Hydrogen-containing glass-based articles having high indentation crack thresholds - Patents.com

Abstract

To provide glasses that exhibit higher performance, such as resistance to damage, for use in portable electronic devices.SOLUTION: Glasses are provided that include a hydrogen-containing layer extending from a surface to a layer depth. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration to the layer depth. The glasses exhibit a high Vickers indentation cracking threshold.SELECTED DRAWING: Figure 9

Description

Related Applications

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 62 / 587,872, filed November 17, 2017, and Dutch Provisional Application No. 2020896, filed May 8, 2018, the contents of which are relied upon and incorporated herein by reference in their entireties.

[0002] This application is also a divisional application of Patent Application No. 2020-526391, filed on November 16, 2018. [Technical Field]

[0003] The present disclosure relates to glass-based articles containing hydrogen, glass compositions utilized to form the glass-based articles, and methods of forming the glass-based articles. [Background technology]

[0004] Portable electronic devices, such as smartphones, tablets, and wearable devices (such as watches and fitness trackers), are becoming smaller and more complex. Accordingly, the materials traditionally used for at least one exterior surface of such portable electronic devices are also becoming more complex. For example, as portable electronic devices become smaller and thinner to meet consumer demand, the display covers and housings used in these portable electronic devices are also becoming smaller and thinner, resulting in higher performance requirements for the materials used to form these components. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a need for materials that exhibit higher performance, such as damage resistance, for use in portable electronic devices. [Means for solving the problem]

[0006] In embodiment (1), a glass-based article is provided. The glass-based article includes SiO2, Al2O3, and PO5; and a hydrogen-containing layer extending from the surface of the glass-based article to a depth thereof. The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the depth thereof, and the depth thereof is greater than 5 μm.

[0007] In an embodiment (2), there is provided the glass-based article according to embodiment (1), wherein the glass-based article has a Vickers crack initiation threshold of 1 kgf (approximately 9.8 N) or more.

[0008] In an embodiment (3), there is provided the glass-based article according to the embodiment (1) or (2), wherein the depth of layer is 10 μm or more.

[0009] In an embodiment (4), there is provided the glass-based article of any one of embodiments (1) to (3), wherein the maximum hydrogen concentration is located at the surface of the glass-based article.

[0010] In an embodiment (5), there is provided the glass-based article of any one of embodiments (1) to (4), further comprising at least one of Li2O, Na2O, K2O, Cs2O, and Rb2O.

[0011] In an embodiment (6), there is provided the glass-based article of any one of embodiments (1) to (5), further comprising KO.

[0012] In an embodiment (7), there is provided the glass-based article of any one of embodiments (1) to (6), wherein the center of the glass-based article comprises between 45 mol% and 75 mol% SiO2; between 3 mol% and 20 mol% Al2O3; between 6 mol% and 15 mol% PO5; and between 6 mol% and 25 mol% KO.

[0013] In an embodiment (8), there is provided the glass-based article of any one of embodiments (1) to (6), wherein the center of the glass-based article comprises between 45 mol% and 75 mol% SiO2; between 3 mol% and 20 mol% Al2O3; between 4 mol% and 15 mol% PO5; and between 11 mol% and 25 mol% KO.

[0014] In an embodiment (9), there is provided the glass-based article of any one of embodiments (1) to (6), wherein the center of the glass-based article comprises: 55 mol% to 69 mol% SiO2; 5 mol% to 15 mol% Al2O3; 6 mol% to 10 mol% PO5; and 10 mol% to 20 mol% KO.

[0015] In an embodiment (10), there is provided the glass-based article of any one of embodiments (7) to (9), wherein the center of the glass-based article comprises: equal to or greater than 0 mol% and equal to or less than 10 mol% CsO; and equal to or greater than 0 mol% and equal to or less than 10 mol% RbO.

[0016] In an embodiment (11), there is provided the glass-based article of any one of embodiments (1) to (10), wherein the glass-based article is substantially free of at least one of lithium and sodium.

[0017] In an embodiment (12), there is provided the glass-based article of any one of embodiments (1) to (11), further comprising a compressive stress layer extending from a surface of the glass-based article to a compressive depth within the glass-based article.

[0018] In an embodiment (13), there is provided the glass-based article of embodiment (12), wherein the compressive stress layer comprises a compressive stress of at least about 100 MPa and a compression depth of at least about 75 μm.

[0019] In a fourteenth aspect, a consumer electronics product is provided. The consumer electronics product includes a housing including a front, a back, and a side; electrical components at least partially within the housing, the electrical components including at least a controller, a memory, and a display, the display being on or adjacent to the front of the housing; and a cover substrate disposed over the display. At least a portion of at least one of the housing or the cover substrate comprises the glass-based article of any one of aspects (1) to (13).

[0020] In embodiment (15), a glass is provided, the glass comprising: 45 mol% to 75 mol% SiO2; 3 mol% to 20 mol% Al2O3; 6 mol% to 15 mol% P2O5; and 6 mol% to 25 mol% K2O.

[0021] In embodiment (16), there is provided the glass of embodiment (15), comprising: 55 mol% to 69 mol% SiO; 5 mol% to 15 mol% AlO; 6 mol% to 10 mol% PO; and 10 mol% to 20 mol% KO.

[0022] In embodiment (17), there is provided the glass of embodiment (15) or (16), further comprising: 0 mol % to 10 mol % CsO; and 0 mol % to 10 mol % RbO.

[0023] In an embodiment (18), there is provided the glass of any one of embodiments (15) to (17), wherein the glass is substantially free of lithium.

[0024] In an embodiment (19), there is provided the glass of any one of embodiments (15) to (18), wherein the glass is substantially free of sodium.

[0025] In embodiment (20), there is provided the glass of any one of embodiments (15) through (19), comprising: 58 mol% to 63 mol% SiO; 7 mol% to 14 mol% AlO; 7 mol% to 10 mol% PO; and 15 mol% to 20 mol% KO.

[0026] In embodiment (21), there is provided the glass of any one of embodiments (15) to (20), wherein the glass has a Vickers crack initiation threshold of 5 kgf (about 49 N) or greater.

[0027] In embodiment (22), there is provided the glass of any one of embodiments (15) to (21), further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0028] In embodiment (23), a glass is provided, the glass comprising 45 mol% to 75 mol% SiO, 3 mol% to 20 mol% AlO, 4 mol% to 15 mol% PO, and 11 mol% to 25 mol% KO.

[0029] In embodiment (24), there is provided the glass of embodiment (23), comprising: 55 mol% to 69 mol% SiO; 5 mol% to 15 mol% AlO; 5 mol% to 10 mol% PO; and 11 mol% to 20 mol% KO.

[0030] In embodiment (25), there is provided the glass of embodiment (23) or (24), further comprising: 0 mol % to 10 mol % CsO; and 0 mol % to 10 mol % RbO.

[0031] In an embodiment (26), there is provided the glass of any one of embodiments (23) to (25), wherein the glass is substantially free of lithium.

[0032] In an embodiment (27), there is provided the glass of any one of embodiments (23) through (26), wherein the glass is substantially free of sodium.

[0033] In embodiment (28), there is provided the glass of any one of embodiments (23) through (27), comprising: from 58 mol% to 63 mol% SiO; from 7 mol% to 14 mol% AlO; from 7 mol% to 10 mol% PO; and from 15 mol% to 20 mol% KO.

[0034] In embodiment (29), there is provided the glass of any one of embodiments (23) through (28), wherein the glass has a Vickers crack initiation threshold of 5 kgf (about 49 N) or greater.

[0035] In embodiment (30), there is provided the glass of any one of embodiments (23) to (29), further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0036] In embodiment (31), a method is provided. The method includes exposing a glass-based substrate to an environment with a relative humidity of 75% or greater to form a glass-based article having a hydrogen-containing layer extending from a surface of the glass-based article to a depth thereof. The glass-based substrate includes SiO, AlO, and PO. The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward a depth thereof, and the depth thereof is greater than 5 μm.

