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WO2021108069A1 - Articles en verre ayant des caractéristiques de surface et leurs procédés de fabrication - Google Patents

Articles en verre ayant des caractéristiques de surface et leurs procédés de fabrication Download PDF

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Publication number
WO2021108069A1
WO2021108069A1 PCT/US2020/057840 US2020057840W WO2021108069A1 WO 2021108069 A1 WO2021108069 A1 WO 2021108069A1 US 2020057840 W US2020057840 W US 2020057840W WO 2021108069 A1 WO2021108069 A1 WO 2021108069A1
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WO
WIPO (PCT)
Prior art keywords
glass
region
mol
glass substrate
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2020/057840
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English (en)
Inventor
Michael Patrick Donovan
Timothy Michael Gross
Guangli Hu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
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Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Publication of WO2021108069A1 publication Critical patent/WO2021108069A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • Embodiments described herein generally relate to ion-exchanged glass articles and methods of making them. Specifically, embodiments described herein relate to ion- exchanged glass articles for use in various industries including, for example, consumer electronics, transportation, architecture, defense, medicine, and packaging, and to methods for making them.
  • Glass can be made as flat as possible in a plane and can be featureless. However, there are applications in which glass shaping or texturing is desirable. Shaping of a glass part can be performed using a thermal forming process including one or more molds for targeting a specific part shape. Such molding processes can be expensive and limited in the curved shapes and dimensions they can successfully form.
  • a first aspect (1) of the present application is directed to a glass article.
  • the glass article includes a glass substrate formed of a glass composition and includes a first surface, a second surface disposed opposite the first surface, and a surface feature.
  • the surface feature includes a convex surface region at the first surface and a concave surface region at the second surface opposite the convex surface region at the first surface, where a concentration of an alkali metal oxide in the glass composition measured in the convex surface region is different from a concentration of the alkali metal oxide in the glass composition measured in the concave surface region.
  • the glass article according to the first aspect (1) is provided and the surface feature is one of a plurality of surface features, each surface feature including a convex surface region at the first surface, a concave surface region at the second surface opposite the convex region at the first surface, and a concentration of an alkali metal measured in the convex surface region that is different from a concentration of the alkali metal oxide measured in the concave surface region.
  • the glass article according aspect (1) or aspect (2) is provided and the concave surface region at the second surface includes a non-chemically strengthened surface region on the second surface surrounded by a chemically strengthened surface region on the second surface.
  • the glass article according to any of aspects (1) - (3) is provided and the convex surface region at the first surface opposite the concave surface region at the second surface includes a chemically strengthened surface region.
  • the glass article according to any of aspects (1) - (4) is provided and the alkali metal oxide includes one or more of: lithium, potassium, or sodium.
  • the glass article according to any of aspects (1) - (5) is provided and the difference between the concentration of the alkali metal oxide in the glass composition measured in the convex surface region and the concentration of the alkali metal oxide in the glass composition measured in the concave surface region is 1 mol% or more.
  • the glass article according to any of aspects (1) - (6) is provided and the glass substrate has a thickness measured from the first surface to the second surface, where a perimeter edge of the convex surface region at the first surface defines a perimeter of the surface feature, and wherein an alkali metal oxide concentration variation through the thickness of the glass substrate within the perimeter of the surface feature is different from an alkali metal oxide concentration variation through the thickness of the glass substrate outside of the perimeter of the surface feature.
  • the glass article according to the seventh aspect (7) is provided and the alkali metal oxide includes one or more of: lithium, potassium, or sodium.
  • the glass article according any of aspects (1) - (8) is provided and the glass substrate has a thickness measured from the first surface to the second surface of 200 microns or less.
  • the glass article according to any of aspects (1) - (9) is provided and the glass substrate has a thickness measured from the first surface to the second surface in a range of 1 micron to 150 microns.
  • the glass article according to any of aspects (1) - (10) is provided and a peak height of the surface feature is in a range of 1 micron to 10 microns.
  • the glass article according to any of aspects (1) - (6) is provided and a perimeter edge of the convex surface region at the first surface defines a perimeter of the surface feature, and the surface feature includes an effective diameter measured from opposing points on the perimeter of the surface feature in a range of 10 microns to 5 millimeters.
  • the glass article according to any of aspects (1) - (6) is provided and the surface feature includes a peak height measured from a plane in which a perimeter edge of the surface features is located on the first surface of the glass substrate to a maximum height of the convex surface region, a perimeter edge of the convex surface region at the first surface defines the perimeter of the surface feature, an effective diameter of the surface feature is measured from opposing points on the perimeter of the concave surface region, and a ratio of the effective diameter to the peak height is in a range of 1 to 5000.
  • the glass article according to any of aspects (1) - (13) is provided and the convex surface region at the first surface has a surface contour that is different from a surface contour of an area on the first surface surrounding the convex surface region.
  • the glass article according to any of aspects (1) - (14) is provided and the concave surface region at the second surface has a surface contour that is different from a surface contour of an area on the second surface surrounding the concave surface region.
  • a sixteenth aspect (16) of the present application is directed to a glass article.
  • the glass articles includes a glass substrate including a first surface, a second surface disposed opposite the first surface, a thickness measured from the first surface to the second surface of 200 microns or less, and a surface feature.
  • the surface feature includes a convex surface region at the first surface and a concave surface region at the second surface opposite the convex surface region at the first surface, where the surface feature has a peak height in a range of 1 micron to 10 microns.
  • the glass article according to the sixteenth aspect (16) is provided and at least a portion of the first surface is chemically strengthened and at least a portion of the second surface is chemically strengthened.
  • the glass article according to either of the sixteenth aspect (16) or the seventeenth aspect (17) is provided and the concave surface region at the second surface is not chemically strengthened, and the convex surface region at the first surface is chemically strengthened.
  • a nineteenth aspect (19) of the present application is directed to a method of making a glass article.
  • the method includes asymmetrically ion-exchanging a discrete portion of a glass substrate including a first surface and a second surface opposite the first surface to form a surface feature on the glass substrate.
  • the surface feature includes a convex surface region at the first surface and a concave surface region at the second surface opposite the convex surface region at the first surface.
  • asymmetrically ion-exchanging the discrete portion includes applying a block coating that is non-ion-exchangeable to the second surface of the glass substrate and exposing the glass substrate to an ion-exchange bath.
  • asymmetrically ion-exchanging the discrete portion includes heat treating a region of the discrete portion, and exposing the glass substrate to an ion-exchange bath.
  • a twenty-second aspect (22) the method according to aspect (21) is provided and the heat treatment is performed before exposing the glass substrate to the ion- exchange bath.
  • the method according to aspect (21) is provided and the heat treatment is performed after exposing the glass substrate to the ion-exchange bath.
  • the method according to any of aspects (21) - (23) is provided and the heat treatment includes exposing the region of the discrete portion to a laser beam.
  • the method according to any of aspects (19) - (24) is provided and the glass substrate has a thickness measured from the first surface to the second surface of 200 microns or less.
  • the method includes asymmetrically ion-exchanging a plurality of discrete portions of the glass substrate to form a plurality of surface features on the glass substrate, each surface feature including a convex surface region at the first surface and a concave surface region at the second surface opposite the convex surface region at the first surface.
  • FIG. 1 illustrates cross-sectional view of a glass article having a surface feature according to some embodiments.
  • FIG. 2 illustrates a cross-sectional view of a glass substrate having an ion- exchange blocked region prior to ion-exchanging according to some embodiments.
  • FIG. 3 illustrates the glass substrate of FIG. 2 after ion-exchanging.
  • FIG. 4 illustrates a perspective view of a curved glass article according to some embodiments.
  • FIG. 5 shows curved glass articles having different curvatures resulting from an asymmetric ion-exchange process according to some embodiments.
