TWI806928B - Hydrogen-containing glass-based articles with high indentation cracking threshold - Google Patents

Abstract

Glass-based articles that include a hydrogen-containing layer extending from the surface of the article to a depth of layer. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration to the depth of layer. The glass-based articles exhibit a high Vickers indentation cracking threshold. Glass compositions that are selected to promote the formation of the hydrogen-containing layer and methods of forming the glass-based article are also provided.

Description

Hydrogen-containing glass substrate objects with high dent cracking threshold

Related applications

This application claims priority to U.S. Provisional Application No. 62/587,872, filed November 17, 2017, the contents of which are believed to be incorporated herein by reference in its entirety, and to NL Application No. 2020896, filed May 8, 2018, which is believed to be incorporated herein by reference in its entirety.

The present disclosure relates to glass-based articles containing hydrogen, glass compositions used to form the glass-based articles, and methods of forming the glass-based articles.

Portable electronics such as smartphones, tablets, and wearable elements such as watches and fitness trackers continue to become smaller and more complex. Accordingly, the materials conventionally used on at least one outer surface of such portable electronic components continue to become more complex. For example, as portable electronic components have become smaller and thinner to meet consumer demands, display covers and housings used in such portable electronic components have also become smaller and thinner, resulting in higher performance requirements for the materials used to form these components.

Therefore, there is a need for materials that exhibit higher performance, such as damage resistance, for use in portable electronic components.

In aspect (1), a glass substrate article is provided. The glass-based object comprises: SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ ; and a hydrogen-containing layer extending from a surface of the glass-based object to a depth of one layer. The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of the layer, and the depth of the layer is greater than 5 μm.

In aspect (2), there is provided the glass substrate article of aspect (1), wherein the glass substrate article has a Vickers crack initiation threshold of greater than or equal to 1 kgf.

In aspect (3), there is provided the glass substrate article of aspect (1) or (2), wherein the depth of the layer is greater than or equal to 10 μm.

In aspect (4), there is provided the glass-based article of any one of aspects (1) to (3), wherein the maximum hydrogen concentration is at the surface of the glass-based article.

In aspect (5), there is provided the glass-based object of any one of aspects (1) to (4), further comprising at least one of Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, and Rb ₂ O.

In aspect (6), there is provided the glass-based article of any one of aspects (1) to (5), further comprising K ₂ O.

In aspect (7), there is provided the glass-based article of any one of aspects (1) to (6), wherein the center of the glass-based article comprises: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; and greater than or equal to 6 mol % to less than or equal to Equivalent to 25 mol% K ₂ O.

In aspect (8), there is provided the glass-based article of any one of aspects (1) to (6), wherein the center of the glass-based article comprises: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 4 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; and greater than or equal to 11 mol % to Less than or equal to 25 mol% K ₂ O.

In aspect (9), there is provided the glass-based article of any one of aspects (1) to (6), wherein the center of the glass-based article comprises: greater than or equal to 55 mol % to less than or equal to 69 mol % of SiO ₂ ; greater than or equal to 5 mol % to less than or equal to 15 mol % of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 10 mol % to Less than or equal to 20 mol% K ₂ O.

In aspect (10), there is provided the glass-based article of any one of aspects (7) to (9), wherein the center of the glass-based article comprises: greater than or equal to 0 mol % to less than or equal to 10 mol % of Cs ₂ O; and greater than or equal to 0 mol % to less than or equal to 10 mol % of Rb ₂ O.

In aspect (11), there is provided the glass-based article of any one of aspects (1) to (10), wherein the glass-based article is substantially free of at least one of lithium and sodium.

In aspect (12), there is provided the glass substrate article of any one of aspects (1) to (11), further comprising a compressive stress layer extending from a surface of the glass substrate article into the glass substrate article to a compression depth.

In aspect (13), there is provided the glass substrate article of aspect (12), wherein the compressive stress layer comprises a compressive stress of at least about 100 MPa, and the depth of compression is at least about 75 μm.

In aspect (14), a consumer electronic product is provided. The consumer electronic product includes: a housing including a front surface, a rear surface, and side surfaces; electrical components at least partially within the housing, the electrical components including at least a controller, a memory, and a display at or adjacent to the front surface of the housing; and a cover substrate disposed on the display. At least a part of at least one of the housing or the cover substrate includes the glass-based article of any one of aspects (1) to (13).

In aspect (15), a glass is provided. The glass comprises: greater than or equal to 45 mol% to less than or equal to 75 mol% of SiO ₂ ; greater than or equal to 3 mol% to less than or equal to 20 mol% of Al ₂ O ₃ ; greater than or equal to 6 mol% to less than or equal to 15 mol% of P ₂ O ₅ ; and greater than or equal to 6 mol% to less than or equal to 25 mol% of K ₂ O.

In aspect (16), the glass of aspect (15) is provided, comprising: SiO ₂ of greater than or equal to 55 mol % to less than or equal to 69 mol %; greater than or equal to 5 mol % to less than or equal to 15 mol % of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 10 mol % to less than or equal to 20 mol % of K ₂ O.

In aspect (17), there is provided the glass of aspect (15) or (16), further comprising: greater than or equal to 0 mol% to less than or equal to 10 mol% of Cs ₂ O; and greater than or equal to 0 mol% to less than or equal to 10 mol% of Rb ₂ O.

In aspect (18), there is provided the glass of any one of aspects (15) to (17), wherein the glass is substantially free of lithium.

In aspect (19), there is provided the glass of any one of aspects (15) to (18), wherein the glass is substantially sodium-free.

In aspect (20), there is provided the glass of any one of aspects (15) to (19), comprising: SiO ₂ of greater than or equal to 58 mol % to less than or equal to 63 mol %; greater than or equal to 7 mol % to less than or equal to 14 mol % of Al ₂ O ₃ ; greater than or equal to 7 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 15 mol % to less than or equal to 20 mol % K ₂ O.

In aspect (21), there is provided the glass of any one of aspects (15) to (20), wherein the glass has a Vickers crack initiation threshold of 5 kgf or greater.

In aspect (22), there is provided the glass of any one of aspects (15) to (21), further comprising at least one of Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, and Rb ₂ O.

In aspect (23), a glass is provided. The glass comprises: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 4 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 25 mol % of K ₂ O.

In aspect (24), the glass of aspect (23) is provided, comprising: greater than or equal to 55 mol % to less than or equal to 69 mol % of SiO ₂ ; greater than or equal to 5 mol % to less than or equal to 15 mol % of Al ₂ O ₃ ; greater than or equal to 5 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 20 mol % of K ₂ O.

In aspect (25), there is provided the glass of aspect (23) or (24), further comprising: greater than or equal to 0 mol% to less than or equal to 10 mol% of Cs ₂ O; and greater than or equal to 0 mol% to less than or equal to 10 mol% of Rb ₂ O.

In aspect (26), there is provided the glass of any one of aspects (23) to (25), wherein the glass is substantially free of lithium.

In aspect (27), there is provided the glass of any one of aspects (23) to (26), wherein the glass is substantially sodium-free.

In aspect (28), there is provided the glass of any one of aspects (23) to (27), comprising: greater than or equal to 58 mol % to less than or equal to 63 mol % of SiO ₂ ; greater than or equal to 7 mol % to less than or equal to 14 mol % of Al ₂ O ₃ ; greater than or equal to 7 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 15 mol % to less than or equal to 20 mol % K ₂ O.

In aspect (29), there is provided the glass of any one of aspects (23) to (28), wherein the glass has a Vickers cracking initiation threshold of greater than or equal to 5 kgf.

In aspect (30), the glass of any one of aspects (23) to (29) is provided, further comprising at least one of Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, and Rb ₂ O.

In aspect (31), a method is provided. The method includes exposing a glass-based substrate to an environment having a relative humidity greater than or equal to 75% to form a glass-based article having a hydrogen-containing layer extending from a surface of the glass-based article to a depth of one layer. The glass base substrate includes SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ . The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of the layer, and the depth of the layer is greater than 5 μm.

