# US 10,307,334 B2 · Glass containers with delamination resistance and improved damage tolerance > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,307,334 B2 - Document ID: US10307334B2 - Status: Granted - Kind: B2 - Application number: 15/656,634 - Filed: 2017-07-21 - Published: 2017-11-09 - Granted: 2019-06-04 - Earliest claimed: 2012-11-30 - Assignees: Corning Incorporated - Applicants: Corning Incorporated - Inventors: Theresa Chang; Paul Stephen Danielson; Steven Edward DeMartino; Andrei Gennadyevich Fadeev; Robert Michael Morena; Santona Pal; John Stephen Peanasky; Robert Anthony Schaut; Christopher Lee Timmons; Natesan Venkataraman; Ronald Luce Verkleeren - Web page: https://patentgrep.com/patent/US10307334B2 ## CPC - A61J 1/1468: {Containers characterised by specific material properties} - A61J 1/065: {Rigid ampoules, e.g. glass ampoules} - B32B 17/06: comprising glass as the main or only constituent of a layer, next to another layer of a specific {material} - B65D 1/0207: {characterised by material, e.g. composition, physical features} - B65D 1/0215: {multilayered (B65D81/3837 takes precedence)} - B65D 1/40: Details of walls (other container details B65D23/00, B65D25/00) - B65D 23/02: Linings or internal coatings - B65D 23/0814: {characterised by the composition of the material} - B65D 23/0821: {consisting mainly of polymeric materials (B65D23/0828 takes precedence)} - 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}) - B65D 25/34: Coverings or external coatings (of containers made by folding or erecting blanks made of paper B65D5/62; covering or external coating for bottles or jars not otherwise provided for B65D23/08; wrappers B65D65/00) - C03B 23/04: Re-forming tubes or rods - C03C 15/02: for making a smooth surface - C03C 17/005: {Coating the outside} - C03C 17/22: with other inorganic material (C03C17/34, C03C17/44 take precedence) - C03C 17/30: with silicon-containing compounds - C03C 17/32: with synthetic or natural resins (C03C17/30 takes precedence) - C03C 17/3405: {with at least two coatings of organic materials (C03C17/36, C03C17/42 take precedence)} - C03C 17/42: at least one coating of an organic material and at least one non-metal coating - C03C 21/002: {to perform ion-exchange between alkali ions (C03C21/005 takes precedence)} - C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - C03C 2217/78: Coatings specially designed to be durable, e.g. scratch-resistant - C03C 2218/111: by dipping, immersion - Y10T 428/13: Hollow or container type article [e.g., tube, vase, etc.] - Y10T 428/131: Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.] - Y10T 428/1317: Multilayer [continuous layer] - Y10T 428/24802: Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] - Y10T 428/315: Surface modified glass [e.g., tempered, strengthened, etc.] - A61J: CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - B65D: CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES - C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES - C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract In embodiments, a delamination resistant glass pharmaceutical package includes a glass body formed from a Type 1 Class glass composition according to ASTM Standard E438-92, the glass body having a wall portion with an inner surface and an outer surface. The glass body may have 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 of the glass body may extend from about 10 nm below the inner surface and have a persistent layer homogeneity. The glass body may also have a surface region extending over the inner surface and having a persistent surface homogeneity such that the glass body is resistant to delamination. ## Claims ### Claim 1 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 glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube; 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 extending from about 10 nm below the inner surface and 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; and a surface region extending over the inner surface and having a persistent surface homogeneity such that the glass body is resistant to delamination 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. ### Claim 2 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the interior region has a thickness TLR of at least about 100 nm. ### Claim 3 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein a depth of the surface region is at least about 10 nm. ### Claim 4 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein a depth of the surface region is at least about 50 nm. ### Claim 5 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed at a temperature greater than or equal to 1100° C. and less than or equal to about 1650° C. ### Claim 6 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, 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. ### Claim 7 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed under processing conditions which imparted a uniform temperature history to the inner surface. ### Claim 8 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the persistent layer homogeneity of the glass body is determined by dynamic secondary ion mass spectroscopy. ### Claim 9 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed from a glass composition which was not phase separated. ### Claim 10 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed from a glass composition that was 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. ### Claim 11 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body is ion-exchange strengthened. ### Claim 12 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body has a delamination factor less than or equal to 10. ### Claim 13 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, 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. ### Claim 14 (depends on 13) The delamination resistant glass pharmaceutical package of claim 13, wherein: the interior region extends from about 10 nm below the inner surface of the glass body into the thickness of the body and having a thickness TLR of at least about 100 nm, 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 concentration of the same constituent component in the glass composition at the mid-point of a thickness of the glass body when the glass body is in an as-formed condition. ### Claim 15 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the interior region extends from about 10 nm below the inner surface of the glass body into the thickness of the glass body and having a thickness TLR of at least about 100 nm. ### Claim 16 (depends on 1) The delamination resistant glass pharmaceutical package of claim 1, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating. ### Claim 17 A delamination resistant glass pharmaceutical package comprising: a glass body formed from an ion-exchangeable Type 1 glass composition according to ASTM Standard E438-92(2011), the glass body having a wall portion with an inner surface, an outer surface, and having a thickness with a mid-point therebetween, wherein the glass body forms the inner surface of the glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube; 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 extending from about 10 nm below the inner surface of the glass body into a thickness of the glass body and having a thickness TLR of at least about 100 nm, wherein an extrema in a layer concentration of each constituent component of the glass composition in the interior region is within ±20% of a concentration of the same constituent component in the glass composition at the mid-point of the thickness the glass body when the glass body is in an as-formed condition; and a surface region extending over the entire inner surface of the glass body to a depth of about 10 nm from the inner surface of the glass body, wherein, for a discrete point on the inner surface of the glass body, an extrema of a surface concentration of each constituent component in the surface region at the discrete point is within ±30% of a concentration 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. ### Claim 18 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the extrema in the layer concentration of each constituent component in the interior region is greater than or equal to about 90% and less than or equal to about 110% of a concentration of the same constituent component at the mid-point. ### Claim 19 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the extrema of the 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 85% and less than or equal to about 115% of the same constituent component in the surface region at any second discrete point on the inner surface when the glass body is in an as-formed condition. ### Claim 20 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body has a delamination factor less than or equal to 10. ### Claim 21 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, 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. ### Claim 22 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body was formed under processing conditions which imparted a uniform temperature history to the inner surface. ### Claim 23 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body was formed from a glass composition which was not phased separated. ### Claim 24 (depends on 17) The delamination resistant glass pharmaceutical package of claim 17, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating. ### Claim 25 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, an outer surface, and having a thickness with a mid-point therebetween and comprising a wall portion that transitions to a floor portion through a heel portion, wherein the glass body forms the inner surface of the glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube; 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>; and a surface region extending over at least the inner surface and having a depth extending from the inner surface of the glass container into the thickness of the glass body, the surface region having a persistent surface homogeneity such that 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. ### Claim 26 (depends on 25) The delamination resistant glass pharmaceutical package of claim 25, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating.