# US 2014/0150499 A1 · Methods for forming delamination resistant glass containers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0150499 A1 - Document ID: US20140150499A1 - Status: Published application - Kind: A1 - Application number: 14/088,556 - Filed: 2013-11-25 - Published: 2014-06-05 - Earliest claimed: 2012-11-30 - Assignees: Corning Incorporated - Applicants: Corning Incorporated - Inventors: Paul Stephen Danielson; Robert Anthony Schaut; Sara Jean Sick - Web page: https://patentgrep.com/patent/US20140150499A1 ## 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 one embodiment, a method of forming a glass container may include forming a glass container comprising a sidewall at least partially enclosing an interior volume. At least a portion of the interior surface of the sidewall may have an interior surface layer with a persistent layer heterogeneity relative to a midpoint of the sidewall. The interior surface layer of the glass container may be removed from the interior surface of the sidewall such that a modified interior surface of the sidewall has an interior region extending from about 10 nm below the modified interior surface into a thickness of the sidewall. The interior region may have a persistent layer homogeneity relative to the midpoint of the sidewall such that the modified interior surface is resistant to delamination. ## Claims ### Claim 1 A method of forming a glass container, the method comprising: forming a glass container comprising a sidewall at least partially enclosing an interior volume, at least a portion of an interior surface of the sidewall having an interior surface layer with a persistent layer heterogeneity relative to a midpoint of the sidewall; and removing the interior surface layer from the interior surface of the sidewall such that a modified interior surface of the sidewall has an interior region extending from about 10 nm below the modified interior surface into a thickness of the sidewall, the interior region having a persistent layer homogeneity relative to the midpoint of the sidewall such that the modified interior surface is resistant to delamination. ### Claim 2 (depends on 1) The method of claim 1, further comprising removing an external surface layer from an external surface of the sidewall. ### Claim 3 (depends on 1) The method of claim 1, wherein the glass container has a delamination factor of less than or equal to 10 after the interior surface layer is removed. ### Claim 4 (depends on 1) The method of claim 1, wherein the interior surface layer is removed from the interior surface of the sidewall with an etchant. ### Claim 5 (depends on 4) The method of claim 4, wherein the etchant comprises hydrofluoric acid. ### Claim 6 (depends on 4) The method of claim 4, wherein the etchant comprises at least one mineral acid. ### Claim 7 (depends on 1) The method of claim 1, wherein the interior surface layer has a thickness greater than or equal to 30 nm. ### Claim 8 (depends on 1) The method of claim 1, wherein an extrema in a layer concentration of each constituent component in the interior surface layer is less than about 80% or greater than about 120% of a bulk concentration of a same constituent component at a midpoint of the sidewall when the glass container is in an as-formed condition. ### Claim 9 (depends on 1) The method of claim 1, wherein the glass container is formed from a Type I, Class A or a Type I, Class B glass according to ASTM Standard E438-92. ### Claim 10 (depends on 1) The method of claim 1, wherein the glass container is formed from a borosilicate glass. ### Claim 11 (depends on 1) The method of claim 1, wherein the interior surface layer is silica-poor. ### Claim 12 (depends on 1) The method of claim 1, wherein an extrema in a layer concentration of each constituent component in the interior region is greater than or equal to about 92% and less than or equal to about 108% of a bulk concentration of a same constituent component at a midpoint of the thickness of the sidewall after the interior surface layer has been removed. ### Claim 13 (depends on 1) The method of claim 1, wherein the modified interior surface of the sidewall comprises a surface region extending over the modified interior surface of the glass container to a depth from about 10 nm to about 50 nm from the interior surface of the glass container; and for a discrete point on the modified interior surface of the glass container, 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 modified interior surface of the glass container after the persistent layer heterogeneity has been removed. ### Claim 14 (depends on 1) The method of claim 1, wherein the modified interior surface of the glass container is substantially free from topographical variations. ### Claim 15 A method for forming a glass container, the method comprising: forming a glass container comprising a sidewall at least partially enclosing an interior volume, at least a portion of an interior surface of the sidewall having an interior surface layer with a persistent layer heterogeneity relative to a midpoint of the sidewall; and etching the interior surface of the sidewall with