# US 2014/0151371 A1 · Glass containers with delamination resistance and improved strength

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- Number: US 2014/0151371 A1
- Document ID: US20140151371A1
- Status: Published application
- Kind: A1
- Application number: 14/075,605
- Filed: 2013-11-08
- Published: 2014-06-05
- 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; Natesan Venkataraman; Ronald Luce Verkleeran
- Web page: https://patentgrep.com/patent/US20140151371A1

## 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 with resistance to delamination and improved strength 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. The glass container may further include a compressively stressed layer extending from the outer surface of the body into the wall thickness. The compressively stressed layer may have a surface compressive stress greater than or equal to 150 MPa.

## Claims

### Claim 1

A glass container comprising:
a 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
a compressively stressed layer extending from the outer surface of the body into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa.

### Claim 2 (depends on 1)

The glass container of claim 1, wherein the surface compressive stress is greater than or equal to 200 MPa.

### Claim 3 (depends on 1)

The glass container of claim 1, wherein the surface compressive stress is greater than or equal to 300 MPa.

### Claim 4 (depends on 1)

The glass container of claim 1, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer greater than or equal to about 3 μm.

### Claim 5 (depends on 1)

The glass container of claim 1, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer greater than or equal to about 25 μm.

### Claim 6 (depends on 1)

The glass container of claim 1, wherein the body is ion-exchange strengthened.

### Claim 7 (depends on 1)

The glass container of claim 1, wherein the body is high-temperature ion-exchange strengthened.

### Claim 8 (depends on 1)

The glass container of claim 1, wherein the body is thermally tempered.

### Claim 9 (depends on 8)

The glass container of claim 8, wherein the compressively stressed layer extends from the outer surface into the wall thickness to a depth of layer of up to 22% of the wall thickness.

### Claim 10 (depends on 1)

The glass container of claim 1, wherein the body comprises laminated glass.

### Claim 11 (depends on 10)

The glass container of claim 10, wherein the laminated glass comprises:
a core layer having a core coefficient of thermal expansion CTEcore; and
at least one cladding layer fused to the core layer and having a second coefficient of thermal expansion CTEclad, wherein CTEcore is not equal to CTEclad.

### Claim 12 (depends on 11)

The glass container of claim 11, wherein:
the at least one cladding layer comprises a first cladding layer and a second cladding layer;
the first cladding layer is fused to a first surface of the core layer and the second cladding layer is fused to a second surface of the core layer; and
CTEcore is greater than CTEclad.

### Claim 13 (depends on 11)

The glass container of claim 11, wherein the compressively stressed layer extends from the outer surface of the body into the wall thickness to a depth of layer which is from about 1 μm to about 90% of the wall thickness.

### Claim 14 (depends on 11)

The glass container of claim 11, wherein the compressively stressed layer extends from the outer surface of the body into the wall thickness to a depth of layer which is from about 1 μm to about 33% of the wall thickness.

### Claim 15 (depends on 11)

The glass container of claim 11, wherein the at least one cladding layer has a delamination factor of less than or equal to 10 after the laminated glass is formed into the glass container.

### Claim 16 (depends on 11)

The glass container of claim 11, wherein the at least one cladding layer forms the inner surface of the body.

### Claim 17 (depends on 1)

The glass container of claim 1 further comprising an inorganic coating positioned on at least a portion of the outer surface of the body, wherein the inorganic coating has a coefficient of thermal expansion which is less than a coefficient of thermal expansion of the body.

### Claim 18 (depends on 1)

The glass container of claim 1, wherein the body has an interior region extending between the inner surface of the body and the outer surface of the body, the interior region having a persistent layer homogeneity.

### Claim 19 (depends on 18)

The glass container of claim 18, wherein the interior region has a thickness of at least 100 nm.

### Claim 20 (depends on 1)

The glass container of claim 1, wherein the inner surface of the body has a persistent surface homogeneity.

### Claim 21 (depends on 20)

The glass container of claim 20, 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 22 (depends on 1)

The glass container of claim 1, wherein the inner surface of the body is etched.

### Claim 23 (depends on 1)

The glass container of claim 1, wherein the inner surface of the body is a barrier coating.

### Claim 24 (depends on 23)

The glass container of claim 23, wherein the barrier coating is a metal nitride coating, a metal oxide coating, a metal sulfide coating, SiO2, diamond-like carbide, graphenes or a carbide coating.

### Claim 25 (depends on 23)

The glass container of claim 23, wherein the barrier coating comprises at least one of Al2O3, TiO2, ZrO2, SnO, SnO2, SiO2, Ta2O5, Nb2O5, Cr2O3, V2O5, ZnO, or HfO2, or combinations thereof.

### Claim 26 (depends on 23)

The glass container of claim 23, wherein the barrier coating comprises at least one of a polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins including polytetrafluorethylenes and other fluoro-substituted polyolefins, perfluoroalkoxy polymers, polyether ether ketones (PEEK), polyamides, epoxies, polyphenolics, polyurethane acrylates, cyclic olefin copolymer and cyclic olefin polymers, polyolefins including polyethylenes, oxidized polyethylenes, polypropylenes, polyethylene/propylene copolymers, polyethylene/vinyl acetate copolymers, polyvinylchloride, polyacrylates, polymethacrylates, polystyrenes, polyterpenes, polyanhydrides, polymaleicanhydrides, polyformaldehydes, polyacetals and copolymers of polyacetals, polysiloxanes of dimethyl or diphenyl or methyl/phenyl mixtures, perfluorinated siloxanes and other substituted siloxanes, polyimides, polycarbonates, polyesters, parafins and waxes, or various combinations thereof.

### Claim 27 (depends on 1)

The glass container of claim 1, wherein the body has at least a class S3 acid resistance or better according to DIN 12116.

