Delamination resistant glass containers with heat-tolerant coatings
Delamination resistant glass containers with heat-tolerant coatings are disclosed. In one embodiment, a glass container may include a glass body having an interior surface, an exterior surface and a wall thickness extending from the exterior surface to the interior surface. At least the interior surface of the glass body is delamination resistant. The glass container may further include a heat-tolerant coating positioned on at least a portion of the exterior surface of the glass body. The heat-tolerant coating may be thermally stable at temperatures greater than or equal to 260° C. for 30 minutes.
1. A glass container comprising:
a glass body having an interior surface and an exterior surface, the glass body formed from an aluminosilicate glass having a Class HGA1 hydrolytic resistance when tested according to the ISO 720 testing standard, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 3 and a threshold diffusivity of greater than about 16 μm 2 /hr at a temperature less than or equal to 450° C., and wherein the aluminosilicate glass comprises alkaline Earth oxides in an amount from 4 mol. % to 8 mol. % less than or equal to 4 mol. % B 2 O 3 , Al 2 O 3 in X mol. %, and alkali oxides in Y mol. %, and wherein a ratio Y:X is greater than or equal to 1; and
a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the heat-tolerant coating is thermally stable at a temperature of at least 260° C. for 30 minutes, and wherein the heat-tolerant coating comprises a polymer selected from the group consisting of polyimides, fluoropolymers, silsesquioxane-based polymers, and silicone resins;
wherein the glass body has an interior region extending between the interior surface of the glass body and the exterior 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 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, and wherein the interior region extends from 10 nm below the interior surface of the glass body to a depth D LR of at least 100 nm from the interior surface of the glass body.
2. The glass container of claim 1 , wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7.
3. The glass container of claim 1 , wherein the heat-tolerant 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.
4. The glass container of claim 1 , wherein the interior 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 aluminosilicate 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.
5. The glass container of claim 4 , wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth D SR of at least 10 nm from the interior surface of the glass body.
6. The glass container of claim 1 , wherein the glass body has a surface region that extends from the interior surface of the glass body into a wall thickness of the glass body, the surface region having 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.
7. The glass container of claim 6 , wherein the surface region extends into a wall thickness of the glass body to a depth D SR of at least 10 nm from the interior surface of the glass body.
8. The glass container of claim 1 , wherein the heat-tolerant coating comprises a coupling agent layer.
9. The glass container of claim 8 , wherein the coupling agent layer comprises at least one silane.
10. The glass container of claim 8 , wherein the heat-tolerant coating comprises a low-friction layer contacting the coupling agent layer.
11. The glass container of claim 1 , wherein the heat-tolerant coating comprises a low-friction layer comprising the polymer.
12. The glass container of claim 1 , wherein a light transmission through the coated portion of 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.
13. The glass container of claim 1 , wherein the glass body has at least a class S3 acid resistance according to DIN 12116.
14. The glass container of claim 1 , wherein the glass body has at least a class A2 base resistance according to ISO 695.
15. The glass container of claim 1 , wherein the glass body has at least a type HgB2 hydrolytic resistance according to ISO 719.
16. The glass container of claim 1 , wherein the glass container is a pharmaceutical package.
17. The glass container of claim 1 , wherein the glass body has a compressive stress greater than or equal to 300 MPa in at least the exterior surface of the glass body and a depth of layer of at least 30 μm.
18. The glass container of claim 1 , wherein the aluminosilicate glass comprises less than 2 mol. % ZrO 2 .
19. A glass container comprising:
a glass body having an interior surface and an exterior surface, the glass body formed from an aluminosilicate glass having a Class HGA1 hydrolytic resistance when tested according to the ISO 720 testing standard, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 3 and a threshold diffusivity of greater than about 16 μm 2 /hr at a temperature less than or equal to 450° C., and wherein the aluminosilicate glass comprises alkaline Earth oxides in an amount from 4 mol. % to 8 mol. % less than or equal to 4 mol. % B 2 O 3 , Al 2 O 3 in X mol. %, and alkali oxides in Y mol. %, and wherein a ratio Y:X is greater than or equal to 1; and
a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7, and wherein the heat-tolerant coating comprises a polymer selected from the group consisting of polyimides, fluoropolymers, silsesquioxane-based polymers, and silicone resins,
wherein the glass body has an interior region extending between the interior surface of the glass body and the exterior 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 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, and wherein the interior region extends from 10 nm below the interior surface of the glass body to a depth D LR of at least 100 nm from the interior surface of the glass body.
20. The glass container of claim 19 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 260° C. for 30 minutes.
21. The glass container of claim 19 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 320° C. for 30 minutes.
22. The glass container of claim 19 , wherein the interior 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 aluminosilicate 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.
23. The glass container of claim 22 , wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth D SR of at least 10 nm from the interior surface of the glass body.
24. The glass container of claim 19 , wherein the glass body comprises an alkali aluminosilicate glass composition.
25. The glass container of claim 19 , wherein the glass body is substantially free from boron and compounds containing boron.
26. The glass container of claim 19 , wherein the aluminosilicate glass comprises less than 2 mol. % ZrO 2 .
27. A glass container comprising:
a glass body having an interior surface and an exterior surface, the glass body formed from an aluminosilicate glass having a Class HGA1 hydrolytic resistance when tested according to the ISO 720 testing standard, wherein at least the interior surface of the glass body has a threshold diffusivity of greater than about 16 μm 2 /hr at a temperature less than or equal to 450° C., and wherein the aluminosilicate glass comprises alkaline Earth oxides in an amount from 4 mol. % to 8 mol. % less than or equal to 4 mol. % B 2 O 3 , Al 2 O 3 in X mol. %, and alkali oxides in Y mol. %, and wherein a ratio Y:X is greater than or equal to 1;
an interior region extending between the interior surface of the glass body and the exterior 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 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, wherein the interior region extends from 10 nm below the interior surface of the glass body to a depth D LR of at least 100 nm from the interior surface of the glass body, and wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 3; and
a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the heat-tolerant coating is thermally stable at a temperature of at least 280° C. for 30 minutes, and wherein the heat-tolerant coating comprises a polymer selected from the group consisting of polyimides, fluoropolymers, silsesquioxane-based polymers, and silicone resins.
28. The glass container of claim 27 , wherein the interior 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 aluminosilicate 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.
29. The glass container of claim 28 , wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth D SR of at least 10 nm from the interior surface of the glass body.
30. The glass container of claim 27 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 320° C. for 30 minutes.
31. The glass container of claim 27 , wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7.
32. The glass container of claim 27 , wherein the glass body comprises an alkali aluminosilicate glass.
33. The glass container of claim 27 , wherein the glass body is substantially free from boron and compounds containing boron.
34. The glass container of claim 27 , wherein the aluminosilicate glass comprises less than 2 mol. % ZrO 2 .
35. A glass container comprising:
a glass body having an interior surface and an exterior surface, the glass body formed from an aluminosilicate glass having a Class HGA1 hydrolytic resistance when tested according to the ISO 720 testing standard, wherein the interior surface 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 aluminosilicate 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, and at least the interior surface of the glass body has a threshold diffusivity of greater than about 16 μm 2 /hr at a temperature less than or equal to 450° C., wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 3, and wherein the aluminosilicate glass comprises alkaline Earth oxides in an amount from 4 mol. % to 8 mol. % less than or equal to 4 mol. % B 2 O 3 , Al 2 O 3 in X mol. %, and alkali oxides in Y mol. %, and wherein a ratio Y:X is greater than or equal to 1; and
a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the heat-tolerant coating is thermally stable at a temperature of at least 260° C. for 30 minutes, and wherein the heat-tolerant coating comprises a polymer selected from the group consisting of polyimides, fluoropolymers, silsesquioxane-based polymers, and silicone resins.
36. The glass container of claim 35 , wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth of at least 10 nm from the interior surface of the glass body.
37. The glass container of claim 35 , wherein:
the glass body has a surface region that extends from the interior surface of the glass body into a wall thickness of the glass body to a depth D SR ; and
the surface region possesses the persistent surface homogeneity.
38. The glass container of claim 37 , wherein the depth D SR of the surface region is at least 10 nm from the interior surface of the glass body.
39. The glass container of claim 35 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 320° C. for 30 minutes.
40. The glass container of claim 35 , wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7.
41. The glass container of claim 35 , wherein the aluminosilicate glass comprises less than 2 mol. % ZrO 2 .
42. A glass container comprising:
a glass body having an interior surface and an exterior surface, the glass body formed from an aluminosilicate glass having a Class HGA1 hydrolytic resistance when tested according to the ISO 720 testing standard, wherein the alkali aluminosilicate glass has a threshold diffusivity of greater than about 16 μm 2 /hr at a temperature less than or equal to 450° C. and is substantially free of boron and compounds of boron such that at least the interior surface of the glass body has a delamination factor of less than or equal to 3, wherein the glass body has an interior region extending between the interior surface of the glass body and the exterior 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 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, and wherein the aluminosilicate glass comprises alkaline Earth oxides in an amount from 4 mol. % to 8 mol. % Al 2 O 3 in X mol. % and alkali oxides in Y mol. %, and wherein a ratio Y:X is greater than or equal to 1; and
a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the heat-tolerant coating is thermally stable at a temperature of at least 260° C. for 30 minutes, and wherein the heat-tolerant coating comprises a polymer selected from the group consisting of polyimides, fluoropolymers, silsesquioxane-based polymers, and silicone resins.