an etchant to remove the interior surface layer such that a modified interior surface of the sidewall has an interior region extending from about 10 nm below the modified interior surface into a thickness of the sidewall, the interior region having a persistent layer homogeneity relative to the midpoint of the sidewall such that the modified interior surface is resistant to delamination. ### Claim 16 (depends on 15) The method of claim 15, further comprising etching an exterior surface of the sidewall. ### Claim 17 (depends on 16) The method of claim 16, wherein the exterior surface is etched to a depth greater than a depth of surface flaws present in the exterior surface of the sidewall. ### Claim 18 (depends on 15) The method of claim 15, wherein the glass container has a delamination factor of less than or equal to 10 after the interior surface layer is removed. ### Claim 19 (depends on 15) The method of claim 15, wherein the etchant comprises hydrofluoric acid. ### Claim 20 (depends on 15) The method of claim 15, wherein the etchant comprises hydrochloric acid. ### Claim 21 (depends on 15) The method of claim 15, wherein the interior surface layer has a thickness greater than or equal to 10 nm. ### Claim 22 (depends on 15) The method of claim 15, wherein the glass container is formed from a Type I, Class A or a Type I, Class B glass according to ASTM Standard E438-92. ### Claim 23 (depends on 15) The method of claim 15, wherein the interior surface layer comprises a sodium borate rich glass material. ### Claim 24 (depends on 15) The method of claim 15, wherein an extrema in a layer concentration of each constituent component in the interior surface layer is less than about 80% or greater than about 120% of a bulk concentration of a same constituent component at a midpoint of the sidewall when the glass container is in an as-formed condition. ### Claim 25 (depends on 15) The method of claim 15, wherein an extrema in a layer concentration of each constituent component in the interior region is greater than or equal to about 92% and less than or equal to about 108% of a bulk concentration of a same constituent component at a midpoint of the thickness of the sidewall after the interior surface layer has been removed. ### Claim 26 (depends on 15) The method of claim 15, wherein the modified interior surface of the sidewall comprises a surface region extending over the modified interior surface of the glass container to a depth from about 10 nm to about 50 nm from the interior surface of the glass container; and for a discrete point on the modified interior surface of the glass container, 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 modified interior surface of the glass container after the persistent layer heterogeneity has been removed. ### Claim 27 (depends on 15) The method of claim 15, wherein an average peak-to-valley roughness per 10,000 μm2 of surface area of the modified interior surface is less than 1 μm. ### Claim 28 A method of forming a glass container, the method comprising: forming a glass container comprising a sidewall at least partially enclosing an interior volume such that at least a portion of an interior surface of the sidewall has an interior surface layer wherein an extrema in a layer concentration of each constituent component in the interior surface layer is less than about 80% or greater than about 120% of a bulk concentration of a same constituent component at a midpoint of the sidewall when the glass container is in an as-formed condition; and removing the interior surface layer from the interior surface of the sidewall such that a modified interior surface of the sidewall has an interior region extending into a thickness of the sidewall wherein an extrema in a layer concentration of each constituent component in the interior region is greater than or equal to about 92% and less than or equal to about 108% of a bulk concentration of a same constituent component at a midpoint of the thickness of the sidewall after the interior surface layer has been removed. ### Claim 29 (depends on 28) The method of claim 28, wherein at least the modified interior surface of the glass container has a delamination factor of less than or equal to 10 after the interior surface layer is removed. ### Claim 30 (depends on 28) The method of claim 28, wherein the glass container is formed from a Type I, Class A or a Type I, Class B glass according to ASTM Standard E438-92. ### Claim 31 (depends on 28) The method of claim 28, wherein an average peak-to-valley roughness per 10,000 μm2 of surface area of the modified interior surface is less than 1 μm. ### Claim 32 (depends on 28) The method of claim 28, wherein the modified interior surface of the sidewall comprises a surface region extending over the modified interior surface of the glass container to a depth from about 10 nm to about 50 nm from the interior surface of the glass container; and for a discrete point on the modified interior surface of the glass container, 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 modified interior surface of the glass container after the interior surface layer has been removed.