In aspect (32), there is provided the method of aspect (31), wherein the glass base substrate has a composition comprising one of: greater than or equal to 55 mol % to less than or equal to 69 mol % of SiO ₂ ; greater than or equal to 5 mol % to less than or equal to 15 mol % of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; and greater than or equal to 10 mol % to less than or equal to 20 mol % ear % K ₂ O.

In aspect (33), there is provided the method of aspect (31), wherein the glass base substrate has a composition comprising one of: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 4 mol % to less than or equal to 15 mol % P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 25 mol % ear % K ₂ O.

In aspect (34), there is provided the method of aspect (31), wherein the glass base substrate has a composition comprising one of: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; and greater than or equal to 6 mol % to less than or equal to 25 mol % % of K ₂ O.

In aspect (35), there is provided the method of any one of aspects (31) to (34), wherein the glass base substrate further comprises: greater than or equal to 0 mol % to less than or equal to 10 mol % of Cs ₂ O; and greater than or equal to 0 mol % to less than or equal to 10 mol % of Rb ₂ O.

In aspect (36), the method of any one of aspects (31) to (35) is provided, further comprising at least one of Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, and Rb ₂ O.

In aspect (37), there is provided the method of any one of aspects (31) to (36), wherein the glass base substrate is substantially free of at least one of lithium and sodium.

In aspect (38), there is provided the method of any one of aspects (31 ) to (37), wherein the exposing occurs at a temperature of greater than or equal to 70°C.

In aspect (39), there is provided the method of any one of aspects (31 ) to (38), wherein the glass substrate article has a Vickers crack initiation threshold greater than or equal to 1 kgf.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, drawings, and appended claims.

In the following description, like reference characters indicate like or corresponding parts throughout the several views shown in the drawings. It should also be understood that terms such as "top", "bottom", "outwardly", "inwardly" and the like are words of convenience and should not be construed as terms of limitation unless otherwise specified. Unless otherwise specified, the recitation of a range of values includes the upper and lower limits of that range, and any subranges therebetween. As used herein, the indefinite articles "a" (a, an) and the corresponding definite article "the" (the) mean "at least one" or "one or more", unless specified otherwise. It should also be understood that the various features disclosed in the specification and drawings can be used in any and all combinations.

As used herein, the term "glass substrate" is used in its broadest sense to include any object made entirely or partially of glass, including glass ceramics (which include a crystalline phase and a residual amorphous glass phase). Unless otherwise specified, all compositions of glasses described herein are expressed in molar percentages (mol %), and compositions are provided on an oxide basis. All temperatures are expressed in degrees Celsius (°C) unless otherwise specified.

Note that the terms "substantially" and "about" may be used herein to denote an inherent degree of uncertainty that may be attributable to any quantitative comparison, value, measurement or other representation. These terms are also used herein to denote the degree to which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. For example, a "substantially _K2O -free" glass is a glass in which _K2O has not been actively added or batched into the glass and may be present as a contaminant in very small amounts, such as in amounts less than about 0.01 mole percent. As used herein, when the term "about" is used to modify a value, the exact value is also revealed. For example, the term "greater than about 10 mol%" also discloses "greater than or equal to about 10 mol%".

Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying Examples and Drawings.

The glass-based article includes a hydrogen-containing layer extending from a surface of the article to a depth of one layer. The hydrogen-containing layer includes a hydrogen concentration from a maximum hydrogen concentration to a decreasing depth of the layer of the glass substrate article. In some embodiments, the maximum hydrogen concentration can be at the surface of the glass substrate article. The glass-based article exhibits a high Vickers dent cracking threshold (eg, greater than or equal to 1 kgf) without the use of conventional strengthening methods (eg, ion exchange of a pair of alkali ions or thermal tempering). A high Vickers dent cracking threshold exhibited by glass-based articles indicates high resistance to damage.

Glass-based articles can be formed by exposing a glass-based substrate to an environment containing water vapor, thereby allowing hydrogen species to penetrate the glass-based substrate and form a glass-based article having a hydrogen-containing layer. As utilized herein, hydrogen species include molecular water, hydroxyl groups, hydrogen ions, and hydronium ions. The composition of the glass-based substrates can be selected to facilitate the interdiffusion of hydrogen species into the glass. As used herein, the term "glass-based substrate" refers to a precursor used to form a glass-based article including a hydrogen-containing layer prior to exposure to a water vapor-containing environment. Similarly, the term "glass-based article" refers to articles that are exposed after including a hydrogen-containing layer.

A representative cross-section of a glass substrate article 100 according to some embodiments is depicted in FIG. 1 . The glass substrate article 100 has a thickness t that extends between a first surface 110 and a second surface 112 . The first hydrogen-containing layer 120 extends from the first surface 110 to a first layer depth, wherein the first layer depth has a depth d1 measured from the first surface 110 into the glass substrate object 100 . The second hydrogen-containing layer 122 extends from the second surface 112 to a second layer depth, wherein the second layer depth has a depth d2 measured from the second surface 112 into the glass substrate article 100 . A region 130 free of hydrogen-added species exists between the first layer depth and the second layer depth.

The hydrogen-containing layer of the glass-based object may have a depth of layer (DOL) greater than 5 μm. In some embodiments, the depth of the layer may be greater than or equal to 10 μm, such as, greater than or equal to 15 μm, greater than or equal to 20 μm, greater than or equal to 25 μm, greater than or equal to 30 μm, greater than or equal to 35 μm, greater than or equal to 40 μm, greater than or equal to 45 μm, greater than or equal to 50 μm, greater than or equal to 55 μm, greater than or equal to 60 μm, greater than or equal to 65 μm, greater than or Equal to 70 μm, greater than or equal to 75 μm, greater than or equal to 80 μm, greater than or equal to 85 μm, greater than or equal to 90 μm, greater than or equal to 95 μm, greater than or equal to 100 μm, greater than or equal to 105 μm, greater than or equal to 110 μm, greater than or equal to 115 μm, greater than or equal to 120 μm, greater than or equal to 125 μm, greater than or equal to 130 μm, greater or equal to 135 μm, greater than or equal to 140 μm, greater than or equal to 145 μm, greater than or equal to 150 μm, greater than or equal to 155 μm, greater than or equal to 160 μm, greater than or equal to 165 μm, greater than or equal to 170 μm, greater than or equal to 175 μm, greater than or equal to 180 μm, greater than or equal to 185 μm, greater than or equal to 190 μm, greater than or equal to 1 95 μm, greater than or equal to 200 μm or greater. In some embodiments, the depth of the layer may be from greater than or equal to 5 μm to less than or equal to 205 μm, such as from greater than or equal to 10 μm to less than or equal to 200 μm, from greater than or equal to 15 μm to less than or equal to 200 μm, from greater than or equal to 20 μm to less than or equal to 195 μm, from greater than or equal to 25 μm to less than or equal to 190 μm, from greater than or equal to 30 μm to less than or equal to 185 μm, from 35 μm to 180 μm, from 40 μm to 175 μm, from 45 μm to 170 μm, from 50 μm to 165 μm, from 55 μm to 160 μm, from 60 μm to 155 μm, from greater than or equal to 65 μm to less than or equal to 150 μm, from greater than or equal to 70 μm to less than or equal to 145 μm, from greater than or equal to 75 μm to less than or equal to 140 μm, from greater than or equal to 80 μm to less than or equal to 135 μm, from greater than or equal to 85 μm to less than or equal to 130 μm, from greater than or equal to 90 μm to less than or equal to 125 μm , from greater than or equal to 95 μm to less than or equal to 120 μm, from greater than or equal to 100 μm to less than or equal to 115 μm, from greater than or equal to 105 μm to less than or equal to 110 μm, or any subrange formed by any of these endpoints. In general, the depth of layer exhibited by glass-based objects is greater than that which can be produced by exposure to the surrounding environment.