[0037] In an embodiment (32), there is provided the method of embodiment (31), wherein the glass-based substrate has a composition including 55 mol% to 69 mol% of SiO; 5 mol% to 15 mol% of AlO; 6 mol% to 10 mol% of PO; and 10 mol% to 20 mol% of KO.

[0038] In an embodiment (33), there is provided the method of embodiment (31), wherein the glass-based substrate has a composition including 45 mol% to 75 mol% of SiO; 3 mol% to 20 mol% of AlO; 4 mol% to 15 mol% of PO; and 11 mol% to 25 mol% of KO.

[0039] In an embodiment (34), there is provided the method of embodiment (31), wherein the glass-based substrate has a composition including 45 mol% to 75 mol% of SiO; 3 mol% to 20 mol% of AlO; 6 mol% to 15 mol% of PO; and 6 mol% to 25 mol% of KO.

[0040] In an embodiment (35), there is provided the method of any one of embodiments (31) to (34), wherein the glass-based substrate further comprises 0 mol% to 10 mol% CsO; and 0 mol% to 10 mol% RbO.

[0041] In embodiment (36), there is provided the method of any one of embodiments (31) to (35), further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0042] In an embodiment (37), the method of any one of embodiments (31) to (36) is provided, wherein the glass-based article is substantially free of at least one of lithium and sodium.

[0043] In an embodiment (38), there is provided the method of any one of embodiments (31) to (37), wherein the exposing is performed at a temperature of 70° C. or higher.

[0044] In an embodiment (39), there is provided the method of any one of embodiments (31) to (38), wherein the glass-based article has a Vickers crack initiation threshold of 1 kgf (about 9.8 N) or greater.

[0045] These and other aspects, advantages and salient features will become apparent from the following detailed description, the accompanying drawings and the appended claims. [Brief explanation of the drawings]

[0046] [Figure 1] FIG. 1 is a cross-sectional view of a glass-based article according to one embodiment. [Figure 2A] FIG. 1 is a plan view of an exemplary electronic device incorporating any of the glass-based articles disclosed herein. [Figure 2B] FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A. [Figure 3] FIG. 1 shows SIMS measurements of hydrogen concentration as a function of depth below the generated surface for glass-based articles formed from glass-based substrates having the composition of Example 1. [Figure 4] FIG. 1 is a photograph showing a Vickers indentation at 5 kgf (approximately 49 N) on a glass-based substrate having the composition of Example 1 before exposure to a water-containing environment. [Figure 5] FIG. 1 is a photograph showing a Vickers indentation at 10 kgf (approximately 98 N) on a glass-based substrate having the composition of Example 1 before exposure to a water-containing environment. [Figure 6] FIG. 1 is a photograph showing a Vickers indentation at 5 kgf (approximately 49 N) on a glass-based article formed by exposing a glass-based substrate having the composition of Example 1 to a water-containing environment. [Figure 7] FIG. 1 is a photograph showing a Vickers indentation at 10 kgf (approximately 98 N) on a glass-based article formed by exposing a glass-based substrate having the composition of Example 1 to a water-containing environment. [Figure 8] FIG. 1 is a photograph showing a Vickers indentation at 20 kgf (approximately 196 N) on a glass-based article formed by exposing a glass-based substrate having the composition of Example 1 to a water-containing environment. [Figure 9] FIG. 1 shows a plot of hydroxyl (βOH) concentration of a 0.5 mm thick glass article as a function of depth from the surface after exposure to a water-containing environment, according to one embodiment. [Figure 10] FIG. 1 shows a plot of hydroxyl (βOH) concentration of a 1.0 mm thick glass article as a function of depth from the surface after exposure to a water-containing environment, according to one embodiment. [Figure 11] FIG. 1 is a side view of a ring-on-ring test apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0047] In the following description, like reference characters designate like or corresponding parts throughout the figures from several defined locations shown in the figures. It is also understood that, unless otherwise specified, terms such as "upper," "lower," "external," and "internal" are words of convenience and should not be construed as limiting terms. Unless otherwise specified, ranges of values, when recited, include both the upper and lower limits of the range, as well as any subranges therebetween. As used herein, the indefinite articles "a," "an," and the corresponding definite article "the" mean "at least one" or "one or more," unless otherwise specified. It is also understood that the various features disclosed in the specification and drawings can be used in any combination.

[0048] As used herein, the term "glass-based" is used in its broadest sense and includes any object made entirely or partially of glass, including glass-ceramics (containing crystalline phases and residual amorphous glass phases). Unless otherwise specified, all compositions of glasses described herein are expressed in terms of mole percent (mol%), and components are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in degrees Celsius (°C).

[0049] It should be noted that the terms "substantially" and "about" may be used herein to express the inherent uncertainty that may result from any quantitative comparison, value, measurement, or other expression. These terms are also used herein to express the degree to which a quantitative expression may vary from the stated standard without resulting in a change in the basic function of the subject matter in question. For example, a glass that is "substantially free of K2O" refers to a glass in which K2O is not actively added or batched into the glass, but may be present as a contaminant in very small amounts, e.g., less than about 0.01 mol%. As used herein, when the term "about" is used to modify a value, the exact value is also disclosed. For example, the term "greater than about 10 mol%" also discloses "10 mol% or greater."

[0050] Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying examples and drawings.

[0051] The glass-based articles disclosed herein include a hydrogen-containing layer extending from the surface to the depth of the article. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration in the glass-based article toward the depth of the layer. In some embodiments, the maximum hydrogen concentration may be located at the surface of the glass-based article. The glass-based articles exhibit a Vickers indentation crack threshold (e.g., 1 kgf (about 9.8 N) or greater) without the use of conventional strengthening methods (e.g., ion exchange of a pair of alkali metal ions or thermal strengthening). A high Vickers indentation crack threshold exhibited by a glass-based article indicates high damage tolerance.

[0052] A glass-based article can be formed by exposing a glass-based substrate to an environment containing water vapor, thereby allowing hydrogen species to infiltrate the glass-based substrate and form a glass-based article having a hydrogen-containing layer. As used herein, hydrogen species include molecular water, hydroxyl, hydrogen ions, and hydronium. The composition of the glass-based substrate can be selected to promote interdiffusion of hydrogen species into the glass. As used herein, the term "glass-based substrate" refers to the precursor prior to exposure to a water vapor-containing environment to form a glass-based article including a hydrogen-containing layer. Similarly, the term "glass-based article" refers to the article including a hydrogen-containing layer after exposure.

[0053] A representative cross-section of a glass-based article 100 according to some embodiments is shown in Figure 1. The glass-based article 100 has a thickness t extending between a first surface 110 and a second surface 112. A first hydrogen-containing layer 120 extends from the first surface 110 to a first depth of layer, where the first depth of layer has a depth d1 measured from the first surface 110 into the glass-based article 100. A second hydrogen-containing layer 122 extends from the second surface 112 to a second depth of layer, where the second depth of layer has a depth d2 measured from the second surface 112 into the glass-based article 100. A region 130 that does not contain added hydrogen species exists between the first depth of layer and the second depth of layer.

