Glass containers with delamination resistance and improved damage tolerance
A delamination resistant glass pharmaceutical container may include a glass body comprising a borosilicate glass having a Type 1 chemical durability according to USP <660>. At least an inner surface of the glass body may have a delamination factor less than or equal to 10. A thermally stable coating may be positioned around at least a portion of the outer surface of the glass body. The thermally stable coating may be an outermost coating on the outer surface of the glass body and the outer surface of the glass body with the thermally stable coating has a coefficient of friction less than or equal to 0.7. The thermally stable coating comprising at least one of a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO 2 , diamond-like carbon, graphene, and a carbide coating.
1. A delamination resistant glass pharmaceutical 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 delamination resistant glass pharmaceutical container does not include a coating on the inner surface of the glass body; and
a thermally stable coating positioned around at least a portion of the outer surface of the glass body, wherein the thermally stable coating is an outermost coating on the outer surface of the glass body and the outer surface of the glass body with the thermally stable coating has a coefficient of friction less than or equal to 0.7;
wherein the thermally stable coating comprising at least one of a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO 2 , diamond-like carbon, graphene, and a carbide coating.
2. The delamination resistant glass pharmaceutical container of claim 1 , wherein the thermally stable coating comprises at least one of TiN, BN, hBN, TiO 2 , Ta 2 O 5 , HfO 2 , Nb 2 O 5 , V 2 O 5 , SiO 2 , MoS 2 , SiC, SnO, SnO 2 , ZrO 2 , Al 2 O 3 , ZnO, and BC.
3. The delamination resistant glass pharmaceutical 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 a layer concentration of each constituent component of the glass composition 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 in the glass composition at the mid-point of the thickness of the glass body when the glass body is in an as-formed condition.
4. The delamination resistant glass pharmaceutical container of claim 3 , wherein the interior region has a thickness of at least 100 nm.
5. The delamination resistant glass pharmaceutical 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 inner surface of the glass body, an extrema of a surface concentration of each constituent component of the glass composition 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 inner surface of the glass body when the glass body is in an as-formed condition.
6. The delamination resistant glass pharmaceutical container of claim 5 , 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.
7. The delamination resistant glass pharmaceutical container of claim 1 , wherein the inner surface of the glass body is etched.
8. The delamination resistant glass pharmaceutical container of claim 1 , wherein the glass body is a mold-formed glass body.
9. The delamination resistant glass pharmaceutical 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.
10. A delamination resistant glass pharmaceutical package comprising:
a glass body formed from a Type 1 glass composition according to ASTM Standard E438-92(2011), the glass body having a wall portion with an inner surface and an outer surface, wherein the glass body forms the inner surface of the delamination resistant glass pharmaceutical package and the glass body has at least a class A2 base resistance or better according to ISO 695, at least a type HGB2 hydrolytic resistance or better according to ISO 719 and Type 1 chemical durability according to USP <660>;
an interior region from about 10 nm below the inner surface of the wall portion and extending into the wall portion, the interior region having a thickness of at least 100 nm, the interior region having a persistent layer homogeneity such that an extrema in a layer concentration of each constituent component of the glass composition 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 in the glass composition at a mid-point of a thickness of the glass body when the glass body is in an as-formed condition;
a surface region extending over the inner surface and having a persistent surface homogeneity such that the glass body is resistant to delamination and, for a discrete point on the inner surface of the glass body, an extrema of a surface concentration of each constituent component of the glass composition 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 inner surface of the glass body when the glass body is in an as-formed condition; and
a thermally stable coating positioned around at least a portion of the outer surface of the glass body, wherein the thermally stable coating is an outermost coating on the outer surface of the glass body and the outer surface of the glass body with the thermally stable coating has a coefficient of friction less than or equal to 0.7;
wherein the thermally stable coating comprising at least one of a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO 2 , diamond-like carbon, graphene, or a carbide coating, and wherein the delamination resistant glass pharmaceutical package does not comprise a boron-rich surface on the inner surface of the glass body.
11. The delamination resistant glass pharmaceutical package of claim 10 , wherein the interior region has a thickness TLR of at least about 100 nm.
12. The delamination resistant glass pharmaceutical package of claim 10 , wherein a depth of the surface region is at least about 10 nm.
13. The delamination resistant glass pharmaceutical package of claim 10 , wherein a depth of the surface region is at least about 50 nm.
14. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body is formed at a temperature greater than or equal to 1100° C. and less than or equal to about 1650° C.
15. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body was formed under processing conditions which mitigated vaporization of species in the glass as compared with processing conditions comprising higher temperatures or faster forming speeds.
16. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body is formed under processing conditions which impart a uniform temperature history to the inner surface.
17. The delamination resistant glass pharmaceutical package of claim 10 , wherein the persistent layer homogeneity of the glass body is determined by dynamic secondary ion mass spectroscopy.
18. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body is formed from a glass composition which is not phase separated.
19. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body is formed from a glass composition that is substantially free from species which significantly volatilize at temperatures that correspond to the glass composition having a viscosity in a range from about 200 poise to about 100 kilopoise.
20. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body is ion-exchange strengthened.
21. The delamination resistant glass pharmaceutical package of claim 10 , wherein the glass body has a delamination factor less than or equal to 10.
22. The delamination resistant glass pharmaceutical package of claim 10 , wherein:
the surface region extends over the inner surface of the glass body to a depth from about 10 nm to about 50 nm from the inner surface of the glass body; and
for a discrete point on the inner surface of the glass body, an extrema of a surface 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 a same constituent component in the surface region at any second discrete point on the inner surface of the glass body when the glass body is in an as-formed condition.
23. The delamination resistant glass pharmaceutical package of claim 10 , wherein:
an extrema in a layer concentration of each constituent component of glass composition 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 a same constituent component in the glass composition at the mid-point of the thickness of the glass body when the glass body is in an as-formed condition.