  • FIG. 6 illustrates a side view of an ion-exchanged glass article having a bend according to some embodiments.
  • FIG. 7 illustrates a perspective view of the glass article of FIG. 6.
  • FIG. 8 illustrates a modeled glass substrate for a finite element analysis.
  • FIG. 9 is a graph of a modeled stress profile for a finite element analysis.
  • FIG. 10 illustrates a side view of a modeled glass article.
  • FIG. 11 is a graph of out-of-plane deformation for modeled glass articles having various thicknesses.
  • FIG. 12A is an optical microscope image of a glass article according to some embodiments.
  • FIG. 12B is an optical microscope image of a glass article according to some embodiments.
  • Glass articles or glass-based articles are used in various industries including, for example, consumer electronics, transportation, architecture, defense, medicine, and packaging.
  • glass articles are used as cover plates or windows for portable or mobile electronic communication and entertainment devices, for example mobile phones, smart phones, tablets, video players, information terminal (IT) devices, laptop computers, navigation systems, watches, smart watches, and televisions, among other devices.
  • IT information terminal
  • glass articles may be used in windows, shower panels, solar panels, and countertops.
  • glass articles are present in automobiles, motorcycles, trains, aircraft, and sea craft, for example boats or personal water crafts (e.g., jet skis). Glass articles can be used in applications that benefit from fracture resistance and thin and lightweight articles.
  • mechanical and chemical reliability of the glass articles is typically driven by functionality, performance, and cost.
  • shaping of glass articles is performed by cutting and edge finishing the glass article, thermal molding the glass article at high temperatures of up to 900°C, surface polishing, cold forming and chemical treatment, e.g., chemical tempering.
  • Other thermal forming processes are also commonly used, for example pressing or slumping methods.
  • these processes can be time consuming and require additional steps to be performed, for example forming and finishing.
  • forming glass articles using known thermal forming processes may be time consuming and expensive.
  • thermal forming processes are generally used to provide a glass article with a curve or bend, and are not used to form local deformations, for example dimples or bumps on a surface of the glass article.
  • Some embodiments described herein relate to glass articles that are formed by asymmetrically ion-exchanging a glass substrate. As a result, shaping of a glass article may be performed simultaneously with chemical strengthening of the glass substrate via ion-exchange when the glass substrate is exposed to an ion-exchange process, for example an ion-exchange bath. Further, some embodiments described herein relate to a glass article having surface features formed by asymmetric ion-exchange so as to produce a glass article having desired surface features, a desired surface texture, and/or desired optical properties.
  • FIG. 1 illustrates a glass article 100 according to some embodiments. Glass article
  • glass substrate 110 having a first surface 112 opposite a second surface 114.
  • Glass substrate 110 may be cut from a glass sheet, a glass ribbon, or other such glass member.
  • glass substrate 110 may be a fusion-drawn glass substrate (having a fusion line).
  • glass substrate 110 may be generally planar except for surface features 120 as described in further detail herein.
  • first surface 112 of glass substrate 110 may be on a first plane and second surface 114 of glass substrate 110 may be on a second plane that is parallel to the first plane.
  • glass substrate 110 can be non-planar (e.g., curved or bent).
  • Glass substrate 110 has a thickness 113, as shown in FIG. 1, where thickness 113 is measured as the shortest distance from first surface 112 to second surface 114 through glass substrate 110. Thickness 113 of glass substrate 110 can be in a range of 1 pm (micrometers, microns) to 200 pm, including subranges. For example, thickness 113 may be , 5 pm, 10 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 75 pm, 80 pm,
  • thickness 113 may be in a range of 1 pm to 190 pm, 1 pm to 180 pm, 1 pm to 170 pm, 1 pm to 160 pm, 1 pm to 150 pm, 1 pm to 140 pm, 1 pm to 130 pm, 1 pm to 120 pm, 1 pm to 110 pm, 1 pm to 100 pm, 1 pm to 90 pm, 1 pm to 80 pm, 1 pm to 70 pm, 1 pm to 60 pm, 1 pm to 50 pm, 1 pm to 40 pm, 1 pm to 30 pm, 1 pm to 20 pm , 1 pm to 10 pm, 1 pm to 5 pm, 5 pm to 190 pm, 10 pm to 180 pm, 20 pm to 170 pm, 30 pm to 160 pm, 40 pm to 150 pm, 50 pm to 160 pm, 60 pm to 150 pm, 70 pm to 150 pm, 80 pm to 140 pm, 90 pm to 130 pm, or 100 pm to 120 pm.
  • the thickness is measured either before formation of any surface features 120 or is measured at a region not including a surface feature 120.
  • thickness 113 may be 200 microns or less. In some embodiments, thickness 113 may be in a range of 1 micron to 150 microns.
  • the amount of local deformation exhibited after an asymmetric ion-exchange process depends in part on thickness 113 of glass substrate 110, as discussed in further detail herein.
  • a thickness significantly greater than 200 pm may not result in visual local deformation that creates concave and convex surface regions as described herein.
  • glass substrate 110 can include an alkali-alumino silicate glass composition or an alkali-containing aluminoborosilicate glass compositions, though other glass compositions are contemplated.
  • Specific examples of glass compositions that may be used for glass substrate 110 include, but are not limited to, a soda-lime silicate glass, an alkali-alumino silicate glass, an alkali-containing borosilicate glass, an alkali- alumino borosilicate glass, an alkali-containing lithium alumino silicate glass, or an alkali-containing phosphate or phosphosilicate glass.
  • Glass substrate 110 has a base composition that may be characterized as ion- exchangeable.
  • ion-exchangeable means that a glass substrate comprising the composition is capable of exchanging first cations located at or near the surface of the substrate with second cations of the same valence.
  • the first ions may be ions of lithium, sodium, potassium, and rubidium.
  • the second ions may be ions of one of sodium, potassium, rubidium, and cesium, with the proviso that the second ion has an ionic radius greater than the ionic radius of the first ion.
  • the first ion is present in the glass-based substrate as an oxide thereof (e.g., LhO, Na?0, K2O, Rb?0, or a combination thereof).
  • oxide thereof e.g., LhO, Na?0, K2O, Rb?0, or a combination thereof.
  • ion-exchanged glass or “chemically strengthened glass” means glass that has been subject to at least one ion-exchange process that exchanges cations located at or near the surface of the glass with cations of the same valence.
  • glass article 100 may include one or more surface features
  • Surface feature 120 formed in glass substrate 110.
  • Surface feature 120 can be formed by a local deformation of glass substrate 110 using methods described herein.
  • Surface feature 120 includes a protrusion defining a portion of first surface 112 of glass substrate 110 and a dimple defining a portion of second surface 114 of glass substrate.
  • Surface feature 120 is fonned in a discrete portion of glass substrate 110 and does not span the entire length or width of glass substrate 110.
  • glass article 100 can include a plurality of surface features
  • surface features 120 may be arranged in one or more rows or columns. In some embodiments, surface features 120 may be arranged in a grid-like pattern. Adjacent rows or columns of surface features 120 may be aligned or staggered. In some embodiments, surface features 120 may be distributed randomly on glass substrate 110. In some embodiments, surface features 120 may be grouped together in one or more particular regions of glass substrate 110 while a remainder of glass substrate 110 is free of surface features 120. For example, a first half of one surface of glass substrate 110 may include a plurality of surface features 120 while a second half of the surface of glass substrate 110 may be free of surface features 120.
  • Glass article 100 may include any number of surface features 120. In some embodiments, glass article 100 may include 20 or more surface features 120. In some embodiments, glass article 100 may include 50 or more surface features 120. In some embodiments, glass article 100 may include 100 or more surface features 120. In some embodiments, glass article 100 may include 1,000 or more surface features 120. In some embodiments, glass article may include three or more surface features 120. In some embodiments, glass article 100 may include surface features 120 spaced apart from each other at a lateral distance of 1 micron or less. In some embodiments, surface features 120 may be spaced apart from each other at a lateral distance in a range of 10 nanometers to 1 micron. The lateral distance between two surface features 120 is a shortest distance between the perimeter edge 126 of two adjacent surface features 120.