[0054] The hydrogen-containing layer of the glass-based article may have a depth of layer (DOL) of greater than 5 μm. In some embodiments, the DOL is 10 μm or greater, e.g., 15 μm or greater, 20 μm or greater, 25 μm or greater, 30 μm or greater, 35 μm or greater, 40 μm or greater, 45 μm or greater, 50 μm or greater, 55 μm or greater, 60 μm or greater, 65 μm or greater, 70 μm or greater, 75 μm or greater, 80 μm or greater, 85 μm or greater, 90 μm or greater, 95 μm or greater, 100 μm or greater, 105 μm or greater, 110 μm or greater. or greater than 115 μm, or greater than 120 μm, or greater than 125 μm, or greater than 130 μm, or greater than 135 μm, or greater than 140 μm, or greater than 145 μm, or greater than 150 μm, or greater than 155 μm, or greater than 160 μm, or greater than 165 μm, or greater than 170 μm, or greater than 175 μm, or greater than 180 μm, or greater than 185 μm, or greater than 190 μm, or greater than 195 μm, or greater than 200 μm. In some embodiments, the depth of the layer is greater than 5 μm and less than or equal to 205 μm, e.g., 10 μm to 200 μm, 15 μm to 200 μm, 20 μm to 195 μm, 25 μm to 190 μm, 30 μm to 185 μm, 35 μm to 180 μm, 40 μm to 175 μm, 45 μm to 170 μm, 50 μm to 165 μm, 55 μm to 160 μm, 60 μm to 650 μm, 70 μm to 750 μm, 80 μm to 850 μm, 90 μm to 950 μm, 100 μm to 1050 μm, 110 μm to 1150 μm, 120 μm to 1250 μm, 130 μm to 1400 μm, 140 μm to 1500 μm, 150 μm to 1650 μm, 160 μm to 1750 μm, 170 μm to 1850 μm, 180 μm to 1950 μm, 190 μm to 2000 μm, 200 μm to 2250 μm, 250 μm to 2600 μm, 260 μm to 2750 μm, 270 μm to 2800 μm, 280 μm to 3000 μm, 290 μm to 3100 μm, 320 μm to 3300 μm, 340 μm to 3500 μm, 350 μm to 3600 μm, 360 μm to 40 The depth of layer may be from 0 to 155 μm, from 65 to 150 μm, from 70 to 145 μm, from 75 to 140 μm, from 80 to 135 μm, from 85 to 130 μm, from 90 to 125 μm, from 95 to 120 μm, from 100 to 115 μm, from 105 to 110 μm, or any subrange formed by any of these endpoints. Generally, the glass-based article exhibits a depth of layer that is greater than the depth of layer that may be produced by exposure to the ambient environment.

[0055] The hydrogen-containing layer of the glass-based article may have a depth of layer (DOL) greater than 0.005t, where t is the thickness of the glass-based article. In some embodiments, the depth of layer may be 0.010t or greater, e.g., 0.015t or greater, 0.020t or greater, 0.025t or greater, 0.030t or greater, 0.035t or greater, 0.040t or greater, 0.045t or greater, 0.050t or greater, 0.055t or greater, 0.060t or greater, 0.065t or greater, 0.070t or greater, 0.075t or greater, 0.080t or greater, 0.085t or greater, 0.090t or greater, 0.095t or greater, 0.10t or greater, 0.15t or greater, 0.20t or greater, or greater than 0.20t. In some embodiments, the DOL is greater than 0.005t and less than or equal to 0.205t, e.g., from 0.010t to 0.200t, from 0.015t to 0.195t, from 0.020t to 0.190t, from 0.025t to 0.185t, from 0.030t to 0.180t, from 0.035t to 0.175t, from 0.040t to 0.170t, from 0.045t to 0.165t, from 0.050t to 0.160t, or from 0.055t The range may be up to and including 0.155t, 0.060t or more and 0.150t or less, 0.065t or more and 0.145t or more, 0.070t or more and 0.140t or more, 0.075t or more and 0.135t or more, 0.080t or more and 0.130t or more, 0.085t or more and 0.125t or more, 0.090t or more and 0.120t or more, 0.095t or more and 0.115t or more, 0.100t or more and 0.110t or more, or any subrange formed by any of these endpoints.

[0056] Depth of layer and hydrogen concentration are measured using secondary ion mass spectrometry (SIMS) techniques known in the art. SIMS techniques can measure hydrogen concentration at a given depth, but cannot distinguish between hydrogen species present in a glass-based article. Therefore, all hydrogen species contribute to the hydrogen concentration measured by SIMS. As used herein, depth of layer (DOL) refers to the initial depth below the surface of a glass-based article, where the hydrogen concentration is equal to the hydrogen concentration at the center of the glass-based article. This definition takes into account the hydrogen concentration of the glass-based substrate before treatment, so depth of layer refers to the depth of hydrogen added by the treatment process. In practice, the hydrogen concentration at the center of the glass-based article can be approximated by the hydrogen concentration at a depth from the surface of the glass-based article where the hydrogen concentration is substantially constant, because the hydrogen concentration is expected to remain unchanged between such a depth and the center of the glass-based article. This approximation allows the DOL to be determined without measuring the hydrogen concentration throughout the entire depth of the glass-based article.

[0057] In some embodiments, the entire thickness of the glass-based article may be part of the hydrogen-containing layer. Such a glass-based article may be produced when treatment of the glass-based substrate continues for a sufficient time and under conditions sufficient for hydrogen species to diffuse from each exposed surface to the center of the glass-based article. In some embodiments, where the surfaces of the glass-based article are exposed to the same treatment conditions, the minimum hydrogen concentration may be located at half the thickness of the glass-based article, such that the hydrogen-containing layer contacts the center of the glass-based article. In such embodiments, the DOL may be located at half the thickness of the glass-based article. In some embodiments, the glass-based article may not include regions that do not contain added hydrogen species. In some embodiments, the glass-based article may be treated in a wet environment such that the concentration of added hydrogen species equilibrates throughout the glass-based article and the hydrogen concentration does not vary with depth below the surface of the glass-based article. Because the hydrogen concentration at the center of the glass-based article is equivalent to the hydrogen concentration at all other depths, glass-based articles according to such embodiments do not exhibit a DOL as defined herein.

[0058] The glass-based article is highly resistant to Vickers indentation cracking. High Vickers indentation cracking resistance imparts high damage tolerance to the glass-based article. Without wishing to be bound by any particular theory, the water content of the glass-based article can reduce the local viscosity of the hydrogen-containing layer, causing local flow instead of cracking. The Vickers indentation cracking threshold of the glass-based article is achieved without the use of traditional strengthening techniques, such as exchanging large alkali metal ions in the glass for smaller alkali metal ions, thermal strengthening, or laminating glass layers using mismatched thermal expansion coefficients. Glass-based articles are typically 1 kgf (approximately 9.8 N) or more, for example, 2 kgf (approximately 19.6 N) or more, 3 kgf (approximately 29.4 N) or more, 4 kgf (approximately 39.2 N) or more, 5 kgf (approximately 49 N) or more, 6 kgf (approximately 58.8 N) or more, 7 kgf (approximately 68.6 N) or more, 8 kgf (approximately 78.4 N) or more, 9 kgf (approximately 88.2 N) or more, 10 kgf (approximately 98 N) or more, 11 kgf (approximately 107.8 N) or more, 12 kgf (approximately 117.6 N) or more, 13 kgf (approximately 127.4 N) or more, 14 kgf (approximately 137.2 N) or more, 15 kgf (approximately 147 N) or more, 16 kgf (approximately 156.8 N) or more, 17 kgf (about 166.6 N) or more, 18 kgf (about 176.4 N) or more, 19 kgf (about 186.2 N) or more, 20 kgf (about 196 N) or more, 21 kgf (about 205.8 N) or more, 22 kgf (about 215.6 N) or more, 23 kgf (about 225.4 N) or more, 24 kgf (about 235.2 N) or more, 25 kgf (about 245 N) or more, 26 kgf (about 254.8 N) or more, 27 kgf (about 264.6 N) or more, 28 kgf (about 274.4 N) or more, 29 kgf (about 284.2 N) or more, 30 kgf (about 294 N) or more, or greater than 30 kgf (about 294 N).In some embodiments, the glass-based article has a compressibility of 1 kgf (about 9.8 N) to 30 kgf (about 294 N), for example, 2 kgf (about 19.6 N) to 29 kgf (about 284.2 N), 3 kgf (about 29.4 N) to 28 kgf (about 274.4 N), 4 kgf (about 39.2 N) to 27 kgf (about 264.6 N), 5 kgf (about 49 N) to 26 kgf (about 254.8 N), 6 kgf (about 58.8 N) to 25 kgf (about 245 N), 7 kgf (about 68.6 N) to 24 kgf (about 235.2 N), 8 kgf (about 78.4 N) to 23 kgf (about 225.4 N), 9 kgf (about 100 N), 12 kgf (about 130 N), 14 kgf (about 150 N), 16 kgf (about 170 N), 18 kgf (about 190 N), 19 kgf (about 200 N), 21 kgf (about 220 N), 22 kgf (about 230 N), 23 kgf (about 245 N), 24 kgf (about 250 N), 25 kgf (about 250 N), 26 kgf (about 254.8 N), 27 kgf (about 264.6 N), 28 kgf (about 274.4 N), 29 kgf (about 29.6 N), 39 kgf (about 29.4 N), 27 kgf (about 264.6 N), 26 kgf (about 254.8 N), 25 kgf (about 245 N), 26 kgf (about 254 and 14 kgf (about 137.2 N) to 17 kgf (about 166.6 N), 15 kgf (about 147 N) to 16 kgf (about 156.8 N), or any subrange formed by any of these endpoints.