### Claim 28 (depends on 1)

The glass container of claim 1, wherein the body has at least a class A2 base resistance or better according to ISO 695.

### Claim 29 (depends on 1)

The glass container of claim 1, wherein the body has at least a type HgB2 hydrolytic resistance or better according to ISO 719.

### Claim 30 (depends on 1)

The glass container of claim 1, wherein the body has at least a type HgA2 hydrolytic resistance or better according to ISO 720.

### Claim 31 (depends on 1)

The glass container of claim 1, wherein the body has a Type 1 chemical durability according to USP <660>.

### Claim 32 (depends on 1)

The glass container of claim 1, wherein the body is a mold-formed body.

### Claim 33 (depends on 1)

The glass container of claim 1, wherein the body is formed with a glass forming process in which the body is monotonically cooled from a glass melt.

### Claim 34 (depends on 1)

The glass container of claim 1, wherein the body is formed from an aluminosilicate glass composition.

### Claim 35 (depends on 1)

The glass container of claim 1, wherein the body is formed from an alkali-aluminosilicate glass composition.

### Claim 36 (depends on 35)

The glass container of claim 35, wherein the alkali-aluminosilicate glass composition is substantially free from boron and compounds containing boron.

### Claim 37 (depends on 35)

The glass container of claim 35, wherein the alkali-aluminosilicate glass composition is substantially free from zinc and compounds containing zinc.

### Claim 38 (depends on 35)

The glass container of claim 35, wherein the alkali-aluminosilicate glass composition is substantially free from phosphorous and compounds containing phosphorous.

### Claim 39 (depends on 1)

The glass container of claim 1, wherein the body is formed from a glass composition comprising:
from about 67 mol. % to about 75 mol. % SiO2;
from about 6 mol. % to about 10 mol. % Al2O3;
from about 5 mol. % to about 12 mol. % alkali oxide, wherein the alkali oxide comprises from about 2.5 mol. % to about 10 mol % Na2O and greater than about 0 mol. % to about 2.5 mol. % K2O;
from about 9 mol. % to about 15 mol. % alkaline earth oxide; and
from about 0 mol. % to about 0.5 mol. % SnO2.

### Claim 40 (depends on 39)

The glass container of claim 39, wherein the glass composition is substantially free from boron and compounds containing boron.

### Claim 41 (depends on 39)

The glass container of claim 39, wherein the glass composition is substantially free from zinc and compounds containing zinc.

### Claim 42 (depends on 39)

The glass container of claim 39, wherein the glass composition is substantially free from phosphorous and compounds containing phosphorous.

### Claim 43 (depends on 1)

The glass container of claim 1, wherein at least the inner surface of the body is formed from a Type I, Class B glass according to ASTM Standard E438-92.

### Claim 44 (depends on 1)

The glass container of claim 1, wherein the glass container is a pharmaceutical package.

### Claim 45

A glass container comprising:
a 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 is formed from a Type I, Class B glass according to ASTM Standard E438-92;
a compressively stressed layer extending into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa; and
a barrier coating positioned on the inner surface of the body such that a composition contained in the glass container contacts the barrier coating and not the inner surface of the body.

### Claim 46 (depends on 45)

The glass container of claim 45, wherein the barrier coating has a delamination factor less than or equal to 10.

### Claim 47 (depends on 45)

The glass container of claim 45, wherein the body is comprises laminated glass.

### Claim 48 (depends on 47)

The glass container of claim 47, wherein the laminated glass comprises:
a core layer having a core coefficient of thermal expansion CTEcore; and
at least one cladding layer fused to the core layer and having a second coefficient of thermal expansion CTEclad, wherein CTEcore is not equal to CTEclad.

### Claim 49 (depends on 48)

The glass container of claim 48, wherein:
the at least one cladding layer comprises a first cladding layer and a second cladding layer;
the first cladding layer is fused to a first surface of the core layer and the second cladding layer is fused to a second surface of the core layer; and
CTEcore is greater than CTEclad.

### Claim 50 (depends on 47)

The glass container of claim 47, wherein the compressively stressed layer has a depth of layer which is from about 1 μm to about 90% of the wall thickness.

### Claim 51 (depends on 47)

The glass container of claim 47, wherein the compressively stressed layer extends to a depth of layer which is from about 1 μm to about 33% of the wall thickness.

### Claim 52 (depends on 47)

The glass container of claim 47 further comprising an inorganic coating positioned on at least a portion of the outer surface of the body, wherein the inorganic coating has a coefficient of thermal expansion which is less than a coefficient of thermal expansion of the body.

### Claim 53

A glass container comprising:
a body having an inner surface, an outer surface and a wall thickness extending from the outer surface to the inner surface, wherein the body is formed from a glass composition which is free from constituent components which form species that volatilize significantly at temperatures corresponding to a viscosity in a range from about 200 poise to about 100 kilopoise; and
a compressively stressed layer extending from the outer surface of the body into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa.

### Claim 54 (depends on 53)

The glass container of claim 53, wherein at least the inner surface of the body has a delamination factor less than or equal to 10.

### Claim 55

A glass container comprising:
a body having an inner surface, an outer surface and a wall thickness extending between the outer surface and the inner surface, wherein the body is formed from a Type I, Class B glass according to ASTM Standard E438-92 and the body is formed under processing conditions which mitigate the vaporization of volatile species in the glass; and
a compressively stressed layer extending from the outer surface of the body into the wall thickness, the compressively stressed layer having a surface compressive stress greater than or equal to 150 MPa.

### Claim 56 (depends on 55)

The glass container of claim 55, wherein at least the inner surface of the body has a delamination factor less than or equal to 10.