The hydrogen-containing layer of the glass-based article may have a depth of layer (DOL) greater than 0.005 t , where t is the thickness of the glass-based article.在一些實施例中，該層深度可大於或等於0.010 t ，諸如，大於或等於0.015 t 、大於或等於0.020 t 、大於或等於0.025 t 、大於或等於0.030 t 、大於或等於0.035 t 、大於或等於0.040 t 、大於或等於0.045 t 、大於或等於0.050 t 、大於或等於0.055 t 、大於或等於0.060 t 、大於或等於0.065 t 、大於或等於0.070 t 、大於或等於0.075 t 、大於或等於0.080 t 、大於或等於0.085 t 、大於或等於0.090 t 、大於或等於0.095 t 、大於或等於0.10 t 、大於或等於0.15 t 、大於或等於0.20 t或更大。在一些實施例中，DOL可自大於0.005 t至小於或等於0.205 t ，諸如，自大於或等於0.010 t至小於或等於0.200 t 、自大於或等於0.015 t至小於或等於0.195 t 、自大於或等於0.020 t至小於或等於0.190 t 、自大於或等於0.025 t至小於或等於0.185 t 、自大於或等於0.030 t至小於或等於0.180 t 、自大於或等於0.035 t至小於或等於0.175 t 、自大於或等於0.040 t至小於或等於0.170 t 、自大於或等於0.045 t至小於或等於0.165 t 、自大於或等於0.050 t至小於或等於0.160 t 、自大於或等於0.055 t至小於或等於0.155 t 、自大於或等於0.060 t至小於或等於0.150 t 、自大於或等於0.065 t至小於或等於0.145 t 、自大於或等於0.070 t至小於或等於0.140 t 、自大於或等於0.075 t至小於或等於0.135 t 、自大於或等於0.080 t至小於或等於0.130 t 、自大於或等於0.085 t至小於或等於0.125 t 、自大於或等於0.090 t至小於或等於0.120 t 、自大於或等於0.095 t至小於或等於0.115 t 、自大於或等於0.100 t至小於或等於0.110 t或由此等端點中之任何者形成之任何子範圍。

Layer depth and hydrogen concentration are measured by secondary ion mass spectrometry (SIMS) techniques known in the art. The SIMS technique is capable of measuring the hydrogen concentration at a given depth, but is not capable of distinguishing the hydrogen species present in glass substrate objects. For this reason, all hydrogen species contribute to the hydrogen concentration measured by SIMS. As used herein, depth of layer (DOL) refers to the first depth below the surface of a glass substrate article at which the hydrogen concentration is equal to the hydrogen concentration at the center of the glass substrate article. This definition accounts for the hydrogen concentration of the glass base substrate before processing, such that the layer concentration refers to the depth of hydrogen added by the processing process. In fact, the hydrogen concentration at the center of the glass substrate article can be estimated from the hydrogen concentration at a depth from the surface of the glass substrate article where the hydrogen concentration becomes substantially constant, since the hydrogen concentration is not expected to change between this depth and the center of the glass substrate article. This estimation allows DOL to be determined without measuring the hydrogen concentration throughout the full depth of the glass substrate object.

In some embodiments, the entire thickness of the glass substrate article may be part of a hydrogen-containing layer. The glass-based article can be produced when the processing of the glass-based substrate is prolonged under sufficient conditions for hydrogen species to diffuse from each exposed surface to the center of the glass-based article. In some embodiments, with the surface of the glass-based article exposed to the same processing conditions, the minimum hydrogen concentration may be at half the thickness of the glass-based article such that the hydrogen-containing layers meet at the center of the glass-based article. In such embodiments, the DOL may be located at half the thickness of the glass substrate article. In some embodiments, the glass substrate articles may not include a region free of added hydrogen species. In some embodiments, the glass-based article may be processed in a wet environment such that the concentration of added hydrogen species is uniform throughout the glass-based article and the hydrogen concentration does not vary with depth below the surface of the glass-based article. Glass-based objects according to these embodiments will not exhibit a DOL as defined herein because the hydrogen concentration at the center of the glass-based object will be equivalent to the hydrogen concentration at all other depths.

These glass substrate articles are highly resistant to Vickers dent cracking. High Vickers dent crack resistance imparts high damage resistance to glass substrate articles. Without wishing to be bound by any particular theory, the water content of the glass substrate article can reduce the local viscosity of the hydrogen-containing layer, allowing localized flow rather than cracking. Vickers dent cracking thresholds for glass-based objects are achieved without the use of conventional strengthening techniques such as exchange of large base ions for smaller base ions in the glass, thermal tempering, or lamination of glass layers with mismatched coefficients of thermal expansion. Glass substrate articles exhibiting a Vickers dent cracking threshold of 1 kgf or greater, such as 2 kgf or greater, 3 kgf or greater, 4 kgf or greater, 5 kgf or greater, 6 kgf or greater, 7 kgf or greater, 8 kgf or greater, 9 kgf or greater, 10 kgf or greater, 11 kgf or greater, 12 kgf or greater, 13 kgf or greater kgf, 14 kgf or more, 15 kgf or more, 16 kgf or more, 17 kgf or more, 18 kgf or more, 19 kgf or more, 20 kgf or more, 21 kgf or more, 22 kgf or more, 23 kgf or more, 24 kgf or more, 25 kgf or more, 26 kgf or more, or 26 kgf or more 27 kgf, greater than or equal to 28 kgf, greater than or equal to 29 kgf, greater than or equal to 30 kgf or greater. In some embodiments, the glass substrate article exhibits a Vickers dent cracking threshold from greater than or equal to 1 kgf to less than or equal to 30 kgf, such as from greater than or equal to 2 kgf to less than or equal to 29 kgf, from greater than or equal to 3 kgf to less than or equal to 28 kgf, from greater than or equal to 4 kgf to less than or equal to 27 kgf, from greater than or equal to 5 kgf to less than or equal to 26 kgf, from greater than or equal to 6 kgf to less than or equal to or equal to 25 kgf, from greater than or equal to 7 kgf to less than or equal to 24 kgf, from greater than or equal to 8 kgf to less than or equal to 23 kgf, from greater than or equal to 9 kgf to less than or equal to 22 kgf, from greater than or equal to 10 kgf to less than or equal to 21 kgf, from greater than or equal to 11 kgf to less than or equal to 20 kgf, from greater than or equal to 12 kgf to less than or equal to 19 kgf, from greater than or equal 13 kgf to less than or equal to 18 kgf, from greater than or equal to 14 kgf to less than or equal to 17 kgf, from greater than or equal to 15 kgf to less than or equal to 16 kgf, or any subrange formed by any of these endpoints.

The Vickers crack initiation threshold (or dent fracture threshold) was measured by Vickers dent measurement. The Vickers crack initiation threshold is a measure of the glass' resistance to dent damage. The test involved the use of a square-based pyramid-shaped diamond indenter with an angle between the faces of 136°, known as a Vickers indenter. The Vickers indenter is the same as that used in standard microhardness testing (as described in ASTM-E384-11). Select a minimum of five specimens representing glass types and/or samples of interest. For each sample, multiple sets of five indentations were introduced into the sample surface. Each set of five dents is introduced under a given load, with each individual dent separated by a minimum of 5 mm and not closer than 5 mm to a specimen edge. For test loads ≥ 2 kg, use an indenter loading/unloading rate of 50 kg/min. For test loads < 2 kg, use a rate of 5 kg/min. A dwell (ie, hold) time of 10 seconds at the target load was utilized. The machine maintains load control during the dwell period. After a period of at least 12 hours, examine the dents under reflected light using a compound microscope at 500X magnification. The presence or absence of intermediate/radial cracks (cracks extending from the dent along a plane perpendicular to the main plane of the article) or specimen fractures were then noted for each dent. Note that the formation of lateral cracks (cracks extending along a plane parallel to the main plane of the article) is not considered indicative of exhibiting threshold behavior, as the formation of medial/radial cracks or specimen fracture is of interest for this test. The sample threshold is defined as the midpoint of the lowest continuous dent load that includes greater than 50% of individual dents meeting the threshold. For example, if within an individual specimen, 2/5 (40%) of the dents induced at a 5 kg load exceeded the threshold and 3/5 (60%) of the dents induced at a 6 kg load exceeded the threshold, then the specimen threshold would be defined as greater than 5 kg. The range (lowest to highest) of all sample midpoints can also be reported for each sample. The pre-test, test and post-test environments were controlled to 23±2°C and 50±5% Rh to minimize changes in the fatigue (stress corrosion) behavior of the specimens.