[0059] The Vickers crack initiation threshold (or indentation failure threshold) was measured with a Vickers indenter. The Vickers crack initiation threshold is a measure of the indentation damage resistance of glass. This test used a square-based, pyramidal diamond indenter with a 136° angle between the faces, known as a Vickers indenter. The Vickers indenter was the same as that used in standard microhardness testing (described in ASTM-E384-11). A minimum of five specimens were selected to represent the glass type and / or sample under consideration. For each specimen, multiple sets of five indentations were made on the specimen surface. Each set of five indentations was made at a given load, with each individual indentation spaced a minimum of 5 mm apart and no closer than 5 mm to the edge of the specimen. For test loads of 2 kg or greater, an indenter loading / unloading rate of 50 kg / min was used. For test loads less than 2 kg, a rate of 5 kg / min was used. A 10-second dwell (i.e., hold) time at the target load was utilized. The machine maintained load control during the dwell period. After at least 12 hours, the indentations were inspected under reflected light at 500X magnification using a compound microscope. The presence or absence of a central / radial crack (a crack extending from the indentation along a plane perpendicular to the major plane of the article) or specimen failure was then recorded for each indentation. Note that because this test focused on the formation of a central / radial crack or specimen failure, the formation of a transverse crack (a crack extending along a plane parallel to the major plane of the article) was not considered an indicator of threshold behavior. The threshold for a specimen is defined as the midpoint of the lowest consecutive indentation load for which more than 50% of the individual indentations meet the threshold. For example, if two out of five (40%) indentations induced by a 5 kg load exceed the threshold within an individual specimen, and three out of five (60%) indentations induced by a 6 kg load exceed the threshold within that specimen, the specimen's threshold is defined as greater than 5 kg. The range of midpoint values ​​(lowest to highest) for all specimens may also be reported for each sample. The environment before, during, and after the test was controlled at 23±2°C and 50±5% RH to minimize variation in the fatigue (stress corrosion) behavior of the specimens.

[0060] Without wishing to be bound by any particular theory, the hydrogen-containing layer of the glass-based article may be the result of interdiffusion of hydrogen species of ions contained in the composition of the glass-based substrate. + and / or H + Monovalent hydrogen-containing species, such as hydronium ions (H3O4), can replace alkali metal ions in glass-based substrate compositions to form glass-based articles. The size of the alkali metal ions that the hydrogen-containing species replaces contributes to the diffusivity of the hydrogen-containing species in the glass-based substrate, as larger alkali metal ions create larger interstitial spaces that facilitate interdiffusion mechanisms. For example, hydronium ions (H3O4) can replace alkali metal ions (H3O4) in glass-based substrate compositions to form glass-based articles. + The ionic radius of ) is close to that of potassium and much larger than that of lithium. The diffusion coefficient of hydrogen-containing species in glass-based substrates was observed to be significantly higher by two orders of magnitude when the glass-based substrate contained potassium than when it contained lithium. This observed behavior may also indicate that hydronium ions are the primary monovalent hydrogen-containing species diffusing within the glass-based substrate. The ionic radii of alkali metal ions and hydronium ions are reported in Table I below. As shown in Table I, the ionic radii of rubidium and cesium are significantly larger than that of the hydronium ion, which may result in higher hydrogen diffusion coefficients than those observed for potassium.

[0061] [Table 1]

[0062] In some embodiments, replacing alkali metal ions in a glass-based substrate with hydrogen-containing ions can create a compressive stress layer that extends from the surface of the glass-based article to a compressive depth within the glass-based article. As used herein, depth of compression (DOC) refers to the depth at which the stress in the glass-based article changes from compressive to tensile. Thus, the glass-based article also includes a tensile stress region with a maximum central tension (CT) such that the forces within the glass-based article are balanced. Without wishing to be bound by theory, the compressive stress region may be the result of replacement with hydrogen-containing ions that have a larger ionic radius than the ions they replace.

[0063] In some embodiments, the compressive stress layer can comprise a compressive stress of 100 MPa or greater, e.g., 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 than 135 MPa. In some embodiments, the compressive stress layer can comprise a compressive stress of 100 MPa or greater to 150 MPa or less, e.g., 105 MPa or greater to 145 MPa, 110 MPa or greater to 140 MPa, 115 MPa or greater to 135 MPa, 120 MPa or greater to 130 MPa, 125 MPa, or any subrange formed from any of these endpoints.

[0064] In some embodiments, the DOC of the compressive stress layer can be 75 μm or more, e.g., 80 μm or more, 85 μm or more, 90 μm or more, 95 μm or more, 100 μm or more, or greater than 100 μm. In some embodiments, the DOC of the compressive stress layer can be 75 μm or more to 115 μm or less, e.g., 80 μm or more to 110 μm or less, 85 μm or more to 105 μm or less, 90 μm or more to 100 μm or less, 95 μm, or any subrange that can be formed from any of these endpoints.

[0065] In some embodiments, the glass-based article can have a DOC of 0.05t or greater, where t is the thickness of the glass-based article, e.g., 0.06t or greater, 0.07t or greater, 0.08t or greater, 0.09t or greater, 0.10t or greater, 0.11t or greater, 0.12t or greater, or greater than 0.12t. In some embodiments, the glass-based article can have a DOC of 0.05t or greater and 0.20t or less, e.g., 0.06t or greater and 0.19t or less, 0.07t or greater and 0.18t or greater, 0.08t or greater and 0.17t or greater, 0.09t or greater and 0.16t or less, 0.10t or greater and 0.15t or less, 0.11t or greater and 0.14t or less, 0.12t or greater and 0.13t or less, or any subrange formed from any of these endpoints.

[0066] In some embodiments, the CT of the glass-based article can be 10 MPa or more, e.g., 11 MPa or more, 12 MPa or more, 13 MPa or more, 14 MPa or more, 15 MPa or more, 16 MPa or more, 17 MPa or more, 18 MPa or more, 19 MPa or more, 20 MPa or more, 22 MPa or more, 24 MPa or more, 26 MPa or more, 28 MPa or more, 30 MPa or more, 32 MPa or more, or greater than 32 MPa. In some embodiments, the CT of the glass-based article can be 10 MPa or more and 35 MPa or less, e.g., 11 MPa or more and 34 MPa or less, 12 MPa or more and 33 MPa or less, 13 MPa or more and 32 MPa or less, 14 MPa or more and 32 MPa or less, 15 MPa or more and 31 MPa or less, 16 MPa or more and 30 MPa or less, 17 MPa or more and 28 MPa or less, 18 MPa or more and 26 MPa or less, 19 MPa or more and 24 MPa or less, 20 MPa or more and 22 MPa or less, or any subrange formed from any of these endpoints.

[0067] Compressive stress (including surface CS) is measured with a surface stress meter using commercially available equipment such as the FSM-6000 (FSM) manufactured by Orihara Seisakusho Co., Ltd. (Japan). Surface stress measurements rely on accurate measurement of the stress-optical coefficient (SOC), which is related to the birefringence of the glass. SOC is also measured according to Procedure C (glass disk method) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of the Stress-Optical Coefficient of Glass," the contents of which are incorporated herein by reference in their entirety. DOC is measured with the FSM. Maximum central tension (CT) values ​​are measured using a scattered light polariscope (SCALP) technique known in the art.