  • surface features 120 may be used to provide glass article
  • surface features 120 may be used to provide glass article 100 with an anti-glare property.
  • surface features 120 may increase a frictional coefficient of first surface 112 and/or second surface 114, thereby increasing frictional contact with glass article 100 when gripped, and thus allowing glass article 100 to be more easily gripped, and/or less likely to slip from a user’s hand.
  • Each surface feature 120 includes a convex surface region 122 at first surface 112.
  • Convex surface region 122 can resemble a bump or a mound on first surface 112 of glass substrate 110. Thus, convex surface region 122 extends above a plane 150 of first surface 112. Plane 150 of first surface 112 is the plane that matches the surface contour of first surface 112 in the absence of surface feature(s) 120. First surface 112 may be flat (as plane 150) or alternatively may be curved. In some cases, plane 150 may be referred to as the surface contour of first surface 112 prior to formation of surface feature(s) 120.
  • Each surface feature 120 also includes a concave surface region 124 at second surface 114 opposite convex surface region 122.
  • Concave surface region 124 can resemble a dimple or cavity on second surface 114 of glass substrate 110.
  • concave surface region 124 is recessed from a plane 152 of second surface 114.
  • Plane 152 of second surface 114 is the plane that matches the surface contour of second surface 114 in the absence of surface feature(s) 120.
  • Second surface 114 may be flat (as plane 152) or alternatively may be curved. In some cases, plane 152 may be referred to as the surface contour of second surface 114 prior to formation of surface feature(s) 120.
  • a convex surface region of a surface feature is defined as a volume including the convex surface of a surface feature and extending from the convex surface to a depth equal to the depth of compression (di, DOC) for the surface on which the convex surface region is formed.
  • a concave surface region of a surface feature is defined as a volume including the concave surface of a surface feature and extending from the concave surface to a depth equal to the depth of compression (d2, DOC) of the convex surface disposed opposite the concave surface.
  • a convex surface region and a concave surface region do not overlap with each other across the thickness of the substrate.
  • Convex surface region 122 has a surface contour that differs from a surface contour of a region 140 on first surface 112 surrounding convex surface region 122.
  • convex surface region 122 has a convex surface contour and region 140 of first surface 112 surrounding convex surface region 122 may be flat.
  • convex surface region 122 may have a convex curvature with a first radius of curvature and region 140 surrounding convex surface region 122 may have a convex curvature with a second radius of curvature different from the first radius of curvature.
  • concave surface region 124 has a surface contour that differs from a surface contour of a region 142 of second surface 114 surrounding concave surface region 124.
  • concave surface region 124 has a concave surface contour and region 142 of second surface 114 surrounding concave surface region 124 may be flat.
  • concave surface region 124 may have a concave curvature with a first radius of curvature and region 142 surrounding concave surface region 124 may have a concave curvature with a second radius of curvature different from the first radius of curvature.
  • Surface feature 120 has an effective diameter 125 defined as a maximum cross- sectional dimension of surface feature 120, as measured from opposing points on a perimeter of surface feature 120 defined by a perimeter edge 126 of convex surface region 122 of surface feature 120 at first surface 112. Perimeter edge 126 of convex surface region 122 is defined by the boundary at which the curvature of first surface 112 changes due to the presence of a surface feature 120.
  • surface feature 120 can have a circular perimeter. However, in some embodiments, the perimeter of surface feature 120 may be oval, elliptical, square, rectangular, or triangular, among other shapes.
  • Effective diameter 125 of surface feature 120 can be in a range of 10 pm (0.01 mm, millimeters) to 5000 pm (5 mm).
  • effective diameter 125 may be 10 pm, 50 pm, 100 pm, 500 pm, 1000 pm, 2000 pm, 3000 pm, 4000 pm, or 5000 pm, or within a range having any two of these values as endpoints, inclusive of the endpoints.
  • the effective diameter may be in a range of 50 pm to 4000 pm, 100 pm to 3000 pm, 500 pm to 2000 pm, or 500 pm to 1000 pm.
  • the term “effective diameter” is utilized to describe the size of a surface feature, but this term should not be interpreted as requiring a surface feature to have a circular diameter or shape.
  • Surface features may have non-circular shapes, and in such embodiments the term “effective diameter” is intended to refer to the maximum cross- sectional dimension of the shape.
  • the “effective diameter” of a surface feature having an oval-shaped perimeter would be length of the oval-shape’s major axis.
  • a plurality of, or all of, a glass article is surface features
  • a plurality of a glass article’s surface features 120 may have different effective diameters.
  • a first surface feature 120 may have a first diameter and a second surface feature 120 may have a second effective diameter that is greater than the first effective diameter.
  • Surface feature 120 has a peak height 127 measured relative to a plane (e.g., plane
  • peak height 127 of surface feature 120 may in a range of 1 pm to 10 pm, including subranges.
  • peak height 127 may be 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, or 10 pm, or within a range having any two of these values as endpoints, inclusive of the endpoints.
  • peak height 127 may be in a range of 2 pm to 9 pm, 3 pm to 8 pm, 4 pm to 7 pm, or 5 pm to 6 pm.
  • a plurality of, or all of, a glass article ’s surface features
  • a plurality of a glass article’s surface features 120 may have different peak heights.
  • a first surface feature 120 may have a first peak height
  • a second surface feature 120 may have a second peak height that is greater than the first peak height.
  • a ratio of the effective diameter to the peak height (125: 127) of surface feature(s) 120 may be 1:1 to 5000:1, 100:1 to 3000:1, or 200:1 to 1000:1.
  • glass substrate 110 may be chemically strengthened by an ion-exchange (IOX) process.
  • a portion of first surface 112 may be chemically strengthened and/or a portion of second surface 114 may be chemically strengthened.
  • a concave surface region 124 at second surface 114 may not be chemically strengthened, while a convex surface region 122 of first surface 112 opposite concave surface region 124 may be chemically strengthened.
  • This asymmetrical chemical strengthening (ion-exchanging) creates convex and concave surface profiles for regions 122 and 124, respectively.
  • concave surface region 124 at second surface 114 includes a non-chemically strengthened surface region on second surface 114 surrounded by a chemically strengthened surface region 142 on second surface 114.
  • convex surface region 122 at first surface 112 opposite concave surface region 124 at second surface 114 includes a chemically strengthened surface region.
  • Surface features 120 may be formed by creating a stress asymmetry in glass substrate 110. Stress asymmetry may be created by asymmetrically ion-exchanging glass substrate 110. In some embodiments, asymmetric ion-exchange may be achieved by blocking ion-exchange at discrete portions of glass substrate 110. For example, a first surface 112 of glass substrate 110 may be ion-exchanged asymmetrically with an opposing second surface 114 of glass substrate 110. In particular, a discrete portion of second surface 114 of glass substrate 110 may be blocked from ion-exchange, while the remainder of second surface 114 and first surface 112 are not blocked from ion-exchange (are capable of being ion-exchanged) in some embodiments.
  • first and second surfaces 112, 114 are ion-exchanged except for the discrete portion of second surface 114 that is blocked from ion-exchange.
  • an ion-exchange process is performed in such an asymmetric manner, an unbalanced stress and/or strain is introduced into the glass substrate 110, resulting in localized bending.
  • stress asymmetry results in a surface feature 120 having concave curvature on second surface 114 at the discrete portion at which ion-exchange is blocked, and a corresponding convex curvature at first surface 112 of glass substrate 110 opposite the discrete portion of second surface 114 that is blocked from ion-exchange. Accordingly, the resulting stress asymmetry results in a localized shape change of glass substrate 110, forming a surface feature 120 at the discrete region that is blocked from ion-exchange.