Without wishing to be bound by any particular theory, the hydrogen-containing layer of the glass-based article may be the result of the interdiffusion of hydrogen species to ions contained in the composition of the glass-based substrate. Monovalent hydrogen-containing species, such as H ₃ O ⁺ and/or H ⁺ , can replace alkali ions contained in the composition of a glass-based substrate to form a glass-based article. The size of the alkali ions replaced by the hydrogen-containing species has an effect on the diffusivity of the hydrogen-containing species in the glass base substrate because larger alkali ions create larger void spaces that facilitate the interdiffusion mechanism. For example, hydronium ion (H ₃ O ⁺ ) has an ionic radius close to that of potassium and much larger than that of lithium. It was observed that the diffusivity of hydrogen-containing species in the glass base substrate was significantly higher by two orders of magnitude when the glass base substrate contained potassium than when the glass base substrate contained lithium. This observed behavior may also indicate that hydronium ions are the predominant monovalent hydrogen-containing species diffusing into the glass base substrate. The ionic radii for the alkali and hydronium ions are reported in Table I below. As shown in Table I, rubidium and cesium have significantly larger ionic radii than hydronium ions, which can lead to higher hydrogen diffusivity than that observed for potassium.

In some embodiments, the displacement of alkali ions in a glass base substrate with hydrogen ions can produce a compressive stress layer extending from the surface of the glass base article into the glass base article to a compressive depth. As used herein, depth of layer (DOC) means the depth at which stress in a glass substrate object changes from compression to tension. Therefore, the glass-based object also contains a tensile stress region with a maximum central tension (CT) such that the forces within the glass-based object are balanced. Without wishing to be bound by any theory, regions of compressive stress may be the result of the exchange of hydrogen-containing ions having an ionic radius greater than one of the ions they replace.

In some embodiments, the compressive stress layer may comprise a compressive stress of 100 MPa or greater, such as 105 MPa or greater, 110 MPa or greater, 115 MPa or greater, 120 MPa or greater, 125 MPa or greater, 130 MPa or greater, 135 MPa or greater, or greater. In some embodiments, the compressive stress layer may comprise a compressive stress ranging from greater than or equal to 100 MPa to less than or equal to 150 MPa, such as from greater than or equal to 105 MPa to less than or equal to 145 MPa, from greater than or equal to 110 MPa to less than or equal to 140 MPa, from greater than or equal to 115 MPa to less than or equal to 135 MPa, from greater than or equal to 120 MPa to less than or equal to 130 MPa, 125 MPa, or from these endpoints Any subrange formed by any of them.

In some embodiments, the DOC of the compressive stress layer may be greater than or equal to 75 MPa, such as, greater than or equal to 80 MPa, greater than or equal to 85 MPa, greater than or equal to 90 MPa, greater than or equal to 95 MPa, greater than or equal to 100 MPa, or greater. In some embodiments, the DOC of the compressive stress layer may be in a range from greater than or equal to 75 μm to less than or equal to 115 μm, such as from greater than or equal to 80 μm to less than or equal to 110 μm, from greater than or equal to 85 μm to less than or equal to 105 μm, from greater than or equal to 90 μm to less than or equal to 100 μm, 95 μm, or any subrange that may be formed from any of these endpoints.

In some embodiments, the glass-based article can have a DOC of 0.05 t or greater, where t is the thickness of the glass-based article, such as 0.06 t or greater, 0.07 t or greater, 0.08 t or greater, 0.09 t or greater, 0.10 t or greater, 0.11 t or greater, 0.12 t or greater, or greater.在一些實施例中，玻璃基底物件可具有自大於或等於0.05 t至小於或等於0.20 t之一DOC，諸如，自大於或等於0.06 t至小於或等於0.19 t 、自大於或等於0.07 t至小於或等於0.18 t 、自大於或等於0.08 t至小於或等於0.17 t 、自大於或等於0.09 t至小於或等於0.16 t 、自大於或等於0.10 t至小於或等於0.15 t 、自大於或等於0.11 t至小於或等於0.14 t 、自大於或等於0.12 t至小於或等於0.13 t或自此等端點中之任何者形成之任何子範圍。

In some embodiments, the CT of the glass substrate article may be greater than or equal to 10 MPa, such as, greater than or equal to 11 MPa, greater than or equal to 12 MPa, greater than or equal to 13 MPa, greater than or equal to 14 MPa, greater than or equal to 15 MPa, greater than or equal to 16 MPa, greater than or equal to 17 MPa, greater than or equal to 18 MPa, greater than or equal to 19 MPa, greater than or equal to 20 MPa, greater than or equal to 22 MPa, greater than or equal to, greater than or equal to 24 MPa, greater than or equal to 26 MPa, greater than or equal to 28 MPa, greater than or equal to 30 MPa, greater than or equal to 32 MPa or greater. In some embodiments, the CT of the glass substrate article can be from greater than or equal to 10 MPa to less than or equal to 35 MPa, such as from greater than or equal to 11 MPa to less than or equal to 34 MPa, from greater than or equal to 12 MPa to less than or equal to 33 MPa, from greater than or equal to 13 MPa to less than or equal to 32 MPa, from greater than or equal to 14 MPa to less than or equal to 32 MPa, from greater than or equal to 15 MPa to less than or equal to 31 MPa, from greater than or equal to 1 6 MPa to less than or equal to 30 MPa, from greater than or equal to 17 MPa to less than or equal to 28 MPa, from greater than or equal to 18 MPa to less than or equal to 26 MPa, from greater than or equal to 19 MPa to less than or equal to 24 MPa, from greater than or equal to 20 MPa to less than or equal to 22 MPa, or any subrange formed from any of these endpoints.

Compressive stress (including surface CS) was measured by a surface strain gauge using a commercially available instrument such as FSM-6000 (FSM) manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely on accurate measurements of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is also measured according to Procedure C (glass dish 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. DOC was measured by FSM. Maximum central tension (CT) values were measured using a scattered light polarizer (SCALP) known in the art.

Glass-based articles may be formed from glass-based substrates of any suitable composition. The composition of the glass-based substrate can be specifically selected to facilitate the diffusion of hydrogen-containing species so that glass-based articles including a hydrogen-containing layer can be efficiently formed. In some embodiments, the glass base substrate may have a composition including SiO ₂ , Al ₂ O ₃ , and P ₂ O ₅ . In some embodiments, the glass base substrate may additionally include an alkali metal oxide, such as at least one of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O. In some embodiments, the glass base substrate can be substantially free or free of at least one of lithium and sodium. In some embodiments, after diffusion of the hydrogen-containing species into the glass base substrate, the glass base article can have an overall composition that is substantially the same as that of the glass base substrate. In some embodiments, hydrogen species may not diffuse into the center of the glass substrate article. In other words, the center of the glass-based article was the area least affected by the water vapor treatment. For this reason, the center of the glass-based article may have a composition that is substantially the same or identical to that of the glass-based substrate prior to processing in an aqueous environment.

The glass base substrate can include any suitable amount of _SiO2 . _Si02 is the largest constituent, and thus, _Si02 is the main constituent of the glass network formed from the glass composition. If the concentration of _SiO2 in the glass composition is too high, the formability of the glass composition can be reduced because the higher concentration of _SiO2 increases the difficulty of melting the glass, which in turn adversely affects the formability of the glass.在一些實施例中，玻璃基底基板可包括自大於或等於45莫耳%至小於或等於75莫耳%之量的SiO ₂ ，諸如，自大於或等於46莫耳%至小於或等於74莫耳%、自大於或等於47莫耳%至小於或等於73莫耳%、自大於或等於48莫耳%至小於或等於72莫耳%、自大於或等於49莫耳%至小於或等於71莫耳%、自大於或等於50莫耳%至小於或等於70莫耳%、自大於或等於51莫耳%至小於或等於69莫耳%、自大於或等於52莫耳%至小於或等於68莫耳%、自大於或等於53莫耳%至小於或等於67莫耳%、自大於或等於54莫耳%至小於或等於66莫耳%、自大於或等於55莫耳%至小於或等於65莫耳%、自大於或等於56莫耳%至小於或等於64莫耳%、自大於或等於57莫耳%至小於或等於63莫耳%、自大於或等於58莫耳%至小於或等於62莫耳%、自大於或等於59莫耳%至小於或等於61莫耳%、60莫耳%或由此等端點中之任何者形成之任何子範圍。 In some embodiments, the glass base substrate can include _Si02 in an amount from greater than or equal to 55 mol % to less than or equal to 69 mol %, such as from greater than or equal to 58 mol % to less than or equal to 63 mol % or any subrange formed from any of these endpoints.