[0068] Glass-based articles can be formed from glass-based substrates having any suitable composition. The composition of the glass-based substrate can be specifically selected to promote the diffusion of hydrogen-containing species, thereby efficiently forming glass-based articles including a hydrogen-containing layer. In some embodiments, the glass-based substrate can have a composition including SiO2, Al2O3, and PO5. In some embodiments, the glass-based substrate can further include at least one of an alkali metal oxide, such as Li2O, Na2O, KO, Rb2O, and Cs2O. In some embodiments, the glass-based substrate can be substantially free of, or free of, at least one of lithium and sodium. In some embodiments, after diffusion of the hydrogen-containing species into the glass-based substrate, the glass-based article can have a bulk composition that is approximately the same as the composition of the glass-based substrate. In some embodiments, hydrogen species may not diffuse to the center of the glass-based article. In other words, the center of the glass-based article is the region least affected by the water vapor treatment. Thus, the center of the glass-based article can have a composition that is substantially the same as, or is the same as, the composition of the glass-based substrate before treatment in the water-containing environment.

[0069] The glass-based substrate can contain any suitable amount of SiO. SiO is the largest component, and therefore, SiO is the main component of the glass network formed from the glass composition. If the concentration of SiO in the glass composition is too high, the formability of the glass composition can be reduced. This is because a higher concentration of SiO makes it more difficult to melt the glass, which also adversely affects the formability of the glass. In some embodiments, the glass-based substrate can include SiO in an amount of 45 mol% or more and 75 mol% or less, e.g., 46 mol% or more and 74 mol% or less, 47 mol% or more and 73 mol% or less, 48 ​​mol% or more and 72 mol% or less, 49 mol% or more and 71 mol% or less, 50 mol% or more and 70 mol% or less, 51 mol% or more and 69 mol% or less, 52 mol% or more and 68 mol% or less, 53 mol% or more and 67 mol% or less, 54 mol% or more and 66 mol% or less, 55 mol% or more and 65 mol% or less, 56 mol% or more and 64 mol% or less, 57 mol% or more and 63 mol% or less, 58 mol% or more and 62 mol% or less, 59 mol% or more and 61 mol% or less, 60 mol%, or any subrange formed by any of these endpoints. In some embodiments, the glass-based substrate can include SiO in an amount of 55 mol% or more and 69 mol% or less, e.g., 58 mol% or more and 63 mol% or less, or any subrange formed by any of these endpoints.

[0070] The glass-based substrate may contain any suitable amount of Al2O3. Al2O3 can function as a glass network former, similar to SiO2. Al2O3 increases the viscosity of a glass composition due to its tetrahedral coordination in a glass melt formed from the glass composition, and if the amount of Al2O3 is too high, the formability of the glass composition decreases. However, when the Al2O3 concentration is balanced with the concentrations of SiO2 and alkali metal oxides in the glass composition, Al2O3 can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass composition in certain forming processes, such as melt-forming processes. The inclusion of Al2O3 in a glass-based substrate prevents phase separation and reduces the number of non-bridging oxygens (NBOs) in the glass. Furthermore, Al2O3 can improve the effectiveness of ion exchange. In some embodiments, the glass-based substrate can include Al2O3 in an amount of 3 mol% or more and 20 mol% or less, e.g., 4 mol% or more and 19 mol% or less, 5 mol% or more and 18 mol% or less, 6 mol% or more and 17 mol% or less, 7 mol% or more and 16 mol% or less, 8 mol% or more and 15 mol% or less, 9 mol% or more and 14 mol% or less, 10 mol% or more and 13 mol% or less, 11 mol% or more and 12 mol% or less, or any subrange formed by any of these endpoints. In some embodiments, the glass-based substrate can include Al2O3 in an amount of 5 mol% or more and 15 mol% or less, e.g., 7 mol% or more and 14 mol% or less, or any subrange formed by any of these endpoints.

[0071] The glass-based substrate can include any amount of P2O5 sufficient to provide a desired hydrogen diffusion coefficient. The inclusion of phosphorus in the glass-based substrate promotes faster interdiffusion, regardless of the exchanging ion pair. Thus, phosphorus-containing glass-based substrates enable the efficient formation of glass-based articles including hydrogen-containing layers. The inclusion of P2O5 also enables the production of glass-based articles with deep layers (e.g., greater than about 10 μm) in relatively short processing times. In some embodiments, the glass-based substrate can include P2O5 in an amount of 4 mol% to 15 mol%, e.g., 5 mol% to 14 mol%, 6 mol% to 13 mol%, 7 mol% to 12 mol%, 8 mol% to 11 mol%, 9 mol% to 10 mol%, or any subrange formed by any of these endpoints. In some embodiments, the glass-based substrate can include P2O5 in an amount of 5 mol% or more and 15 mol% or less, e.g., 6 mol% or more and 15 mol% or less, 5 mol% or more and 10 mol% or less, 6 mol% or more and 10 mol% or more, 7 mol% or more and 10 mol% or less, or any subrange formed by any of these endpoints.

[0072] The glass-based substrate can include any suitable amount of alkali metal oxide. The alkali metal oxide promotes ion exchange. The alkali metal oxides in the glass composition (e.g., LiO, NaO, and KO, as well as other alkali metal oxides including CsO and RbO) are sometimes collectively referred to as "R2O," and R2O can be expressed in mole percent. In some embodiments, the glass-based substrate may be substantially free of or free of at least one of lithium and sodium. In embodiments, the glass composition includes R2O in an amount of 6 mol% or more, e.g., 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, 15 mol% or more, 16 mol% or more, 17 mol% or more, 18 mol% or more, 19 mol% or more, 20 mol% or more, 21 mol% or more, 22 mol% or more, 23 mol% or more, or 24 mol% or more. In one or more embodiments, the glass composition includes RO in an amount of 25 mol% or less, e.g., 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, or 7 mol% or less. It is understood that any of the above ranges may be combined with any other range in an embodiment. In some embodiments, the glass composition comprises RO in an amount of from 6.0 mol% to 25.0 mol%, e.g., from 7.0 mol% to 24.0 mol%, from 8.0 mol% to 23.0 mol%, from 9.0 mol% to 22.0 mol%, from 10.0 mol% to 21.0 mol%, from 11.0 mol% to 20.0 mol%, from 12.0 mol% to 19.0 mol%, from 13.0 mol% to 18.0 mol%, from 14.0 mol% to 17.0 mol%, or from 15.0 mol% to 16.0 mol%, and all ranges and subranges therebetween.

[0073] In some embodiments, the alkali metal oxide can be KO. The inclusion of KO allows for efficient exchange of hydrogen species into the glass substrate when exposed to a water-containing environment. In embodiments, the glass-based substrate can include KO in an amount of 6 mol% to 25 mol%, e.g., 7 mol% to 24 mol%, 8 mol% to 23 mol%, 9 mol% to 22 mol%, 10 mol% to 21 mol%, 11 mol% to 20 mol%, 12 mol% to 19 mol%, 13 mol% to 18 mol%, 14 mol% to 17 mol%, 15 mol% to 16 mol%, or any subrange formed from any of these endpoints. In some embodiments, the glass-based substrate can include KO in an amount of 10 mol% or more and 25 mol% or less, e.g., 10 mol% or more and 20 mol% or less, 11 mol% or more and 25 mol% or less, 11 mol% or more and 20 mol% or more, 15 mol% or more and 20 mol% or less, or any subrange formed from any of these endpoints.

[0074] The glass-based substrate can include RbO in any suitable amount, in some embodiments, from 0 mol% to 10 mol%, e.g., from 1 mol% to 9 mol%, from 2 mol% to 8 mol%, from 3 mol% to 7 mol%, from 4 mol% to 6 mol%, 5 mol%, or any subrange formed from any of these endpoints.

[0075] The glass-based substrate can include CsO in any suitable amount, in some embodiments, from 0 mol% to 10 mol%, e.g., from 1 mol% to 9 mol%, from 2 mol% to 8 mol%, from 3 mol% to 7 mol%, from 4 mol% to 6 mol%, 5 mol%, or any subrange formed from any of these endpoints.