  • Asymmetric ion-exchange methods described herein are designed to impart ion- exchange in some regions of the glass substrate 110 and no ion-exchange to minimal ion- exchange in other regions of glass substrate 110. In this way, due to the varying degrees of ion-exchange on surfaces of glass substrate 110, curvature is imparted to glass article 100 in a controlled manner. By intentionally creating asymmetric ion-exchange, chemical strengthening and 3D shaping can be fulfilled in a single step.
  • a stress asymmetry may be created by heat treating a discrete surface region (for example, a region at first surface 112 or a region at second surface 114) of glass substrate 110 before and/or after an ion-exchange process, for example, before and/or after exposing glass substrate to an ion-exchange bath.
  • a heat treatment performed before an ion-exchange process can change the diffusivity of ions into a surface region of glass substrate 110 during an ion-exchange process relative to the surface region opposing the heat-treated surface region to create stress asymmetry in glass substrate 110 where the heat treatment was performed.
  • a heat treatment performed after an ion-exchange process can relax stresses in a surface region created during an ion- exchange process relative to the surface region opposing the heat-treated surface region to create stress asymmetry in glass substrate 110 where the heat treatment was performed.
  • This asymmetric stress can create surface features 120 with a convex surface region 122 and a concave surface region 124.
  • heat treating a surface region can be performed using a laser beam, for example a CO2 laser, or using a hot wire. If performed before an ion-exchange process, such a heat treatment can be described as creating a difference in the fictive temperature of glass substrate 110 between first surface 112 and second surface 114.
  • Using a heat treatment can make a localized change in fictive temperature relative to the bulk glass before ion-exchange. This will cause an ion- diffusivity gradient relative to the bulk. If a heat treatment is performed after an ion- exchange process, it can cause a stress relaxation gradient if the glass is heated above its glass transition temperature.
  • Asymmetrically ion-exchanging glass substrate 110 to create a stress asymmetry results in the concentration of an alkali metal oxide measured at convex surface region 122 being different from a concentration of the same alkali metal oxide measured at concave surface region 124.
  • concave surface region 124 can be non-ion- exchanged, and convex surface region 122 can be ion-exchanged, resulting in a different concentration of an alkali metal oxide in the convex surface region 122 compared to concave surface region 124.
  • a difference in an alkali metal oxide concentration measured at the convex surface region 122 compared to the concentration of the alkali metal oxide measured at the concave surface region 124 may be 1 mol% or more.
  • the difference in an alkali metal oxide concentration measured at the convex surface region 122 compared to the concentration of the alkali metal oxide measured at the concave surface region 124 may be 1 mol% to 10 mol%, including subranges.
  • the difference may be 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
  • the difference in an alkali metal oxide concentration measured at the convex surface region 122 compared to the concentration of the alkali metal oxide measured at the concave surface region 124 may be in a range of 2 mol% to 9 mol%, 3 mol% to 8 mol%, 4 mol% to 7 mol%, or 5 mol% to 6 mol%.
  • an alkali metal oxide concentration measured at the convex surface region 122 may be 1 mol% to 10 mol% greater than the concentration of the alkali metal oxide measured at the concave surface region 124, including subranges.
  • the alkali metal oxide concentration measured at the convex surface region 122 may be 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol% greater than the concentration of the alkali metal oxide measured at the concave surface region 124, or within a range having any two of these values as endpoints, inclusive of the endpoints.
  • an alkali metal oxide concentration measured at the convex surface region 122 may be 2 mol% to 9 mol%, 3 mol% to 8 mol%, 4 mol% to 7 mol%, or 5 mol% to 6 mol% greater than the concentration of the alkali metal oxide measured at the concave surface region 124.
  • an alkali metal oxide concentration in mol% at a convex surface region, a concave surface region, or at any other surface region of a glass article is measured using secondary ion mass spectroscopy to measure a mol% of an alkali metal oxide concentration at a certain depth in convex surface region 122, concave surface region 124, or any other surface region of a glass article. For comparison purposes, concentration measurements are reported at the same depth within the regions.
  • the alkali metal oxide includes one or more of lithium, potassium, or sodium.
  • the alkali metal oxide may be lithium oxide (LhO).
  • the alkali metal oxide may be potassium oxide (K2O).
  • the alkali metal oxide may be sodium oxide (Na?0).
  • an increase in concentration of potassium oxide at a surface of glass substrate 110 may occur due to an exchange of sodium ions with potassium ions at the surface.
  • the ion-exchange process results in an increased concentration of potassium oxide in glass substrate at and near surfaces of the glass substrate.
  • an alkali metal oxide concentration variation through the thickness of glass substrate 110 within a perimeter of a surface feature 120 may be different from an alkali metal oxide concentration variation through the thickness of glass substrate 110 outside of the perimeter of a surface feature 120.
  • regions 140, 142 surrounding surface feature 120 may be ion-exchanged, whereas concave surface region 124 of surface feature 120 is not ion-exchanged, and thus concave surface region 124 has a different concentration variation of alkali metal oxide than surrounding regions 140,
  • glass article 100 includes one or more regions under compressive stress (e.g., regions 160, 161) extending from first surface 112 and second surface 114 of glass article 100 to a depth of compression (DOC, di, d2) and a second region (central region 162) under a tensile stress or CT extending from the DOC into the central or interior region of glass article 100.
  • DOC refers to the depth at which the stress within the glass article changes from compressive to tensile.
  • the stress crosses from a positive (compressive) stress to a negative (tensile) stress and thus exhibits a stress value of zero.
  • Ion-exchanged compressive stress regions 160, 161 have a concentration of a metal oxide that is different at two or more points through a thickness of glass article 100.
  • compression or compressive stress (CS) is expressed as a negative ( ⁇ 0) stress and tension or tensile stress is expressed as a positive (> 0) stress.
  • the CS typically has a maximum at the surface of the glass, and the CS varies with distance d from the surface according to a function. Referring again to FIG.
  • a first compressive stress region 160 extends from first surface 112 to a depth di and a second compressive stress region 161 extends from second surface 114 to a depth d2. Together, these segments define a compression or CS of glass article 100.
  • compressive stress including surface CS
  • FSM surface stress meter
  • FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan).
  • SOC stress optical coefficient
  • SOC is measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.
  • the CS of one or more compressive stress regions of a glass article is from greater than or equal to 400 MPa to less than or equal to 800 MPa, for example from greater than or equal to 425 MPa to less than or equal to 775 MPa, from greater than or equal to 450 MPa to less than or equal to 750 MPa, from greater than or equal to 475 MPa to less than or equal to 725 MPa, from greater than or equal to 500 MPa to less than or equal to 700 MPa, from greater than or equal to 525 MPa to less than or equal to 675 MPa, from greater than or equal to 550 MPa to less than or equal to 650 MPa, or from greater than or equal to 575 MPa to less than or equal to 625 MPa, and all ranges and sub-ranges between the foregoing values having any two of the above-listed values as endpoints, including the endpoints.
  • the compressive stress of both regions 160 and 161 is balanced by stored tension in the central region 162 of glass article 100, with the exception of any region occupied by a surface feature 120.
  • CT values are reported as maximum CT values.
  • depth of compression means the depth at which the stress in the chemically strengthened substrates described herein changes from compressive stress to tensile stress. Depth of compression may be measured by a surface stress meter or a scattered light polariscope (SCALP) depending on the ion exchange treatment and the thickness of the article being measured.
  • SCALP scattered light polariscope
  • a surface stress meter for example, the FSM-6000 is used to measure stress and depth of compression.
  • the exchange depth of sodium may indicate the depth of compression while the exchange depth of potassium ions may indicate a change in the magnitude of the compressive stress (but not necessarily) the change in stress from compressive to tensile.
  • depth of layer means the depth that the ions have exchanged into the substrate (e.g., sodium, potassium).
  • the maximum central tension when the maximum central tension cannot be measured directly by SCALP (as when the article being measured is thinner than about 400 microns) the maximum central tension can be approximated by the product of a maximum compressive stress and a depth of compression divided by the difference between the thickness of the substrate and twice the depth of compression, wherein the compressive stress and depth of compression are measured by FSM.
  • the refracted near- field (RNF) method also may be used to derive a graphical representation of the stress profile.
  • RNF refracted near- field
  • the maximum central tension value provided by SCALP is utilized in the RNF method.
  • the graphical representation of the stress profile derived by RNF is force balanced and calibrated to the maximum central tension value provided by a SCALP measurement.
  • the RNF method is described in U.S. Patent No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample”, which is incorporated herein by reference in its entirety.
  • the RNF method includes placing a glass article adjacent to a reference block, generating a polarization-switched light beam that is switched between orthogonal polarizations at a rate of froml Hz to 50 Hz, measuring an amount of power in the polarization-switched light beam and generating a polarization-switched reference signal, wherein the measured amounts of power in each of the orthogonal polarizations are within 50% of each other.
  • the method further includes transmitting the polarization-switched light beam through the glass sample and reference block for different depths into the glass sample, then relaying the transmitted polarization-switched light beam to a signal photodetector using a relay optical system, with the signal photodetector generating a polarization-switched detector signal.
  • the method also includes dividing the detector signal by the reference signal to form a normalized detector signal and determining the profile characteristic of the glass sample from the normalized detector signal.
  • the precise sample speed SS and exposure times ⁇ E to reduce the measurement noise in the polarimeter to an acceptable level when measuring a sample to characterize at least one stress-related characteristic depends on a number of factors. These factors include the characteristics of the image sensing device (e.g., the gain, image capture rate (frames/second), pixel size, internal pixel average techniques, etc.), as well as the nature of the no-stress-related (NSR) scattering feature(s), the intensity of the input light beam, the number of polarization states used, etc. Other factors include the measurement wavelength of the light beam from the laser source and the intensity of the scattered light beam.
  • Example measurement wavelengths can include 640 nanometers (nm), 518 nm and 405 nm.
  • Example exposure times can range from 0.05 millisecond to 100 milliseconds.
  • Example frame rates can range from 10 to 200 frames per second.
  • Example calculations of the optical retardation can utilize from two to two-hundred frames over a measurement time t M of from 0.1 seconds to 10 seconds.
  • the DOC of a surface region adjacent to the convex surface region is measured and the DOC of that surface region is equated to the DOC of the convex surface region.
  • a glass article may have a maximum CT greater than or equal to 35 MPa, for example greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, greater than or equal to 90 MPa, greater than or equal to 100 MPa, or greater than or equal to 110 MPa.
  • the glass article may have a maximum CT less than or equal to 110 MPa, for example less than or equal to 100 MPa, less than or equal to 90 MPa, less than or equal to 80 MPa, less than or equal to 70 MPa, less than or equal to 60 MPa, less than or equal to 50 MPa, or less than or equal to 40 MPa, and all ranges and sub-ranges between the foregoing values. In some embodiments, any of the above ranges may be combined with any other range.
  • the glass article may have a maximum CT from greater than or equal to 35 MPa to less than or equal to 110 MPa, for example from greater than or equal to 40 MPa to less than or equal to 100 MPa, from greater than or equal to 50 MPa to less than or equal to 90 MPa, or from greater than or equal to 60 MPa to less than or equal to 80 MPa. Any of the above ranges may be combined to form range having any two of the above- listed CT values as endpoints, including the endpoints.
  • DOC can be provided in some embodiments herein as a portion of the thickness
  • a glass article may have a depth of compression (DOC) from greater than or equal to 0.15t to less than or equal to 0.25t, for example from greater than or equal to 0.18t to less than or equal to 0.22t, or from greater than or equal to 0.19t to less than or equal to 0.21t.
  • DOC depth of compression
  • a glass article may have a DOC from greater than or equal to 0.16 to less than or equal to 0.2t, for example from greater than or equal to 0.17t to less than or equal to 0.25t, from greater than or equal to 0.18t to less than or equal to 0.25t, from greater than or equal to 0.19t to less than or equal to 0.25t, from greater than or equal to 0.20t to less than or equal to 0.25t, from greater than or equal to 0.2 It to less than or equal to 0.25t, from greater than or equal to 0.22t to less than or equal to 0.25t, from greater than or equal to 0.23t to less than or equal to 0.25t, or from greater than or equal to 0.24t to less than or equal to 0.25t.
  • a glass article may have a DOC from greater than or equal to 0.15t to less than or equal to 0.24t, for example from greater than or equal to 0.15t to less than or equal to 0.23t, from greater than or equal to 0.15t to less than or equal to 0.22t, from greater than or equal to 0.15t to less than or equal to 0.2 It, from greater than or equal to 0.15t to less than or equal to 0.20t, from greater than or equal to 0.15t to less than or equal to 0.19t, from greater than or equal to 0.15t to less than or equal to 0.18t, from greater than or equal to 0.15t to less than or equal to 0.17t, or from greater than or equal to 0.15tto less than or equal to 0.16t.
  • a glass article may have a DOC of 0.20t or more.
  • a glass article may have a DOC of 0.15t or more.
  • Compressive stress layers may be formed in a glass article by exposing the glass article to an ion-exchange solution.
  • the ion-exchange solution may be molten nitrate salt.
  • the ion-exchange solution may be molten KNO3, molten NaNCb, or combinations thereof.
  • the ion- exchange solution may comprise less than about 95% molten KNO3, for example less than about 90% molten KNO3, less than about 80% molten KNO3, less than about 70% molten KNO3, less than about 60% molten KNO3, or less than about 50% molten KNO3.
  • the ion-exchange solution may comprise about 5% or more molten NaNCb, for example about 10% or more molten NaNCb, about 20% or more molten NaNCb, about 30% or more molten NaNCb, or about 40% or more molten NaNCb.
  • the ion-exchange solution may comprise about 95% molten KNO3 and about 5% molten NaNCb, about 94% molten KNO3 and about 6% molten NaNCb, about 93% molten KNO3 and about 7% molten NaNCb, about 80% molten KNO3 and about 20% molten NaNCb, about 75% molten KNO3 and about 25% molten NaNCb, about 70% molten KNO3 and about 30% molten NaNCb, about 65% molten KNO3 and about 35% molten NaNCb, or about 60% molten KNO3 and about 40% molten NaNCb, and all ranges and sub-ranges between the foregoing values.
  • the ion-exchange solution may include lithium salts, for example LiNCb.
  • a glass composition may be exposed to an ion-exchange solution by dipping a glass article made from the glass composition into a bath of the ion-exchange solution, spraying the ion-exchange solution onto a glass article made from the glass composition, or otherwise physically applying the ion-exchange solution to a glass article made from the glass composition.
  • the ion-exchange solution may, according to embodiments, be at a temperature from greater than or equal to 400 °C to less than or equal to 500 °C, for example from greater than or equal to 410 °C to less than or equal to 490 °C, from greater than or equal to 420 °C to less than or equal to 480 °C, from greater than or equal to 430 °C to less than or equal to 470 °C, or from greater than or equal to 440 °C to less than or equal to 460 °C, and all ranges and sub-ranges between the foregoing values and having any two of the above-listed temperature values as endpoints, including the endpoints.
  • the temperature of the ion- exchange solution may be 450 °C.
  • the glass composition may be exposed to the ion-exchange solution for a duration from greater than or equal to 4 hours to less than or equal to 24 hours, for example from greater than or equal to 8 hours to less than or equal to 20 hours, or from greater than or equal to 12 hours to less than or equal to 16 hours, and all ranges and sub-ranges between the foregoing values and having any two of the above-listed time values as endpoints, including the endpoints.
  • the ion-exchange process may be performed in an ion-exchange solution under processing conditions that provide an improved compressive stress profile as disclosed, for example, in U.S. Patent Application Publication No. 2016/0102011, which is incorporated herein by reference in its entirety.
  • the ion-exchange process may be selected to form a parabolic stress profile in the glass articles, for example those stress profiles described in U.S. Patent Application Publication No. 2016/0102014, which is incorporated herein by reference in its entirety.
  • a composition at the surface of a glass article may be different than the composition of the as-formed glass article (i.e., the glass article before it undergoes an ion-exchange process).
  • the glass composition at or near the center of the depth of the glass article will, in some embodiments, still have the composition of the as-formed glass article.
  • glass compositions disclosed in this application are compositions of the glass article near the center of the depth of the article where the composition is unaffected by an ion-exchange process, i.e., the composition of the as- formed glass article.
  • the weight of the glass article increases due to the presence of the larger alkali metal ions in the composition, for example Na+ or K+ being exchanged into the glass for Li+ or Na+, respectively.
  • the percent weight gain of the glass article is from greater than or equal to 0.4% to less than or equal to 1.2%, for example from greater than or equal to 0.5% to less than or equal to 1.1%, from greater than or equal to 0.6% to less than or equal to 1%, or from greater than or equal to 0.7% to less than or equal to 0.9%, an all ranges and sub-ranges between the foregoing values and having any two of the above-listed weight gain values as endpoints, including the endpoints.
  • asymmetric ion-exchange of glass substrate 110 is achieved by applying a block coating 130 that is non-ion- exchangeable to a discrete portion of first or second surface 112, 114 of glass substrate 110.
  • a “block coating” is a layer of material that is non-porous or substantially non-porous to alkali metals used for glass ion-exchange.
  • block coatings 130 are not ion-exchangeable and/or do not allow ions to penetrate therethrough to exchange with the underlying substrate.
  • Substantially non-porous means any penetration of alkali metals into the block coating is de minimus and does not result in measureable ion-exchange.
  • block coatings are able to withstand ion-exchange conditions (e.g., temperatures of 350°C to 500°C) in that they do not degrade or react in the presence of an ion-exchange bath.
  • any optically transparent (at VIS: 350-750nm or higher wavelength) inorganic coating material may be suitable for making a block coating 130.
  • the block coatings can include one or more inorganic dielectric materials.
  • the inorganic dielectric material may be selected from the group of: alkali-free glass, S1O2, AI2O3, T1O2, AIN, (AlN)x(Ab03)i-x, wherein 0.3 ⁇ x ⁇ 0.37, S13N4, SiON, TiN, MgCFAhCb, ZrCh, Nb 2 0s, Ta2O5.Gr mixtures thereof.
  • the block coating may be aluminum oxynitride (AION).
  • block coating 130 can survive up to 500°C without delamination from glass substrate 110 at 400°C to 480°C in an ion-exchange process.
  • Thickness and placement of block coatings 130 can be controlled at ⁇ 1 nm by most coating processes, which allows for precise design of the areas that are ion- exchanged (no block coating applied) relative to those that are not (block coating applied).
  • Any coating equipment that can deliver dielectric materials to form coatings e.g., transparent coatings, may be suitable for depositing a block coating layer.
  • Coating processes include, but are not limited to, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), and atomic layer deposition (ALD).
  • PVD techniques may include: sputter technique, ion- assisted-electron beam (IAD-EB), thermal evaporation, ion beam, and/or laser ablation.
  • a block coating 130 may have a thickness in a range of 1 nm (nanometers) to 100 nm, including subranges.
  • block coating 130 may have a thickness of 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm,
  • block coating 130 nay have a thickness in a range of 10 nm to 90 nm, 20 nm to 80 nm, 30 nm to 70 nm, 40 nm to 60 nm, or 50 nm to 60 nm.
  • a block coating 130 may be applied in a single layer or in multiple layers. The multiple layers may have the same or different compositions.
  • Glass substrate 110 having a discrete region(s) with a block coating 130 applied thereto may then be exposed to an ion-exchange process, for example, exposed to an ion- exchange bath, so as to ion-exchange ion-exchangeable regions of glass substrate 110 surrounding region(s) coated with block coating 130.
  • This asymmetric ion-exchange results in local deformation of glass substrate 110 and formation of a surface feature 120 at the location(s) of block coating 130.
  • glass substrate 110 may be simultaneously shaped while being ion-exchanged. This can reduce manufacturing costs and increase efficiency by eliminating the need for a chemical strengthening process and a separate glass shaping process.
  • asymmetric ion-exchange may result in a non- uniform strain, which creates a controlled bending and designed shape.
  • a discrete portion of second surface 114 of glass substrate 110 is coated with a block coating 130 and surrounding region 140 of second surface 114 is uncoated.
  • first surface 112 of glass substrate 110 is also not coated with a block coating.
  • concave surface region 124 is formed at the location of block coating 130 and convex surface region 122 at first surface 112 is formed opposite the discrete portion of second surface 114 coated with block coating 130.
  • the concentration of the same alkali oxide will be different from areas of second surface surrounding block coating 130. It is expected that the concentration of the alkali metal oxide under the block coating 130 is unchanged relative to the base composition of glass substrate.
  • the concentration of the alkali metal oxide may be zero or less than 0.1 mol% for a base glass composition devoid of the alkali metal oxide, or including only trace amounts the alkali metal oxide.
  • asymmetric stress may be achieved by heat treatment of glass substrate 110.
  • heat treatment can be performed using a laser beam, for example a CO2 laser, or using a hot wire.
  • one or more discrete regions of first surface 112 and/or second surface 114 of glass substrate 110 are heat treated after glass substrate 110 is exposed to an ion-exchange process.
  • the heat treatment may relax the compressive stresses created by the ion-exchange process, which results in the formation of a surface feature 120.
  • Such post-ion-exchange heat treatment of a discrete region may relax compressive stresses by heating the region to a temperature above the annealing point of the glass composition from which glass substrate 110 is made.
  • one or more discrete regions of first surface 112 and/or second surface 114 of glass substrate 110 are heat treated prior to exposing glass substrate 110 to an ion-exchange process.
  • a 3D shape change may occur during an ion- exchange process.
  • the heat treatment creates a difference in fictive temperature on a surface or between surfaces of glass substrate 110.
  • This fictive temperature difference can be used to create a stress asymmetry.
  • the change in fictive temperature results in different rates of ion diffusivity into glass substrate 110 during ion- exchange.
  • the resultant stress differences due to the different ion diffusivities can result in local shape change based on the thickness of the glass and amount of asymmetry in the glass.
  • FIG 4 shows a curved glass article 400 according to some embodiments.
  • Asymmetric ion- exchange may be used to form a bend or a curve in a glass substrate 410.
  • the curve may be a simple curve, such that the curve has a single radius of curvature, or the curve may be a complex curve in which the glass substrate has multiple radii of curvature.
  • glass substrate 410 may be formed in a sinusoidal or S-shape.
  • a surface of glass substrate 410 may have a concave surface region and also a convex surface region in some embodiments.
  • Curved or bent substrates may be formed using a block coating, a heat treatment as described herein, or a combination thereof.
  • a block coating was applied to a second surface 414 of glass substrate 410, which forms the concave surface of glass substrate 410. Strong stress asymmetry from an ion- exchange process made thin glass substrate 410 bend into a rolled shape with a first surface 412 of glass substrate rolled over itself.
  • Glass substrate 410 had a thickness of about 67 microns, a length of about 180 mm, and a width of about 105.2 mm.
  • the block coating was aluminum oxynitride (AION).
  • the block coating was deposited using ion assisted sputtering with the following coating parameters: 1-hour deposition, 4 kW (kilowatt) power to the aluminum target, 70 standard cubic centimeters per minute (seem) argon to the magnetron, 10 seem argon to the ion gun, 2 seem O2 to the ion gun, and 44 seem N2 to the ion gun.
  • the thickness of the deposited block coating was about 100 nm.
  • Glass substrate 410 had a composition consistent with Composition 1 in Table 1. Glass substrate 410 was ion-exchanged at 410 °C for 45 minutes in a 100% NKO3 molten salt bath.
  • Glass article 500 has a thickness of 200 pm, a length of 180 mm, and a width of 105. 2 mm.
  • Glass article 550 has a thickness of 100 pm, a length of 160 mm, and a width of 100 mm.
  • a block coating of AION was applied to a second surface 502, 552 of each glass article 500, 550 to create a concave surface of glass articles 500, 550 after ion-exchange.
  • the block coating was deposited using ion assisted sputtering with the following coating parameters: 1-hour deposition, 4 kW power to the aluminum target, 70 seem of argon to the magnetron, 10 seem of argon to the ion gun, 2 seem O2 to the ion gun, and 44 seem N2 to the ion gun.
  • the thickness of the deposited block coating on both articles 500, 550 was about 100 nm.
  • Glass article 500 having a greater thickness resulted in a greater radius of curvature than glass article 550 having a smaller thickness.
  • Glass articles 500, 550 had a composition consistent with Composition 1 in Table 1.
  • Glass articles 500, 550 were ion- exchanged at 410 °C for 45 minutes in a 100% NKO3 molten salt bath.
  • a curved or bent glass article may be formed by creating a bend in a glass substrate.
  • FIGS. 6 and 7 show a glass article 600 having a bend 620 according to some embodiments.
  • Glass article 600 includes a glass substrate 610 with a thickness of about 67 pm and glass composition consistent with Composition 1 in Table 1.
  • Glass substrate 610 was subjected to an ion-exchange process to create a compressive stress region at first surface 612, a compressive stress region at surface 614, and a central tension region between the two compressive stress regions.
  • the ion-exchange process included ion-exchanging glass substrate 610 at 410 °C for 45 minutes in a 100% NKO3 molten salt bath.
  • the initial compressive stress at surfaces 612 and 614 of glass substrates was about 845 MPa and depth of layer (DOL) of 16 pm.
  • DOL refers to the depth within a glass article at which an ion of a metal oxide diffuses into the glass article where the concentration of the ion reaches a minimum value.
  • second surface 614 of glass substrate 610 was heated at a center of glass substrate 610 along a width thereof with a multi-pass CO2 laser.
  • the CO2 laser had a diameter in a range from 0.5 mm to 20 mm and a power in a range of 1 watt to 1000 watts. Heating of glass substrate 610 along the center line using the CO2 laser resulted in formation of bend 620 along the center line that was heated by the laser. The heating caused relaxation of the compressive stress at second surface 614, resulting in an asymmetric stress concentration and a shape change.
  • FIGS. 8-11 illustrate the FEA model and results of the model.
  • Glass substrates having a length of 5 mm, a width of 5 mm, and a thickness of 50 pm, 75 pm, and 500 pm were modeled.
  • the glass substrates were modeled as having a composition consistent with Composition 1 in Table 1 below, and the material properties of a glass with this composition.
  • FIG. 8 illustrates a modeled glass substrate 810 with a region 820 having a diameter of 200 pm on a second surface 814 blocked from ion-exchange. The remainder of the area for second surface 814 was modeled as being unblocked by a block coating. Additionally, a first surface 812 of modeled glass substrate opposite second surface 814 was modeled as being unblocked by a block coating.
  • FIG. 9 shows a graph 900 of the modeled compressive stress profiles applied to each of the modeled glass substrates 810.
  • the stress profile included a compressive stress of about 855 MPa at first surface 812 and second surface 814 and a depth of compression (DOC) of about 12 pm for first surface 812 and second surface 814.
  • the stress profile was applied to first surface 812 and second surface 814, with the expectation that the stress profile was not applied to region 820 at second surface 814 (because this region is modeled as not ion-exchanged).
  • the resulting modeled glass article 800 for the 75-micron thick modeled glass substrate 810 with the stress profile applied is shown in FIG. 10.
  • Modeled glass article 800 displayed bending away from the region 820 modeled as being blocked with a block coating (i.e., non-ion-exchanged) thereby resulting in a surface feature including a recess at second surface 814 and a protrusion at first surface 812 opposite second surface 814.
  • a block coating i.e., non-ion-exchanged
  • the asymmetrical stress effect may extend beyond a blocked region.
  • the effective diameter of a surface feature may be larger than the diameter of the blocked region.
  • the size of the effective diameter of a surface feature compared to the diameter of a blocked region can depend on various variables, including the thickness of a glass substrate and the ion-exchange conditions.
  • FIG. 11 shows a graph 1100 of out-of-plane-deformation (i.e., peak height) for each modeled glass substrate 810.
  • Each modeled glass substrate 810 demonstrated bending at the location modeled as being blocked by a block coating resulting in a surface feature as described herein.
  • the amount of deformation depends in part on the thickness of the modeled glass substrate 810.
  • the 50-micron thick glass substrate had a maximum out-of-plane-deformation of about 3 microns and an effective diameter of about 5000 microns.
  • the 75-micron thick modeled glass substrate had a maximum out-of-plane-deformation of about 1.5 microns and an effective diameter of about 5000 microns.
  • the 500-micron thick glass substrate had a maximum out-of-plane- deformation of less than 0.5 microns and an effective diameter of about 200 microns.
  • the amount of out-of-plane-deformation increases, as well as the effective diameter of a surface feature. This results in surface features having greater peak heights.
  • glass thickness is a factor in the amount of out-of-plane deformation exhibited by a glass article after asymmetric ion-exchange, it is understood that other factors affect the degree of out-of-plane deformation, for example the glass composition, the diameter of a block coated region, and the conditions of an ion- exchange process, for example the amount of time glass substrate is exposed to ion- exchange bath.
  • FIGS. 12A and 12B show optical microscope images 1200 and 1250 of two surface features on a glass article according to some embodiments.
  • the glass article had a thickness of 50 microns and a composition consistent with Composition 1 in Table 1.
  • Image 1200 shows a convex surface region of a surface feature 1202 having an effective diameter of about 120 microns.
  • Image 1250 shows a concave surface region of a surface feature 1252 having an effective diameter of about 500 microns.
  • the glass article was ion-exchanged at about 420°C for 35 minutes in 100% KNO3 salt solution.
  • glass is meant to include any material made at least partially of glass, including glass and glass-ceramics.
  • Glass-ceramics include materials produced through controlled crystallization of glass. In embodiments, glass-ceramics have about 30% to about 90% crystallinity.
  • Non-limiting examples of glass ceramic systems that may be used include LhO x AkCb x nSiCh (i.e. LAS system), MgO c AI2O3 x nSiCh (i.e. MAS system), and ZnO x AI2O3 x nSiCL (i.e. ZAS system).
  • suitable glass examples include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass.
  • the glass may either include lithia (lithium oxide) or be free of lithia.
  • the substrate may include crystalline substrates, for example glass ceramic substrates (which may be strengthened or non-strengthened) or may include a single crystal structure, for example sapphire.
  • the substrate includes an amorphous base (e.g., glass) and a crystalline cladding (e.g., sapphire layer, a polycrystalline alumina layer and/or or a spinel (MgAhC ⁇ ) layer).
  • amorphous base e.g., glass
  • a crystalline cladding e.g., sapphire layer, a polycrystalline alumina layer and/or or a spinel (MgAhC ⁇ ) layer.
