# US 10,307,333 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 10,307,333 B2 - Document ID: US10307333B2 - Status: Granted - Kind: B2 - Application number: 14/075,620 - Filed: 2013-11-08 - Published: 2014-06-05 - 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; Dana Craig Bookbinder - Web page: https://patentgrep.com/patent/US10307333B2 ## 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 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 ### Claim 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. ### Claim 2 (depends on 1) 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. ### Claim 3 (depends on 2) 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. ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) 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. %. ### Claim 6 (depends on 5) The glass container of claim 5, wherein the interior region has a thickness of at least 100 nm. ### Claim 7 (depends on 5) 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. ### Claim 8 (depends on 1) 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. %. ### Claim 9 (depends on 8) The glass container of claim 8, wherein the persistent surface homogeneity extends into the wall thickness of the glass body to a depth DSR of at least 10 nm from the inner surface of the glass body. ### Claim 10 (depends on 1) The glass container of claim 1, wherein the inner surface of the glass body was etched. ### Claim 11 (depends on 1) The glass container of claim 1, wherein the inner surface of the glass body was acid etched. ### Claim 12 (depends on 1) 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. ### Claim 13 (depends on 1) 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. ### Claim 14 (depends on 1) 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. ### Claim 15 (depends on 1) 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. ### Claim 16 (depends on 1) The glass container of claim 1, wherein the glass body is a mold-formed body. ### Claim 17 (depends on 1) 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. ### Claim 18 (depends on 1) 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). ### Claim 19 (depends on 18) 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. ### Claim 20 (depends on 1) The glass container of claim 1, wherein the glass container is a pharmaceutical package. ### Claim 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. ### Claim 22 (depends on 21) 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. ### Claim 23 (depends on 21) The glass container of claim 21, wherein the transient coating comprises one or more polysaccharides. ### Claim 24 (depends on 21) The glass container of claim 21, wherein the transient coating comprises polyacrylic acid or a derivative of polyacrylic acid. ### Claim 25 (depends on 23) The glass container of claim 23, wherein the transient coating comprises an inorganic salt. ### Claim 26 (depends on 21) 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. ### Claim 27 (depends on 21) 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. %. ### Claim 28 (depends on 27) The glass container of claim 27, wherein the interior region has a thickness of at least 100 nm. ### Claim 29 (depends on 21) 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. %. ### Claim 30 (depends on 29) The glass container of claim 29, wherein the persistent surface homogeneity extends into the wall thickness of the body to a depth DSR of at least 10 nm from the inner surface of the body. ### Claim 31 (depends on 21) The glass container of claim 21, wherein the inner surface of the body comprises glass and was etched. ### Claim 32 (depends on 21) The glass container of claim 21, wherein the inner surface of the body comprises glass and was acid etched. ### Claim 33 (depends on 21) 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. ### Claim 34 (depends on 21) 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. ### Claim 35 (depends on 21) 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. ### Claim 36 (depends on 21) 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. ### Claim 37 (depends on 21) 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. ### Claim 38 (depends on 21) 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). ### Claim 39 (depends on 38) 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. ### Claim 40 (depends on 21) The glass container of claim 21, wherein the glass container is a pharmaceutical package. ### Claim 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. ### Claim 42 (depends on 41) 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. ### Claim 43 (depends on 41) 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. ### Claim 44 (depends on 41) 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. ### Claim 45 (depends on 41) 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. %. ### Claim 46 (depends on 45) The glass container of claim 45, wherein the interior region has a thickness of at least 100 nm. ### Claim 47 (depends on 41) 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. %. ### Claim 48 (depends on 47) The glass container of claim 47, wherein the persistent surface homogeneity extends into the wall thickness of the body to a depth DSR of at least 10 nm from the inner surface of the body. ### Claim 49 (depends on 41) The glass container of claim 41, wherein the inner surface of the body comprises glass and was etched. ### Claim 50 (depends on 41) The glass container of claim 41, wherein the inner surface of the body comprises glass and was acid etched. ### Claim 51 (depends on 41) 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. ### Claim 52 (depends on 41) 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. ### Claim 53 (depends on 41) 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. ### Claim 54 (depends on 41) 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. ### Claim 55 (depends on 41) The glass container of claim 41, wherein the body is a glass body and is mold-formed. ### Claim 56 (depends on 55) 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. ### Claim 57 (depends on 41) 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). ### Claim 58 (depends on 57) 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. ### Claim 59 (depends on 41) The glass container of claim 41, wherein the glass container is a pharmaceutical package. ### Claim 60 (depends on 41) The glass container of claim 41, wherein the coupling agent layer has a thickness of less than or equal to 100 nm. ### Claim 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. ### Claim 62 (depends on 61) 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. ### Claim 63 (depends on 61) 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. ### Claim 64 (depends on 61) 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. ### Claim 65 (depends on 61) 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.