[0076] In some embodiments, the glass-based substrate can have a composition including 45 mol% to 75 mol% SiO, 3 mol% to 20 mol% AlO, 6 mol% to 15 mol% PO, and 6 mol% to 25 mol% KO.

[0077] In some embodiments, the glass-based substrate can have a composition including 45 mol% to 75 mol% SiO, 3 mol% to 20 mol% AlO, 4 mol% to 15 mol% PO, and 11 mol% to 25 mol% KO.

[0078] In some embodiments, the glass-based substrate can have a composition including 55 mol% to 69 mol% SiO, 5 mol% to 15 mol% AlO, 6 mol% to 10 mol% PO, and 10 mol% to 20 mol% KO.

[0079] In some embodiments, the glass-based substrate can have a composition including 55 mol% to 69 mol% SiO, 5 mol% to 15 mol% AlO, 5 mol% to 10 mol% PO, and 11 mol% to 20 mol% KO.

[0080] In some embodiments, the glass-based substrate can have a composition including 58 mol% to 63 mol% SiO, 7 mol% to 14 mol% AlO, 7 mol% to 10 mol% PO, and 15 mol% to 20 mol% KO.

[0081] In some embodiments, the glass-based substrate may exhibit a Vickers crack initiation threshold of 5 kgf (about 49 N) or greater, e.g., 6 kgf (about 58.8 N) or greater, 7 kgf (about 68.6 N) or greater, 8 kgf (about 78.4 N) or greater, 9 kgf (about 88.2 N) or greater, 10 kgf (about 98 N) or greater, or greater than 10 kgf (about 98 N).

[0082] The glass-based substrate may have any suitable shape. In some embodiments, the glass-based substrate may have a thickness of 2 mm or less, e.g., 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 than 300 μm. In some embodiments, the glass-based substrate may be in a plate or sheet shape. In some other embodiments, the glass-based substrate may have a 2.5D or 3D shape. As used herein, a "2.5D shape" refers to a sheet-shaped article having at least one major surface that is at least partially non-planar and a second major surface that is substantially planar. As used herein, a "3D shape" refers to an article having first and second opposing major surfaces that are at least partially non-planar.

[0083] Glass-based articles can be produced from glass-based substrates by exposing them to water vapor under any suitable conditions. Exposure can be carried out in any suitable apparatus, such as an oven with relative humidity control. In some embodiments, the glass-based substrate can be exposed to an environment having a relative humidity of 75% or greater, e.g., 80% or greater, 85% or greater, 90% or greater, 95% or greater, 99% or greater, or greater than 99%. In some embodiments, the glass-based substrate can be exposed to an environment having a relative humidity of 100%.

[0084] In some embodiments, the glass-based substrate can be exposed to an environment at a temperature of 70°C or higher, e.g., 75°C or higher, 80°C or higher, 85°C or higher, 90°C or higher, 95°C or higher, 100°C or higher, 105°C or higher, 110°C or higher, 115°C or higher, 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, 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, or greater than 200°C. In some embodiments, the glass-based substrate can be exposed to an environment at a temperature of from 70°C to 210°C, e.g., from 75°C to 205°C, from 80°C to 200°C, from 85°C to 195°C, from 90°C to 190°C, from 95°C to 185°C, from 100°C to 180°C, from 105°C to 175°C, from 110°C to 170°C, from 115°C to 165°C, from 120°C to 160°C, from 125°C to 155°C, from 130°C to 150°C, from 135°C to 145°C, 140°C, or any subrange formed by these endpoints.

[0085] In some embodiments, the glass-based substrate can be exposed to a water vapor-containing environment for a time sufficient to provide a desired degree of diffusion of hydrogen-containing species and a desired layer depth. In some embodiments, the glass-based substrate can be exposed to a water vapor-containing environment for 1 day or more, e.g., 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, 45 days or more, 50 days or more, 55 days or more, 60 days or more, 65 days or more, or more than 65 days. In some embodiments, the glass-based substrate can be exposed to a water vapor-containing environment for a period of 1 to 70 days, e.g., 2 to 65 days, 3 to 60 days, 4 to 55 days, 5 to 45 days, 6 to 40 days, 7 to 35 days, 8 to 30 days, 9 to 25 days, 10 to 20 days, 15 days, or any subrange formed from any of these endpoints. The exposure conditions can be modified to shorten the time required to achieve a desired amount of diffusion of hydrogen-containing species into the glass-based substrate. For example, the temperature and / or relative humidity can be increased to shorten the time required to achieve a desired degree of diffusion and depth of hydrogen-containing species into the glass-based substrate.

[0086] The glass-based articles disclosed herein may be incorporated into another article, such as an article with a display (or display article) (e.g., consumer electronics products, including cell phones, tablets, computers, navigation systems, wearable devices (e.g., watches), etc.), a building article, a transportation article (e.g., automobiles, trains, aircraft, watercraft, etc.), a specialized appliance article, or any article requiring some degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. An exemplary article incorporating any of the glass-based articles disclosed herein is shown in Figures 2A and 2B. Specifically, Figures 2A and 2B show a consumer electronic device 200 including a housing 202 having a front surface 204, a back surface 206, and sides 208; electrical components (not shown) at least partially within or entirely within the housing and including at least a controller, memory, and a display 210 located on or adjacent to the front surface of the housing; and a cover substrate 212 located on or over the front surface of the housing to cover the display. In some embodiments, at least a portion of one of the cover substrate 212 and the housing 202 may include any of the glass-based articles disclosed herein.

[0087] Illustrative Embodiments Glass compositions particularly suitable for forming the glass-based articles described herein were formed into glass-based substrates. The compositions of Examples 1-6 are listed in Table II below. Density was 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 was 10 -7 The viscosity is expressed in units of / °C and was determined using a push rod dilatometer in accordance with ASTM E228-11. Strain points and annealing points were determined using the beam bending viscosity method of ASTM C598-93(2013). Softening points were determined using the parallel plate viscosity method of ASTM C1351M-96(2012). The temperatures at which the viscosity of the glass was 200P, 35,000P, and 200,000P were measured for the resulting compositions in accordance with ASTM C965-96(2012), entitled "Standard Practice for Measuring the Viscosity of Glasses Above Their Softening Points."

[0088] [Table 2]

[0089] A glass-based 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-based article comprising a hydrogen-containing layer of the type described herein.

[0090] The hydrogen-containing layer depth was measured by SIMS before and after exposure. The results of the SIMS hydrogen concentration measurements are shown in Figure 3, where the hydrogen concentration curve 301 for the untreated glass-based substrate has a layer depth of approximately 5 μm, and the hydrogen concentration curve 302 for the glass-based article has a layer depth of approximately 30 μm. The exposed glass-based article was measured to a depth of approximately 25 μm, and the layer depth was determined by extrapolating curve 303. The hydrogen diffusion coefficient (D) was calculated based on the measurements using the general formula DOL = √(D × time).

[0091] The Vickers indentation crack threshold was measured before and after exposure to a water vapor-containing environment. The Vickers indentation results for the glass-based substrate before exposure are shown in Figures 4 and 5 after indentation with 5 kgf (approximately 49 N) and 10 kgf (approximately 98 N), respectively. As shown in Figures 4 and 5, the glass-based substrate had a Vickers crack initiation threshold higher than 5 kgf (approximately 49 N) but lower than 10 kgf (approximately 98 N). The Vickers indentation results for the exposed glass-based article are shown in Figures 6, 7, and 8 after indentation with 5 kgf (approximately 49 N), 10 kgf (approximately 98 N), and 20 kgf (approximately 196 N), respectively. As shown in Figures 6, 7, and 8, the Vickers indentation crack threshold of the glass-based article exceeded 20 kgf (approximately 196 N).