  • the glass composition for a glass substrate discussed herein may include 40 mol% to 90 mol% S1O2 (silicon oxide).
  • the glass composition may include 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, or 90 mol% SiC , or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 55 mol% to 70 mol% SiC .
  • the glass composition may include 57.43 mol% to 68.95 mol% SiC .
  • the glass composition for a glass substrate discussed herein may include 1 mol% to 10 mol% B2O3 (boron oxide).
  • the glass composition may include 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol% ,7 mol%, 8 mol%, 9 mol%, or 10 mol% B2O3, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 3 mol% to 6 mol% B2O3.
  • the glass composition may include 3.86 mol% to 5.11 mol% B2O3.
  • the glass composition may not include B2O3.
  • the glass composition for a glass substrate discussed herein may include 5 mol% to 30 mol% AI2O3 (aluminum oxide).
  • the glass composition may include 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol% AI2O3, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 10 mol% to 20 mol% AI2O3.
  • the glass composition may include 10.27 mol% to 16.10 mol% AI2O3.
  • the glass composition for a glass substrate discussed herein may include 1 mol% to 10 mol% P2O5 (phosphorus oxide).
  • the glass composition may include 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol% P2O5, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 2 mol% to 7 mol% P2O5.
  • the glass composition may include 2.47 mol% to 6.54 mol% P2O5.
  • the glass composition may not include P2O5.
  • the glass composition for a glass substrate discussed herein may include 5 mol% to 30 mol% Na 2 0 (sodium oxide). In some embodiments, the glass composition may include 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol% Na20, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the glass composition may include 10 mol% to 20 mol% Na 2 0. In some embodiments, the glass composition may include 10.82 mol% to 17.05 mol% Na 2 0.
  • the glass composition for a glass substrate discussed herein may include 0.01 mol% to 0.05 mol% K2O (potassium oxide).
  • the glass composition may include 0.01 mol%, 0.02 mol%, 0.03 mol%, 0.04 mol%, or 0.05 mol% K2O, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 0.01 mol% K2O. In some embodiments, the glass composition may not include K2O.
  • the glass composition for a glass substrate discussed herein may include 1 mol% to 10 mol% MgO (magnesium oxide).
  • the glass composition may include 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol% MgO, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 2 mol% to 6 mol% MgO.
  • the glass composition may include 2.33 mol% to 5.36 mol% MgO.
  • the glass composition may not include MgO.
  • the glass composition for a glass substrate discussed herein may include 0.01 mol% to 0.1 mol% CaO (calcium oxide).
  • the glass composition may include 0.01 mol%, 0.02 mol%, 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.06 mol%, 0.07 mol%, 0.08 mol%, 0.09 mol%, or 0.1 mol% CaO, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 0.03 mol% to 0.06 mol% CaO.
  • the glass composition for glass layers discussed herein may include 0.01 mol% to 5 mol% CaO. In some embodiments, the glass composition may include 0.01 mol%, 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, or 5 mol% CaO, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the glass composition may not include CaO.
  • the glass composition for a glass substrate discussed herein may include 0.01 mol% to 0.05 mol% Fe 2 0 3 (iron oxide).
  • the glass composition may include 0.01 mol%, 0.02 mol%, 0.03 mol%, 0.04 mol%, or 0.05 mol% FeiCb, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 0.01 mol% Fe 2 C> 3. In some embodiments, the glass composition may not include Fe 2 C> 3.
  • the glass composition for a glass substrate discussed herein may include 0.5 mol% to 2 mol% ZnO (zinc oxide). In some embodiments, the glass composition may include 0.5 mol%, 1 mol%, 1.5 mol%, or 2 mol% ZnO, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the glass composition may include 1.16 mol% ZnO. In some embodiments, the glass composition may not include ZnO.
  • the glass composition for a glass substrate discussed herein may include 1 mol% to 10 mol% LhO (lithium oxide).
  • the glass composition may include 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol% LhO, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 5 mol% to 7 mol% LhO.
  • the glass composition may include 6.19 mol% LhO.
  • the glass composition may not include LhO.
  • the glass composition for glass layers discussed herein may include 0.01 mol% to 0.3 mol% SnC (tin oxide).
  • the glass composition may include 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.15 mol%, 0.2 mol%, 0.25 mol%, or 0.3 mol%, SnCh, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • the glass composition may include 0.01 mol% to 0.2 mol% SnC .
  • the glass composition may include 0.04 mol% to 0.17 mol% SnC .
  • the glass composition for a glass substrate discussed herein may be a composition including a value for R2O (alkali metal oxide(s)) + RO (alkali earth metal oxide(s)) in a range of 10 mol% to 30 mol%.
  • R2O + RO may be 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, or a mol% within any range having any two of these values as endpoints, inclusive of the endpoints.
  • R2O + RO may be in a range of 15 mol% to 25 mol%.
  • R2O + RO may be in a range of 16.01 mol% to 20.61 mol%.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • the term “about” refers to a value that is within ⁇ 10% of the value stated. For example, about 3 wt% can include any number between 2.7 wt% and 3.3 wt%.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Articles en verre ayant subi un échange d'ions comprenant une ou plusieurs caractéristiques de surface ayant une région de surface convexe au niveau d'une première surface de l'article en verre et une région de surface concave au niveau d'une seconde surface de l'article en verre opposée à la région de surface convexe. Un ou plusieurs procédés d'échange d'ions peuvent être utilisés pour créer la(les) caractéristique(s) de surface. Une concentration d'un oxyde de métal alcalin dans la composition de verre de l'article en verre mesurée dans la région de surface convexe peut être différente d'une concentration de l'oxyde de métal alcalin dans la composition de verre mesurée dans la région de surface concave.
PCT/US2020/057840 2019-11-25 2020-10-29 Articles en verre ayant des caractéristiques de surface et leurs procédés de fabrication Ceased WO2021108069A1 (fr)

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US62/939,995 2019-11-25

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013031851A1 (fr) * 2011-08-30 2013-03-07 エルシード株式会社 Procédé de production par gravure à sec d'un substrat en verre portant un film concave-convexe, substrat en verre portant un film concave-convexe, pile solaire et son procédé de production
WO2015016361A1 (fr) * 2013-08-01 2015-02-05 積水化学工業株式会社 Intercalaire pour verre stratifié et verre stratifié
US20180151408A1 (en) * 2015-07-24 2018-05-31 Asahi Glass Company, Limited Glass substrate, laminated substrate, laminated substrate manufacturing method, laminate, package, and glass substrate manufacturing method
US10035331B2 (en) * 2011-06-24 2018-07-31 Corning Incorporated Light-weight hybrid glass laminates
US10286631B2 (en) * 2015-06-03 2019-05-14 Precision Glass Bending Corporation Bent, veneer-encapsulated heat-treated safety glass panels and methods of manufacture

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10035331B2 (en) * 2011-06-24 2018-07-31 Corning Incorporated Light-weight hybrid glass laminates
WO2013031851A1 (fr) * 2011-08-30 2013-03-07 エルシード株式会社 Procédé de production par gravure à sec d'un substrat en verre portant un film concave-convexe, substrat en verre portant un film concave-convexe, pile solaire et son procédé de production
WO2015016361A1 (fr) * 2013-08-01 2015-02-05 積水化学工業株式会社 Intercalaire pour verre stratifié et verre stratifié
US10286631B2 (en) * 2015-06-03 2019-05-14 Precision Glass Bending Corporation Bent, veneer-encapsulated heat-treated safety glass panels and methods of manufacture
US20180151408A1 (en) * 2015-07-24 2018-05-31 Asahi Glass Company, Limited Glass substrate, laminated substrate, laminated substrate manufacturing method, laminate, package, and glass substrate manufacturing method

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