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 formed from an aluminosilicate glass composition having a Class HGA1 hydrolytic resistance when tested according to the ISO 720:1985 testing standard, the glass body having an interior surface and an exterior surface, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 10 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 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 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; 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;
wherein the glass container is a pharmaceutical package, the aluminosilicate glass composition comprises X mol. % of Al 2 O 3 and Y mol. % of alkali oxides and a ratio Y:X is greater than or equal to about 1 and less than or equal to about 2, the aluminosilicate glass composition comprises CaO and MgO in amounts such that a molar ratio of CaO/(CaO+MgO) is less than about 0.5, and a molar ratio of B 2 O 3 /(R 2 O—Al 2 O 3 ) in the aluminosilicate glass composition is from 0 to about 0.3.
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 region has a thickness T LR of at least about 100 nm.
5. The glass container of claim 1 , wherein the interior region extends from 10 nm below the interior surface of the glass body and has a thickness T LR of at least about 100 nm.
6. 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 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 persistent surface homogeneity extends into a wall thickness of the glass body to a depth from about 10 nm to about 50 nm from the interior surface of the glass body.
8. 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.
9. The glass container of claim 8 , wherein the surface region 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.
10. The glass container of claim 1 , wherein the heat-tolerant coating comprises a coupling agent layer.
11. The glass container of claim 10 , wherein the coupling agent layer comprises at least one silane.
12. The glass container of claim 10 , wherein the heat-tolerant coating further comprises a low-friction layer contacting the coupling agent layer.
13. The glass container of claim 1 , wherein the heat-tolerant coating comprises a low-friction layer comprising the polymer.
14. The glass container of claim 1 , wherein a light transmission through a 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.
15. The glass container of claim 1 , wherein the glass body has at least a class S3 acid resistance according to DIN 12116 dated March 2001.
16. The glass container of claim 1 , wherein the glass body has at least a class A2 base resistance according to ISO 695:1991.
17. The glass container of claim 1 , wherein the glass body has at least a type HgB2 hydrolytic resistance according to ISO 719:1985.
18. 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.
19. The glass container of claim 1 , wherein the polymer is selected from the group consisting of polyimides, polybenzimidazoles, polysulfones, polyetheretherketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, polyaromatic heterocyclic polymers, silsesquioxane-based polymers, and silicone resins.
20. The glass container of claim 1 , wherein the aluminosilicate glass composition comprises one or more of:
Al 2 O 3 in an amount of from about 5 mol. % to about 7 mol. %;
alkali oxides in an amount greater than or equal to about 8 mol. %;
Na 2 O in an amount greater than or equal to 8 mol. %;
K 2 O in an amount of from about 0.01 mol. % to about 3 mol. %;
alkaline earth oxides in an amount of from about 4 mol. % to about 8 mol. %; or
CaO in an amount of from 0 mol. % to about 5 mol. %.
21. A glass container comprising:
a glass body formed from an aluminosilicate glass composition having a Class HGA1 hydrolytic resistance when tested according to the ISO 720:1985 testing standard, the glass body having an interior surface and an exterior surface, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 10 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 glass body has an interior region extending from below the interior surface of the glass body and into a wall thickness 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; 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;
wherein the glass container is a pharmaceutical package, the aluminosilicate glass composition comprises X mol. % of Al 2 O 3 and Y mol. % of alkali oxides and a ratio Y:X is greater than or equal to about 1 and less than or equal to about 2, the aluminosilicate glass composition comprises CaO and MgO in amounts such that a molar ratio of CaO/(CaO+MgO) is less than about 0.5, and a molar ratio of B 2 O 3 /(R 2 O—Al 2 O 3 ) in the aluminosilicate glass composition is from 0 to about 0.3.
22. The glass container of claim 21 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 260° C. for 30 minutes.
23. The glass container of claim 21 , wherein the heat-tolerant coating is thermally stable at a temperature of at least 320° C. for 30 minutes.
24. The glass container of claim 21 , wherein the interior region extends from 10 nm below the interior surface of the glass body and has a thickness T LR of at least about 100 nm.
25. The glass container of claim 21 , 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 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.
26. The glass container of claim 25 , wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth from about 10 nm to about 50 nm from the interior surface of the glass body.
27. The glass container of claim 21 , wherein the glass body comprises an alkali aluminosilicate glass composition.
28. The glass container of claim 21 , wherein the glass body is substantially free from boron and compounds containing boron.
29. The glass container of claim 21 , wherein the polymer is selected from the group consisting of polyimides, polybenzimidazoles, polysulfones, polyetheretherketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, polyaromatic heterocyclic polymers, silsesquioxane-based polymers, and silicone resins.
30. The glass container of claim 21 , wherein the aluminosilicate glass composition comprises one or more of:
Al 2 O 3 in an amount of from about 5 mol. % to about 7 mol. %;
alkali oxides in an amount greater than or equal to about 8 mol. %;
Na 2 O in an amount greater than or equal to 8 mol. %;
K 2 O in an amount of from about 0.01 mol. % to about 3 mol. %;
alkaline earth oxides in an amount of from about 4 mol. % to about 8 mol. %; or
CaO in an amount of from 0 mol. % to about 5 mol. %.