, wherein the glass container is a pharmaceutical package.

41. A glass container comprising:

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

660>

, 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 wherein the glass container does not include a coating on the inner surface of the body; and

a tenacious organic coating positioned around at least a portion of the outer surface of the body, wherein the tenacious organic coating is thermally stable at a temperature of at least about 250°

C. for 30 minutes and the outer surface of the body with the tenacious organic coating has a coefficient of friction less than or equal to 0.7;

wherein the tenacious organic coating comprises a polymer layer and a coupling agent layer.

42. The glass container of claim 41, wherein the tenacious organic coating is thermally stable at a temperature of at least about 280°

C. for 30 minutes.

43. The glass container of claim 41, wherein a light transmission through the glass container is greater than or equal to about 55% of a light transmission through an uncoated glass article for wavelengths from about 400 nm to about 700 nm.

44. The glass container of claim 41, wherein 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 41, 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. %.

46. The glass container of claim 45, wherein the interior region has a thickness of at least 100 nm.

47. The glass container of claim 41, 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. %.

48. The glass container of claim 47, 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 body.

49. The glass container of claim 41, wherein the inner surface of the body comprises glass and was etched.

50. The glass container of claim 41, wherein the inner surface of the body comprises glass and was acid etched.

51. The glass container of claim 41, wherein the glass of the body has at least a class S3 acid resistance or better according to DIN 12116 dated March 2001.

52. The glass container of claim 41, wherein the glass of the body has at least a class A2 base resistance or better according to ISO 695:

1991.

53. The glass container of claim 41, wherein the glass of the body has at least a type HgB2 hydrolytic resistance or better according to ISO 719:

1985.

54. The glass container of claim 41, wherein the glass of the body has at least a type HgA2 hydrolytic resistance or better according to ISO 720:

1985.

55. The glass container of claim 41, wherein the body is a glass body and is mold-formed.

56. The glass container of claim 55, wherein the body is a glass body and was formed with a glass forming process in which the glass body was monotonically cooled from a glass melt.

57. The glass container of claim 41, wherein the glass of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92 (2011).

58. The glass container of claim 57, wherein the Type I, Class B glass according to ASTM Standard E438-92 (2011) is substantially free from zinc and compounds containing zinc.

59. The glass container of claim 41, wherein the glass container is a pharmaceutical package.

60. The glass container of claim 41, wherein the coupling agent layer has a thickness of less than or equal to 100 nm.

61. 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 borosilicate glass according to ASTM Standard E438-92 (2011), wherein at least the inner surface of the glass body has a delamination factor less than or equal to 10, and wherein the glass container does not include a coating on the inner surface of the glass body; and

an inorganic lubricous coating positioned around at least a portion of the outer surface of the glass body, wherein the lubricous coating is an outermost coating on the outer surface of the glass body, the lubricous coating is thermally stable at a temperature of at least about 250°

C. for 30 minutes, the outer surface of the glass body with the lubricous coating has a coefficient of friction less than or equal to 0.7, and the glass body was formed under processing conditions that comprise monotonic cooling which mitigated the vaporization of volatile species in the glass wherein the inorganic lubricous coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO₂, diamond-like carbon, graphenes, or a carbide coating.

62. The glass container of claim 61, wherein the glass 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 body is 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 a temperature of at least about 280°

C. for 30 minutes.

65. The glass container of claim 61, wherein the inorganic lubricous coating comprises at least one of TiN, BN, hBN, TiO₂, Ta₂O₅, HfO₂, Nb₂O₅, V₂O₅, SiO₂, MoS₂, SiC, SnO, SnO₂, ZrO₂, Al₂O₃, BN, ZnO, or BC.