[0092] Glass-based substrates containing the compositions of Comparative Examples 1-3 and having a thickness of 1 mm were also prepared and exposed to an environment of 85% relative humidity for 30 days. The compositions of Comparative Examples 1-3 are reported in Table III below. The Vickers indentation crack threshold was measured before and after exposure to the water vapor-containing environment, and the hydrogen-containing layer depth was measured by SIMS after exposure. The hydrogen diffusion coefficient was calculated based on the measured values.

[0093] [Table 3]

[0094] As shown in Table III, the glass composition of Example 1 exhibited a hydrogen diffusion coefficient two orders of magnitude higher than that of Comparative Example 3, which also contained potassium but no phosphorus. These results indicate that the presence of phosphorus in the glass composition significantly increases the hydrogen diffusion coefficient. Similarly, the glass composition of Comparative Example 3 exhibited a hydrogen diffusion coefficient two orders of magnitude higher than that of Comparative Examples 1 and 2, which contained lithium and sodium, respectively. The difference in hydrogen diffusion coefficient between the potassium-containing glass composition and the lithium- and sodium-containing glass compositions indicates that alkali metal ions with larger ionic radii enable faster hydrogen diffusion.

[0095] Glass-based substrates containing the glass composition of Example 6 were produced in 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 7 days to produce glass-based articles of the type described herein. The glass-based articles exhibited a compressive stress region extending from the surface to the compression depth. The 0.5 mm glass-based article had a measured maximum compressive stress of 124 MPa, and the 1.0 mm glass-based article had a measured maximum compressive stress of 137 MPa. The 0.5 mm glass-based article had a measured maximum central tension of 32 MPa, and the 1.0 mm glass-based article had a measured maximum central tension of 15 MPa. The 0.5 mm glass-based article had a compressed depth of 101 μm, and the 1.0 mm glass-based article had a compressed depth of 99 μm.

[0096] After exposure to a 100% relative humidity environment at 200°C for 7 days, samples were cut from the center of 0.5 mm and 1.0 mm thick glass-based articles formed from glass-based substrates containing the glass composition of Example 6. 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 under the following conditions: CaF / InSb, 64 scans, 16 cm -1 The scan was performed with a resolution of 10 μm, an aperture of 10 μm, and a step of 10 μm. The scan started at the surface of the sample and continued to approximately the midpoint of the thickness. The spectrum was generated for "dry" silica, with a hydroxyl (βOH) concentration of 3900 cm -1 (max) and 3550 cm -1 The calculations were performed using parameters of (minimum). Because it was not possible to distinguish between bound and molecular hydroxyls due to the multicomponent nature of the glass-based articles, the plots report the concentration of total hydroxyl content. Measured hydroxyl concentration profiles for 0.5 mm and 1.0 mm thick samples are shown in Figures 9 and 10, respectively. As shown in Figures 9 and 10, the depth within the sample where the measured hydroxyl content becomes substantially constant and equivalent to the hydroxyl content at the center of the article was approximately 200 μm, as measured by FTIR, indicating the background hydroxyl content of the precursor glass-based substrate. The appearance of the buried hydroxyl concentration peak in Figures 9 and 10 is an artifact of the measurement method.

[0097] Square samples having the composition of Example 1 were prepared with a thickness of 1 mm and sides of 50 mm. Five of these samples were then treated at 200°C for 121 hours in a 100% relative humidity environment. The compressive stress (CS) and depth of compression (DOC) of the treated samples were then measured by FSM, with a CS of 167 MPa and a DOC of 73 μm. The five steam-treated samples and three control samples not exposed to steam treatment were then subjected to abrasive ring-on-ring (AROR) testing. The strength and peak load of each tested sample are shown in Table IV. As shown in Table IV, the steam-treated samples exhibited significantly increased peak load and strength compared to the untreated control samples.

[0098] [Table 4]

[0099] The AROR test is a surface strength measurement for examining flat glass specimens, and ASTM C1499-09(2013), entitled "Standard Test Method for Equibiaxial Bending Strength of Advanced Ceramics at Ambient Temperature," is the basis for the AROR test method used herein. The contents of ASTM C1499-09 are incorporated herein by reference in their entirety. Prior to the ring-on-ring test, the glass specimens are polished using 90-grit silicon carbide (SiC) particles delivered to the glass sample using the method and apparatus described in Appendix A2, entitled "Polishing Procedure," in ASTM C158-02(2012), entitled "Standard Test Method for Strength of Glass in Bending (Measurement of Modulus of Rupture)." The contents of ASTM C158-02, and particularly Appendix 2, are incorporated herein by reference in their entirety.

[0100] The surfaces of the glass-based article samples were abraded prior to the ring-on-ring test as described in ASTM C158-02, Appendix 2, to normalize and / or control the surface defect state of the samples using the apparatus shown in Figure A2.1 of ASTM C158-02. The abrasive material was sandblasted onto the surface of the glass-based article at an air pressure of 5 psi (approximately 34 kPa). After the air flow was established, the abrasive material was sandblasted 1 cm. 3 of abrasive material is added to the funnel and the sample is sandblasted.

[0101] In the AROR test, a glass-based article having at least one wear surface is placed between two concentric rings of different sizes to measure equibiaxial flexural strength (i.e., the maximum stress the material can withstand when subjected to bending between two concentric rings), as shown in Figure 11. In the AROR configuration 400, a polished glass-based article 410 is supported by a support ring 420 having a diameter D2. A force F is applied to the surface of the glass-based article by a load ring 430 having a diameter D1 via a load cell (not shown).

[0102] The ratio of the diameters of the load ring to the support ring, D1 / D2, can range from 0.2 to 0.5. In some embodiments, D1 / D2 is 0.5. The load ring 430 and the support ring 420 are preferably concentrically aligned to within 0.5% of the support ring diameter D2. The load cell used for testing is preferably accurate to within ±1% at any load within the selected range. Testing is performed at a temperature of 23±2°C and a relative humidity of 40±10%.

[0103] In the fixture design, the radius r of the protruding surface of the load ring 430 is in the range h / 2≦r≦3h / 2, where h is the thickness of the glass-based article 410. The load ring 430 and the support ring 420 are made of hardened steel with a hardness of HRc>40. The AROR fixture is commercially available.

[0104] The intended failure mechanism of the AROR test is to observe failure of the glass-based article 410 originating at surface 430a within the loading ring 430. Failures occurring outside of this region, i.e., between the loading ring 430 and the support ring 420, are excluded from data analysis. However, due to the thinness and high strength of the glass-based article 410, large deflections exceeding half the specimen thickness h are sometimes observed. Therefore, it is not uncommon for a high percentage of failures to originate below the loading ring 430. Without knowing the stress development both inside and below the ring (collected via strain gauge analysis) and the origin of failure for each specimen, stress cannot be accurately calculated. Therefore, the AROR test focuses on the peak load at failure as the measured response.

[0105] While exemplary embodiments have been set forth for purposes of illustration, the foregoing description should not be deemed to limit the scope of this disclosure or the appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to those skilled in the art without departing from the spirit and scope of this disclosure or the appended claims.

[0106] Preferred embodiments of the present invention will be described below in detail.

[0107] Embodiment 1 A glass-based article, SiO2, Al2O3 and P2O5; and a hydrogen-containing layer extending from the surface of the glass-based article to a layer depth; Including, The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth, and The glass-based article, wherein the depth of layer is greater than 5 μm.

[0108] Embodiment 2 2. The glass-based article of embodiment 1, wherein the glass-based article has a Vickers crack initiation threshold of at least 1 kgf (about 9.8 N).

[0109] Embodiment 3 3. The glass-based article of claim 1 or 2, wherein the depth of layer is at least about 10 μm.

[0110] Embodiment 4 4. The glass-based article of any one of claims 1 to 3, wherein the maximum hydrogen concentration is located at a surface of the glass-based article.

[0111] Embodiment 5 5. The glass-based article of any one of claims 1 to 4, further comprising at least one of Li2O, Na2O, K2O, Cs2O, and Rb2O.

[0112] Embodiment 6 6. The glass-based article of any one of claims 1 to 5, further comprising KO.