The glass-based substrate can include any suitable amount of Al ₂ O ₃ . Al ₂ O ₃ can act as a glass network former, similar to SiO ₂ . Al ₂ O ₃ can increase the viscosity of the glass composition due to its tetrahedral coordination in the glass melt formed from the glass composition, thereby reducing the formability of the glass composition when the amount of Al ₂ O ₃ is too high. However, when the concentration _{of Al2O3} is balanced against the concentration of _SiO2 and the concentration of alkali oxides in the glass composition, _Al2O3 can lower the liquidus temperature of _the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as fusion forming processes. The inclusion of Al ₂ O ₃ in the glass base substrate prevents phase separation and reduces the number of non-bridging oxygen (NBO) in the glass. In addition, Al ₂ O ₃ can improve the effectiveness of ion exchange.在一些實施例中，玻璃基底基板可包括自大於或等於3莫耳%至小於或等於20莫耳%之量的Al ₂ O ₃ ，諸如，自大於或等於4莫耳%至小於或等於19莫耳%、自大於或等於5莫耳%至小於或等於18莫耳%、自大於或等於6莫耳%至小於或等於17莫耳%、自大於或等於7莫耳%至小於或等於16莫耳%、自大於或等於8莫耳%至小於或等於15莫耳%、自大於或等於9莫耳%至小於或等於14莫耳%、自大於或等於10莫耳%至小於或等於13莫耳%、自大於或等於11莫耳%至小於或等於12莫耳%或由此等端點中之任何者形成之任何子範圍。 In some embodiments, _the glass base substrate can include _Al2O3 in an amount from greater than or equal to 5 mol % to less than or equal to 15 mol %, such as from greater than or equal to 7 mol % to less than or equal to 14 mol % or any subrange formed from any of these endpoints.

The glass base substrate can include any amount _{of P2O5} sufficient to produce the desired hydrogen diffusivity. The inclusion of phosphorus in the glass base substrate promotes faster interdiffusion independent of exchanged ion pairs. Accordingly, phosphorous-containing glass-based substrates allow efficient formation of glass-based articles that include hydrogen-containing layers. The inclusion of P ₂ O ₅ also allows the generation of glass-based objects with deep layer depths (eg, greater than about 10 μm) in relatively short processing times. In some _embodiments , the glass base substrate may include _P2O5 in an amount from 4 mol % or greater to 15 mol % or less, such as from 5 mol % or greater to 14 mol % Less than or equal to 10 mol % or any subrange formed by any of these endpoints. In some embodiments, the glass base substrate may include _P2O5 in an amount from 5 mol % or more _to 15 mol % or less, such as from 6 mol % or more to 15 mol % or less, 5 mol % or more to 10 mol % or less, 6 mol % or more to 10 mol % or less, 7 mol % or more to 10 mol % or less, or any of these endpoints any subrange of .

The glass base substrate can include any suitable amount of alkali metal oxide. Alkali metal oxides facilitate ion exchange. The sum of alkali metal oxides (eg, _Li2O , _Na2O , and K2O, and other alkali metal oxides including _Cs2O and _Rb2O ) in the glass composition may be referred to as " _R2O , _{" and R2O may} be expressed in mole percent. In some embodiments, the glass base substrate can be substantially free or free of at least one of lithium and sodium.在一些實施例中，玻璃組合物包含大於或等於6莫耳%之量的R ₂ O，諸如，大於或等於7莫耳%、大於或等於8莫耳%、大於或等於9莫耳%、大於或等於10莫耳%、大於或等於11莫耳%、大於或等於12莫耳%、大於或等於13莫耳%、大於或等於14莫耳%、大於或等於15莫耳%、大於或等於16莫耳%、大於或等於17莫耳%、大於或等於18莫耳%、大於或等於19莫耳%、大於或等於20莫耳%、大於或等於21莫耳%、大於或等於22莫耳%、大於或等於23莫耳%或大於或等於24莫耳%。在一或多個實施例中，玻璃組合物包含小於或等於25莫耳%之量的R ₂ O，諸如，小於或等於24莫耳%、小於或等於23莫耳%、小於或等於22莫耳%、小於或等於21莫耳%、小於或等於20莫耳%、小於或等於19莫耳%、小於或等於18莫耳%、小於或等於17莫耳%、小於或等於16莫耳%、小於或等於15莫耳%、小於或等於14莫耳%、小於或等於13莫耳%、小於或等於12莫耳%、小於或等於11莫耳%、小於或等於10莫耳%、小於或等於9莫耳%、小於或等於8莫耳%或小於或等於7莫耳%。 It should be understood that any of the above ranges may be combined with any other range in an embodiment.在一些實施例中，玻璃組合物包含自大於或等於6.0莫耳%至小於或等於25.0莫耳%之量的R ₂ O，諸如，自大於或等於7.0莫耳%至小於或等於24.0莫耳%、自大於或等於8.0莫耳%至小於或等於23.0莫耳%、自大於或等於9.0莫耳%至小於或等於22.0莫耳%、自大於或等於10.0莫耳%至小於或等於21.0莫耳%、自大於或等於11.0莫耳%至小於或等於20.0莫耳%、自大於或等於12.0莫耳%至小於或等於19.0莫耳%、自大於或等於13.0莫耳%至小於或等於18.0莫耳%、自大於或等於14.0莫耳%至小於或等於17.0莫耳%或自大於或等於15.0莫耳%至小於或等於16.0莫耳%，及在前述值之間的所有範圍及子範圍。

In some embodiments, the alkali metal oxide can be K ₂ O. The inclusion of _K2O allows efficient exchange of hydrogen species into the glass substrate after exposure to an aqueous environment.在一些實施例中，玻璃基底基板可包括自大於或等於6莫耳%至小於或等於25莫耳%之量的K ₂ O，諸如，自大於或等於7莫耳%至小於或等於24莫耳%、自大於或等於8莫耳%至小於或等於23莫耳%、自大於或等於9莫耳%至小於或等於22莫耳%、自大於或等於10莫耳%至小於或等於21莫耳%、自大於或等於11莫耳%至小於或等於20莫耳%、自大於或等於12莫耳%至小於或等於19莫耳%、自大於或等於13莫耳%至小於或等於18莫耳%、自大於或等於14莫耳%至小於或等於17莫耳%或自大於或等於15莫耳%至小於或等於16莫耳%，或自此等端點中之任何者形成之任何子範圍。 In some embodiments, the glass-based substrate may include _K20 in an amount from 10 mol% or more to 25 mol% or less, such as from 10 mol% or more to 20 mol% or less, from 11 mol% or more to 25 mol% or less, from 11 mol% or more to 20 mol% or less, from 15 mol% or more to 20 mol% or less, or anywhere between these endpoints Any subrange formed by any.

The glass base substrate can include any suitable amount of _Rb2O . In some embodiments, the glass base substrate may include _Rb20 in an amount from greater than or equal to 0 mol % to less than or equal to 10 mol %, such as from greater than or equal to 1 mol % to less than or equal to 9 mol %, from greater than or equal to 2 mol % to less than or equal to 8 mol %, from greater than or equal to 3 mol % to less than or equal to 7 mol %, from greater than or equal to 4 mol % to less than or equal to 6 mol %, 5 mol %, or any of these endpoints any subrange of .