43. The glass container of claim 42 , wherein the alkali aluminosilicate glass composition is substantially free of phosphorous and compounds containing phosphorous.
44. The glass container of claim 42 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 320° C. for 30 minutes.
45. The glass container of claim 42 , wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7.
46. The glass container of claim 42 , wherein the glass body is ion-exchange strengthened.
47. The glass container of claim 42 , wherein the glass body has a compressive stress greater than or equal to 300 MPa in at least the exterior surface of the glass body and a depth of layer of at least 3 μm.
48. The glass container of claim 42 , wherein the heat-tolerant coating comprises a coupling agent layer comprising at least one of:
a first silane, a hydrolysate thereof, or an oligomer thereof; or
a chemical formed from the oligomerization of at least the first silane and a second silane, wherein the first silane and the second silane are different.
49. The glass container of claim 48 , wherein the first silane is an aromatic silane.
50. The glass container of claim 49 , wherein the first silane comprises at least one amine moiety.
51. The glass container of claim 49 , wherein the first silane is an aromatic alkoxysilane, an aromatic acyloxysilane, an aromatic halogen silane, or an aromatic aminosilane.
52. The glass container of claim 49 , wherein the coupling agent comprises at least one of:
a mixture of the first silane and the second silane, wherein the second silane is an aliphatic silane; or
a chemical formed from the oligomerization of at least the first silane and the second silane.
53. The glass container of claim 52 , wherein the first silane is an aromatic alkoxysilane comprising at least one amine moiety and the second silane is an aliphatic alkoxysilane comprising at least one amine moiety.
54. The coated pharmaceutical package of claim 52 , wherein the first silane is selected from the group consisting of aminophenyl alkoxysilanes, aminophenyl acyloxysilanes, aminophenyl halosilanes, 3-(m-aminophenoxy)propyl alkoxysilanes, 3-(m-aminophenoxy)propyl acyloxysilanes, 3-(m-aminophenoxy)propyl halosilanes, N-phenylaminopropyl alkoxysilanes, N-phenylaminopropyl acyloxysilanes, N-phenylaminopropyl halosilanes, (chloromethyl)phenyl alkoxysilanes, (chloromethyl)phenyl acyloxysilanes, (chloromethyl)phenyl halosilanes, hydrolysates thereof, and oligomers thereof, and the second silane is selected from the group consisting of 3-aminopropyl alkoxysilanes, 3-aminopropyl acyloxysilanes, 3-aminopropyl halosilanes, N-(2-aminoethyl)-3-aminopropyl alkoxysilanes, N-(2-aminoethyl)-3-aminopropyl acyloxysilanes, N-(2-aminoethyl)-3-aminopropyl halosilanes, vinyl alkoxysilanes, vinyl acyloxysilanes, vinyl halosilanes, vinyl aminosilanes, methyl alkoxysilanes, methyl acyloxysilanes, methyl halosilanes, methyl aminosilanes, N-phenylaminopropyl alkoxysilanes, N-phenylaminopropyl acyloxysilanes, N-phenylaminopropyl halosilanes, (N-phenylamino)methyl alkoxysilanes, (N-phenylamino)methyl acyloxysilanes, (N-phenylamino)methyl halosilanes, N-(2-Vinylbenzylaminoethyl)-3-aminopropyl alkoxysilanes, N-(2-Vinylbenzylaminoethyl)-3-aminopropyl acyloxysilanes, N-(2-Vinylbenzylaminoethyl)-3-aminopropyl halosilanes, hydrolysates thereof, and oligomers thereof.
55. The glass container of claim 52 , wherein the first silane is aminophenyltrimethoxy silane and the second silane is 3-aminopropyltrimethoxy silane.
56. The glass container of claim 48 , wherein the heat-tolerant coating further comprises a low-friction layer comprising the polymer.
57. The glass container of claim 56 , wherein the polymer is a polyimide.
58. The glass container of claim 57 , wherein the polyimide is formed from the polymerization of:
at least one monomer comprising at least two amine moieties; and
at least one monomer comprising at least two anhydride moieties and having a benzophenone structure.
59. The glass container of claim 42 , wherein the glass container is a pharmaceutical package for containing a pharmaceutical formulation.
60. The glass container of claim 42 , wherein the aluminosilicate glass comprises less than 2 mol. % ZrO 2 .