[0113] Embodiment 7 The center of the glass-based article is 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 6 mol% to 15 mol% P2O5; and 6 mol% or more and 25 mol% or less of K2O 7. The glass-based article of any one of embodiments 1 to 6, comprising:

[0114] Embodiment 8 The center of the glass-based article is 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 4 mol% to 15 mol% P2O5; and 11 mol% or more and 25 mol% or less of K2O 7. The glass-based article of any one of embodiments 1 to 6, comprising:

[0115] Embodiment 9 The center of the glass-based article is 55 mol% or more and 69 mol% or less of SiO2; 5 mol% or more and 15 mol% or less of Al2O3; 6 mol% to 10 mol% P2O5; and 10 mol% or more and 20 mol% or less of K2O 7. The glass-based article of any one of embodiments 1 to 6, comprising:

[0116] Embodiment 10 The center of the glass-based article is 0 mol% to 10 mol% CsO; and 0 mol% to 10 mol% RbO 10. The glass-based article of any one of embodiments 7 to 9, comprising:

[0117] Embodiment 11 11. The glass-based article of any one of claims 1 to 10, wherein the glass-based article is substantially free of at least one of lithium and sodium.

[0118] Embodiment 12 12. The glass-based article of any one of claims 1 to 11, further comprising a compressive stress layer extending from a surface of the glass-based article to a compressive depth within the glass-based article.

[0119] Embodiment 13 13. The glass-based article of embodiment 12, wherein the compressive stress layer comprises a compressive stress of 100 MPa or more, and the compression depth is 75 μm or more.

[0120] Embodiment 14 A household electronic product, the housing, including the front, back and sides; an electrical component at least partially within the housing, the electrical component including at least a controller, a memory, and a display, the display being located on or adjacent to a 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 comprises the glass-based article of any one of claims 1 to 13.

[0121] Embodiment 15 It is glass, 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 6 mol% to 15 mol% P2O5; and 6 mol% or more and 25 mol% or less of K2O Including glass.

[0122] Embodiment 16 55 mol% or more and 69 mol% or less of SiO2; 5 mol% or more and 15 mol% or less of Al2O3; 6 mol% to 10 mol% P2O5; and 10 mol% or more and 20 mol% or less of K2O 16. The glass of embodiment 15, comprising:

[0123] Embodiment 17 0 mol% to 10 mol% CsO; and 0 mol% to 10 mol% RbO 17. The glass of embodiment 15 or 16, further comprising:

[0124] Embodiment 18 18. The glass of any one of claims 15 to 17, wherein the glass is substantially free of lithium.

[0125] Embodiment 19 19. The glass of any one of claims 15 to 18, wherein the glass is substantially free of sodium.

[0126] Embodiment 20 58 mol% or more and 63 mol% or less of SiO2; 7 mol% or more and 14 mol% or less Al2O3; 7 mol% or more and 10 mol% or less of P2O5; and 15 mol% or more and 20 mol% or less of K2O 20. The glass of any one of claims 15 to 19, comprising:

[0127] Embodiment 21 21. The glass of any one of claims 15 to 20, wherein the glass has a Vickers crack initiation threshold of 5 kgf (about 49 N) or greater.

[0128] Embodiment 22 22. The glass of any one of embodiments 15 to 17, 20, and 21, further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0129] Embodiment 23 It is glass, 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 4 mol% to 15 mol% P2O5; and 11 mol% or more and 25 mol% or less of K2O Including glass.

[0130] Embodiment 24 55 mol% or more and 69 mol% or less of SiO2; 5 mol% or more and 15 mol% or less of Al2O3; 5 mol% or more and 10 mol% or less of P2O5; and 11 mol% or more and 20 mol% or less of K2O 24. The glass of embodiment 23, comprising:

[0131] Embodiment 25 0 mol% to 10 mol% CsO; and 0 mol% to 10 mol% RbO 25. The glass of embodiment 23 or 24, further comprising:

[0132] Embodiment 26 26. The glass of any one of claims 23 to 25, wherein the glass is substantially free of lithium.

[0133] Embodiment 27 27. The glass of any one of claims 23 to 26, wherein the glass is substantially free of sodium.

[0134] Embodiment 28 58 mol% or more and 63 mol% or less of SiO2; 7 mol% or more and 14 mol% or less Al2O3; 7 mol% or more and 10 mol% or less of P2O5; and 15 mol% or more and 20 mol% or less of K2O 28. The glass of any one of embodiments 23 to 27, comprising:

[0135] Embodiment 29 29. The glass of any one of claims 23 to 28, wherein the glass has a Vickers crack initiation threshold of 5 kgf (about 49 N) or greater.

[0136] Embodiment 30 30. The glass of any one of embodiments 23 to 25, 28, and 29, further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0137] Embodiment 31 1. A method comprising: exposing the glass-based substrate to an environment having a relative humidity of 75% or greater to form a glass-based article having a hydrogen-containing layer extending from the surface to a depth of the glass-based article. Including, the glass-based substrate contains SiO2, Al2O3, and P2O5; The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth; and The method wherein the depth of the layer is 5 μm or greater.

[0138] Embodiment 32 The glass-based substrate is 55 mol% or more and 69 mol% or less of SiO2; 5 mol% or more and 15 mol% or less of Al2O3; 6 mol% to 10 mol% P2O5; and 10 mol% or more and 20 mol% or less of K2O 32. The method of embodiment 31, having a composition comprising:

[0139] Embodiment 33 The glass-based substrate is 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 4 mol% to 15 mol% P2O5; and 11 mol% or more and 25 mol% or less of K2O 32. The method of embodiment 31, having a composition comprising:

[0140] Embodiment 34 The glass-based substrate is 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less Al2O3; 6 mol% to 15 mol% P2O5; and 6 mol% or more and 25 mol% or less of K2O 32. The method of embodiment 31, having a composition comprising:

[0141] Embodiment 35 The glass-based substrate is 0 mol% to 10 mol% CsO; and 0 mol% to 10 mol% RbO 35. The method of any one of embodiments 31 to 34, further comprising:

[0142] Embodiment 36 36. The method of any one of embodiments 31 to 35, further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0143] Embodiment 37 37. The method of any one of claims 31 to 36, wherein the glass-based article is substantially free of at least one of lithium and sodium.

[0144] Embodiment 38 38. The method of any one of embodiments 31 to 37, wherein said exposing is performed at a temperature of 70° C. or greater.

[0145] Embodiment 39 39. The method of any one of claims 31 to 38, wherein the glass-based article has a Vickers crack initiation threshold of 1 kgf (about 9.8 N) or greater.

Claims

1. A glass article strengthened by water treatment, The main components are SiO 2 and Al 2 O 3 , 4 mol % or more and 15 mol % or less of P 2 O 5 , and 11 mol% or more and 25 mol% or less of K ２ O. The glass article comprises: the surface of the glass article; a hydrogen-containing layer extending from the surface of the glass article to a depth into the glass article; and a compressive stress layer of hydrogen species extending from the surface of the glass article to a compression depth into the glass article; Including, the depth of layer is a first depth below the surface where the hydrogen concentration matches the hydrogen concentration at the center of the glass article, and the compression depth is a depth where stress in the glass article changes from compressive to tensile; the depth of the layer is greater than 5 μm from the surface; The compressive stress layer has a compressive stress of at least 100 MPa. Glass articles.

2. The glass article of claim 1 , wherein the hydrogen species comprises one or more of molecular water, hydroxyl, hydrogen ions, and hydronium.

3. 10. The glass article of claim 1, wherein the surface is a first surface of the glass article, the glass article further having a second surface and a thickness between the first surface and the second surface, and the depth of layer is greater than 0.005 times the thickness of the glass article.

4. 10. The glass article of claim 1, wherein the surface is a first surface of the glass article, the glass article further having a second surface and a thickness between the first surface and the second surface, and the glass article has a 3D shape such that the first surface and the second surface are at least partially non-planar.

5. Electrical components, including displays; and a cover for covering the display; 10. A device comprising: a glass article according to claim 1, wherein at least a portion of the cover comprises the glass article according to claim 1.

Images