The glass base substrate can include any suitable amount of _Cs2O . In some embodiments, the glass base substrate may comprise _Cs20 in an amount from greater than or equal to 0 mol % to less than or equal to 10 mol %, such as from greater than or equal to 1 mol % to less than or equal to 9 mol %, from greater than or equal to 2 mol % to less than or equal to 8 mol %, from greater than or equal to 3 mol % to less than or equal to 7 mol %, from greater than or equal to 4 mol % to less than or equal to 6 mol %, 5 mol %, or any of these endpoints any subrange of .

In some embodiments, the glass-based substrate may have a composition comprising one of: from greater than or equal to 45 mol % to less than or equal to 75 mol % SiO ₂ ; from greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; from greater than or equal to 6 mol % to less than or equal to 15 mol % P ₂ O ₅ ; and from greater than or equal to 6 mol % to less than or equal to 25 mol % K ₂ O.

In some embodiments, the glass base substrate can have a composition comprising one of: from greater than or equal to 45 mol % to less than or equal to 75 mol % SiO ₂ ; from greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; from greater than or equal to 4 mol % to less than or equal to 15 mol % P ₂ O ₅ ; and from greater than or equal to 11 mol % to less than or equal to 25 mol % K ₂ O.

In some embodiments, the glass base substrate can have a composition comprising one of: from greater than or equal to 55 mol % to less than or equal to 69 mol % SiO ₂ ; from greater than or equal to 5 mol % to less than or equal to 15 mol % Al ₂ O ₃ ; from greater than or equal to 6 mol % to less than or equal to 10 mol % P ₂ O ₅ ; and from greater than or equal to 10 mol % to less than or equal to 20 mol % K ₂ O.

In some embodiments, the glass-based substrate can have a composition comprising one of: from greater than or equal to 55 mol % to less than or equal to 69 mol % SiO ₂ ; from greater than or equal to 5 mol % to less than or equal to 15 mol % Al ₂ O ₃ ; from greater than or equal to 5 mol % to less than or equal to 10 mol % P ₂ O ₅ ; and from greater than or equal to 11 mol % to less than or equal to 20 mol % K ₂ O.

In some embodiments, the glass base substrate can have a composition comprising one of: from greater than or equal to 58 mol % to less than or equal to 63 mol % SiO ₂ ; from greater than or equal to 7 mol % to less than or equal to 14 mol % Al ₂ O ₃ ; from greater than or equal to 7 mol % to less than or equal to 10 mol % P ₂ O ₅ ; and from greater than or equal to 15 mol % to less than or equal to 20 mol % K ₂ O.

In some embodiments, the glass base substrate may exhibit a Vickers crack initiation threshold of 5 kgf or greater, such as 6 kgf or greater, 7 kgf or greater, 8 kgf or greater, 9 kgf or greater, 10 kgf or greater, or greater.

The glass base substrate can have any suitable geometry. In some embodiments, the glass base substrate may have a thickness of 2 mm or less, such as 1 mm or less, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, or less. In some embodiments, the glass base substrate may have been in the form of a plate or sheet. In some other embodiments, the glass base substrate may have a 2.5D or 3D shape. As used herein, "2.5D shape" refers to a sheet-shaped object having at least one major surface that is at least partially uneven, and a second major surface that is substantially flat. As used herein, a "3D shape" refers to an object having first and second opposing major surfaces that are at least partially uneven.

Glass-based articles can be produced from glass-based substrates by exposure to water vapor under any suitable conditions. Exposure can be performed in any suitable unit, such as an oven with relative humidity control. In some embodiments, the glass-based substrate may be exposed to an environment having a relative humidity of one of 75% or greater, such as 80% or greater, 85% or greater, 90% or greater, 95% or greater, 99% or greater, or greater. In some embodiments, the glass-based substrate can be exposed to an environment having 100% relative humidity.

In some embodiments, the glass base substrate may be exposed to an environment at a temperature of 70°C or greater, such as 75°C or greater, 80°C or greater, 85°C or greater, 90°C or greater, 95°C or greater, 100°C or greater, 105°C or greater, 110°C or greater, 115°C or greater, 120°C or greater, 125°C or greater, 130°C or greater, 130°C or greater, 1 35°C, 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, 180°C or higher, 185°C or higher, 190°C or higher, 195°C or higher, 200°C or higher. In some embodiments, the glass base substrate may be exposed to an environment at a temperature from 70°C or greater to 210°C or less, such as from 75°C or greater to 205°C or less, from 80°C or greater to 200°C or less, from 85°C or greater to 195°C or less, from 90°C or greater to 190°C or less, from 90°C or greater to 185°C or less, from 10°C or greater. 0°C to less than or equal to 180°C, from greater than or equal to 105°C to less than or equal to 175°C, from greater than or equal to 110°C to less than or equal to 170°C, from greater than or equal to 115°C to less than or equal to 165°C, from greater than or equal to 120°C to less than or equal to 160°C, from greater than or equal to 125°C to less than or equal to 155°C, from greater than or equal to 130°C to less than or equal to 150°C, from greater than or equal to 135°C to less than Or equal to 145°C, 140°C, or any subrange formed from these endpoints.

In some embodiments, the glass base substrate may be exposed to an environment containing water vapor for a period of time sufficient to produce a desired degree of diffusion of hydrogen-containing species and a desired depth of layer. In some embodiments, the glass base substrate can be exposed to an environment containing water vapor for 1 day or more, such as 2 days or more, 3 days or more, 4 days or more, 5 days or more, 6 days or more, 7 days or more, 8 days or more, 9 days or more, 10 days or more, 15 days or more, 20 days or more, 25 days or more, 30 days or more, 35 days or more, 40 days or more , greater than or equal to 45 days, greater than or equal to 50 days, greater than or equal to 55 days, greater than or equal to 60 days, greater than or equal to 65 days or more. In some embodiments, the glass base substrate can be exposed to an environment containing water vapor for a period of time ranging from 1 day or more to 70 days or less, such as from 2 days or more to 65 days or less, from 3 days or more to 60 days or less, from 4 days or more to 55 days or less, from 5 days or more to 45 days or less, from 6 days or more to 40 days or less, from 7 days or more to 35 days or less, from 7 days or more to 35 days or less, or equal to 8 days to less than or equal to 30 days, from greater than or equal to 9 days to less than or equal to 25 days, from greater than or equal to 10 days to less than or equal to 20 days, 15 days, or any subrange formed from any of these endpoints. The exposure conditions can be modified to reduce the time necessary to produce a desired amount of hydrogen-containing species diffusion into the glass base substrate. For example, temperature and/or relative humidity can be increased to reduce the time required to achieve a desired degree of hydrogen-containing species diffusion and layer depth into the glass base substrate.

The glass-based objects disclosed herein can be incorporated into another object, such as an object (or display object) having a display (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable elements (e.g., watches), and the like), architectural objects, transportation objects (e.g., automobiles, trains, airplanes, marine vessels, etc.), electrical objects, or any object requiring certain transparency, scratch resistance, abrasion resistance, or a combination thereof. An exemplary object of any of the glass substrate objects disclosed herein is also shown in Figures 2A and 2B. Specifically, FIGS. 2A and 2B show a consumer electronics component 200 comprising: a housing 202 having a front 204, a rear 206, and side surfaces 208; electrical components (not shown) at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or on the front surface of the housing such that it is over the display. In some embodiments, at least a portion of one of the cover substrate 212 and the housing 202 can include any of the glass substrate articles disclosed herein. Exemplary embodiment

Glass compositions particularly suitable for the formation of glass-based articles herein are formed into glass-based substrates. The compositions of Examples 1 to 6 are described in Table II below. Density is determined using the buoyancy method of ASTM C693-93 (2013). The coefficient of linear thermal expansion (CTE) over the temperature range of 25°C to 300°C is expressed as 10 ^-7 /°C and determined according to ASTM E228-11 using a push rod dilatometer. The beam bending viscosity method of ASTM C598-93 (2013) is used to determine the strain point and annealing point. The softening point was determined using the parallel plate viscosity method of ASTM C1351M-96 (2012). According to ASTM C965-96 (2012) entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point", the temperature at which the glass has a viscosity of 200P, 35,000P, and 200,000P is measured for the resulting composition.

A glass base substrate comprising the composition of Example 1 and having a thickness of 1 mm was exposed to an environment of 85% relative humidity for 65 days to form a glass base article comprising a hydrogen-containing layer of the type described herein.

The depth of the hydrogen-containing layer was measured by SIMS before and after exposure. The results of the SIMS hydrogen concentration measurements are shown in Figure 3, where the as-received glass substrate hydrogen concentration curve 301 has a layer depth of about 5 μm and the glass substrate object hydrogen concentration curve 302 has a layer depth of about 30 μm. The exposed glass substrate article was measured to a depth of about 25 μm, and curve 303 was extrapolated to determine the layer depth. Based on the measured values, the hydrogen diffusivity (D) is calculated using the general formula DOL = sqrt(D·time).

The Vickers dent cracking threshold was measured before and after exposure to water vapor. The results of Vickers indentation of the exposed front glass base substrates after indentation at 5 kgf and 10 kgf respectively are shown in Fig. 4 and Fig. 5 . As shown in Figures 4 and 5, the glass base substrate has a Vickers crack initiation threshold above 5 kgf but below 10 kgf. The results of Vickers indentation of exposed glass substrate objects after indentation at 5 kgf, 10 kgf and 20 kgf are shown in Figs. 6, 7 and 8, respectively. As demonstrated by Figures 6, 7 and 8, the Vickers dent cracking threshold for glass substrate objects is greater than 20 kgf.

A glass base substrate comprising the compositions of Comparative Examples 1 to 3 and having a thickness of 1 mm was also prepared and exposed to an environment of 85% relative humidity for 30 days. The compositions of Comparative Examples 1 to 3 are reported in Table III below. The Vickers dent cracking threshold was measured before and after exposure to an environment containing water vapor, and the depth of the hydrogen-containing layer was measured by SIMS after exposure. Hydrogen diffusivity was calculated based on the measured values.

As shown in Table III, the glass composition of Example 1 exhibited a monohydrogen diffusivity two orders of magnitude higher than the glass composition of Comparative Example 3, which also included potassium but did not include phosphorus. These results indicate that the presence of phosphorus in the glass composition exhibits increased hydrogen diffusivity. Similarly, the glass composition of Comparative Example 3 exhibited a hydrogen diffusivity two orders of magnitude higher than that of Comparative Examples 1 and 2 including lithium and sodium, respectively. The difference in hydrogen diffusivity between potassium-containing glass compositions and lithium- and sodium-containing glass compositions indicates that alkali ions with larger ionic radii allow for faster hydrogen diffusivity.

Glass base substrates comprising the glass composition of Example 6 were produced with thicknesses of 0.5 mm and 1.0 mm. The glass-based substrates were exposed to a 100% relative humidity environment at a temperature of 200°C for a period of 7 days to produce glass-based articles of the type described herein. The glass-based objects exhibit a region of compressive stress extending from the surface to a compression depth. The maximum compressive stress measured for a 0.5 mm glass substrate object was 124 Mpa, and the maximum compressive stress measured for a 1.0 mm glass substrate object was 137 Mpa. The maximum central tensile measured for a 0.5 mm glass substrate object was 32 MPa, and the maximum compressive stress measured for a 1.0 mm glass substrate object was 15 MPa. The compression depth was 101 μm for the 0.5 mm glass substrate object and 99 μm for the 1.0 mm glass substrate object.

Heart-cut samples of 0.5 mm and 1.0 mm thick glass-based objects were also formed from glass-based substrates comprising the glass composition of Example 6 after exposure to a 100% relative humidity environment at 200°C for 7 days. The samples were then polished to a width of 0.5 mm and subjected to Fourier-transform infrared spectroscopy (FTIR) analysis. FTIR analysis was performed with the following conditions: CaF/InSb, 64 scans, 16 cm ⁻¹ resolution, 10 μm aperture and 10 μm steps. The scan originates at the surface of the sample and continues to approximately the midpoint of the thickness. Spectra were generated relative to "dry" silica and hydroxyl (βOH) concentrations were calculated using the 3900 cm ⁻¹ max and 3550 cm ⁻¹ min parameters. Due to the multicomponent nature of the glass-based objects, it is not possible to distinguish between bound and molecular hydroxyl groups, so the curves report the concentration of the total hydroxyl content. The measured hydroxyl concentrations of 0.5 mm thick and 1.0 mm thick samples are shown in Figures 9 and 10, respectively. As shown in Figures 9 and 10, the measured hydroxyl content becomes substantially constant and equivalent to a concentration within the sample of approximately 200 μm of the hydroxyl content at the center of the object (indicative of the background hydroxyl content of the precursor glass substrate object), as measured by FTIR. The appearance of the buried hydroxyl concentration peaks in Figures 9 and 10 is an artifact of the measurement method.

Square samples with the composition of Example 1 were prepared, with a thickness of 1 mm and a side of 50 mm. Five of these samples were then processed in a 100% relative humidity environment at 200°C for 121 hours. Then the compressive stress (compressive stress; CS) and depth of compression (DOC) of the processed sample were measured by FSM, so as to obtain a CS of 167 MPa and a DOC of 73 μm. Five steam-treated samples and three control samples not exposed to steam treatment were subjected to an abraded ring-on-ring (AROR) test. The strength and peak load of each tested sample are reported in Table IV. As shown in Table IV, the steam treated samples exhibited greatly increased peak load and strength compared to the untreated control samples.

The AROR test is a surface strength measurement for testing flat glass specimens, and ASTM C1499-09 (2013) entitled "Standard Test Method for Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperature" serves as the basis for the AROR test method utilized herein. The contents of ASTM C1499-09 are incorporated herein by reference in their entirety. Using the method and apparatus described in Appendix 2 entitled "abrasion Procedures" of ASTM C158-02 (2012) entitled "Standard Test Methods for Strength of Glass by Flexure (Determination of Modulus of Rupture)", the glass samples were ground with 90 grit silicon carbide (SiC) particles delivered to the glass samples prior to ring-to-ring testing. The contents of ASTM C158-02 and the contents of Appendix 2 are specifically incorporated herein by reference in their entirety.

Prior to ring-to-ring testing, the surface of the glass-based article sample was ground as described in ASTM C158-02, Appendix 2, to normalize and/or control the surface defect profile of the sample using the apparatus shown in Figure A2.1 of ASTM C158-02. The abrasive material was blasted onto the surface of the glass-based article at an air pressure of 5 psi. After air flow was established, 1 cm ³ of abrasive material was poured into the furnace and the samples were grit blasted.

For the AROR test, a glass substrate article having at least one abrasive surface as shown in Figure 11 was placed between two concentric rings of different sizes to determine the equibiaxial flexural strength (i.e., the maximum stress the material can support when subjected to flexure between the two concentric rings). In AROR configuration 400, ground glass substrate article 410 is supported by a support ring 420 having a diameter D2. A force F is applied to the surface of the glass substrate article by a load cell (not shown) via a loading ring 430 having a diameter D1.

The diameter ratio D1/D2 of the loading ring to the support ring may be in a range from 0.2 to 0.5. In some embodiments, D1/D2 is 0.5. Loading ring 430 and support ring 420 should be concentrically aligned to within 0.5% of support ring diameter D2. The dynamometer used for testing shall be accurate to within ±1% at any load within the selected range. Test at a temperature of 23±2°C and a relative humidity of 40±10%.

For the jig design, the radius r of the protruding surface of the loading ring 430 is in the range of h/2≦r≦3h/2, where h is the thickness of the glass substrate article 410 . The loading ring 430 and the support ring 420 are made of hardened steel with a hardness HRc>40. AROR clamps are commercially available.

The intended failure mechanism for the AROR test was to observe fracture of the glass substrate article 410 originating from the surface 430a within the load ring 430 . Faults occurring outside this region (ie, between the loading ring 430 and the support ring 420 ) were ignored in the data analysis. However, due to the thinness and high strength of the glass substrate object 410, large deflections exceeding the sample thickness h were sometimes observed. Therefore, it is not uncommon to observe a high percentage of failures originating from under the load ring 430 . Without knowledge of the stress development inside and below the ring (collected via strain gauge analysis) and the source of the failure in each specimen, the stresses could not be accurately calculated. In response to the measurement, the AROR test therefore focuses on the peak load at the fault.

While typical embodiments have been set forth for purposes of illustration, the foregoing description should not be considered as a limitation on the scope of the disclosure or of the appended claims. Accordingly, various modifications, adaptations and substitutions may occur to those skilled in the art without departing from the spirit and scope of this disclosure or the appended claims.

100‧‧‧glass substrate objects 110‧‧‧first surface 112‧‧‧Second surface 120‧‧‧The first hydrogen-containing layer 122‧‧‧The second hydrogen-containing layer 130‧‧‧No added hydrogen substance area 200‧‧‧Consumer electronic components 202‧‧‧Shell 204‧‧‧Front 206‧‧‧rear 208‧‧‧side surface 210‧‧‧display 212‧‧‧Cover substrate 301‧‧‧Hydrogen concentration curve of original glass base substrate 302‧‧‧Hydrogen concentration curve of glass substrate object 303‧‧‧Extrapolated curve 400‧‧‧AROR configuration 410‧‧‧Grinding glass substrate objects 420‧‧‧Support ring 430‧‧‧Loading ring 430a‧‧‧surface d1‧‧‧depth d2‧‧‧depth t‧‧‧thickness D1‧‧‧Diameter of loading ring D2‧‧‧Support ring diameter F‧‧‧force

Figure 1 is a representation of a cross-section of a glass substrate article according to one embodiment.

FIG. 2A is a plan view of an exemplary electronic component incorporating any of the glass substrate articles disclosed herein.

Figure 2B is a perspective view of the exemplary electronic component of Figure 2A.

FIG. 3 is a measurement of hydrogen concentration by SIMS as a function of depth below the surface for a glass-based article formed from a glass-based substrate having the composition of Example 1. FIG.

Figure 4 is a photograph of a Vickers indent at 5 kgf in a glass base substrate having the composition of Example 1 before exposure to an aqueous environment.

Figure 5 is a photograph of a Vickers indent at 10 kgf in a glass base substrate having the composition of Example 1 before exposure to an aqueous environment.

Figure 6 is a photograph of a Vickers indent at 5 kgf in a glass base article formed by exposing a glass base substrate having the composition of Example 1 to an aqueous environment.

Figure 7 is a photograph of a Vickers indent at 10 kgf in a glass base article formed by exposing a glass base substrate having the composition of Example 1 to an aqueous environment.

Figure 8 is a photograph of a Vickers indent at 20 kgf in a glass base article formed by exposing a glass base substrate having the composition of Example 1 to an aqueous environment.

Figure 9 is a graph of hydroxyl group (BOH) concentration as a function of depth from the surface for a 0.5 mm thick glass object after exposure to an aqueous environment, according to one embodiment.

Figure 10 is a graph of hydroxyl group (BOH) concentration as a function of depth from the surface for a 1.0 mm thick glass object after exposure to an aqueous environment, according to one embodiment.

Figure 11 is a side view of the ring-to-ring test setup.

Domestic deposit information (please note in order of depositor, date, and number) none

Overseas storage information (please note in order of storage country, organization, date, and number) none

Claims (10)

A glass substrate article comprising: SiO₂;Al₂o₃; Greater than or equal to 4 mol% to less than or equal to 15 mol% of P₂o₅one or more alkali metal oxides, alkali metal ions having an ionic radius of 0.133 nm, 0.152 nm or 0.167 nm, wherein the one or more alkali metal oxides comprise greater than or equal to 6 mol% to less than or equal to 25 mol% of K₂O; and a hydrogen-containing layer extending from a surface of the glass substrate article to a depth of a layer, wherein: monovalent hydrogen-containing species in the hydrogen-containing layer replaces a portion of ions having an ionic radius of 0.133 nm, 0.152 nm, or 0.167 nm such that a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the layer depth; and the layer depth is greater than 5 μm. The glass substrate article of claim 1, wherein the glass substrate article is characterized by at least one of: a Vickers cracking initiation threshold of at least 1 kgf, or the layer depth is at least about 10 μm. The glass base article as described in claim 1 or 2, wherein the center of the glass base article comprises: greater than or equal to 45 mol % to less than or equal to 75 mol % of SiO ₂ ; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; and greater than or equal to 6 mol % to less than or equal to 15 mol % of P ₂ O ₅ . The glass-based article of claim 1 or 2, wherein the glass-based article is substantially free of at least one of lithium and sodium. The glass substrate article as described in claim 1 or 2, further comprising a compressive stress layer extending from a surface of the glass substrate article into the glass substrate article to a compression depth, wherein the compression stress layer contains a compression stress greater than or equal to 100Mpa, and the compression depth is greater than or equal to 75 μm. A consumer electronic product comprising: a housing including a front surface, a rear surface, and side surfaces; electrical components at least partially within the housing, the electrical components including at least a controller, a memory, and a display at or adjacent to the front surface of the housing; and a cover substrate disposed on the display, wherein at least a portion of at least one of the housing or the cover substrate Comprising the glass substrate object as described in Claim 1 or 2. A glass comprising: greater than or equal to 45 mol% to less than or equal to 75 mol% of SiO₂;Al greater than or equal to 3 mol% to less than or equal to 20 mol%₂o₃; Greater than or equal to 6 mol% to less than or equal to 15 mol% of P₂o₅one or more alkali metal oxides, alkali metal ions having an ionic radius of 0.133 nm, 0.152 nm or 0.167 nm, wherein the one or more alkali metal oxides comprise greater than or equal to 6 mol% to less than or equal to 25 mol% of K₂O; and a hydrogen-containing layer extending from a surface of the glass to a depth of one layer, wherein monovalent hydrogen-containing species in the hydrogen-containing layer replaces a portion of ions having an ionic radius of 0.133 nm, 0.152 nm, or 0.167 nm such that a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of the layer. A glass comprising: greater than or equal to 45 mol% to less than or equal to 75 mol% of SiO₂; greater than or equal to 3 mol% to less than or equal to 20 mol% Al₂o₃; Greater than or equal to 4 mol% to less than or equal to 15 mol% of P₂o₅one or more alkali metal oxides, alkali metal ions having an ionic radius of 0.133 nm, 0.152 nm or 0.167 nm, wherein the one or more alkali metal oxides comprise greater than or equal to 6 mol% to less than or equal to 25 mol% of K₂O; and a hydrogen-containing layer extending from a surface of the glass to a depth of one layer, wherein monovalent hydrogen-containing species in the hydrogen-containing layer replaces a portion of ions having an ionic radius of 0.133 nm, 0.152 nm, or 0.167 nm such that a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of the layer. The glass according to claim 7 or 8, wherein the glass is characterized by at least one of the following: substantially free of at least one of lithium and sodium, or a Vickers crack initiation threshold greater than or equal to 5kgf. A method of forming a glass-based article comprising the steps of: exposing a glass-based substrate to an environment having a relative humidity greater than or equal to 75% to form a glass-based article having a hydrogen-containing layer extending from a surface of the glass-based article to a layer depth where the glass base substrate contains: SiO₂;Al₂o₃; Greater than or equal to 4 mol% to less than or equal to 15 mol% of P₂o₅one or more alkali metal oxides, alkali metal ions having an ionic radius of 0.133 nm, 0.152 nm or 0.167 nm, wherein the one or more alkali metal oxides comprise greater than or equal to 6 mol% to less than or equal to 25 mol% of K₂O; and wherein the monovalent hydrogen-containing species in the hydrogen-containing layer replaces a portion of ions having an ionic radius of 0.133 nm, 0.152 nm, or 0.167 nm such that a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the layer depth; and the layer depth is greater than or equal to 5 μm.