Hydrogen-containing glass articles with high indentation crack threshold

Abstract

To provide glass articles that exhibit higher performance, such as damage resistance, for use in portable electronic devices. [Solution] A glass is provided comprising a hydrogen-containing layer extending from the surface to the layer depth, and a compressive stress layer extending from the surface to the compression depth. The hydrogen concentration in the hydrogen-containing layer decreases from the maximum hydrogen concentration towards the layer depth, and the hydrogen species include one or more of molecular water, hydroxyl, hydrogen ions, and hydronium. The glass exhibits a high Vickers indentation crack threshold.

Description

Related Applications

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 62 / 587,872, filed Nov. 17, 2017, and Korean Application No. 2020896, filed May 8, 2018, the contents of both applications are relied upon and incorporated herein by reference in their entirety.

[0002] Also, this application is a divisional application of Japanese Patent Application No. 2020-526391, filed Nov. 16, 2018.

Technical Field

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

Background Art

[0004] Portable electronic devices, such as smartphones, tablets, and wearable devices (e.g., watches and fitness trackers, etc.), are becoming increasingly smaller and more complex. Thus, the materials conventionally used on at least one outer surface of such portable electronic devices are also becoming increasingly complex. For example, as portable electronic devices are increasingly miniaturized and thinned to meet consumer demands, the display covers and housings used in these portable electronic devices are also increasingly miniaturized and thinned, and as a result, the performance requirements for the materials used to form these components are becoming higher.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, there is a need for materials with higher performance, such as damage resistance, for use in portable electronic devices.

Means for Solving the Problems

[0006] Embodiment (1) provides a glass-based article. The glass-based article comprises SiO2, Al2O3, and P2O5; and a hydrogen-containing layer extending from the surface of the glass-based article to a layer depth. The hydrogen concentration in the hydrogen-containing layer decreases from the maximum hydrogen concentration towards the layer depth, and the layer depth is greater than 5 μm.

[0007] Embodiment (2) provides the glass-based article described in Embodiment (1), wherein the glass-based article has a Vickers crack initiation threshold of 1 kgf (approximately 9.8 N) or more.

[0008] Embodiment (3) provides a glass-based article according to Embodiment (1) or (2), wherein the layer depth is 10 μm or more.

[0009] Embodiment (4) provides a glass-based article according to any one of embodiments (1) to (3), wherein the maximum hydrogen concentration is located on the surface of the glass-based article.

[0010] Embodiment (5) provides a glass-based article according to any one of embodiments (1) to (4), further comprising at least one of Li2O, Na2O, K2O, Cs2O, and Rb2O.

[0011] Embodiment (6) provides a glass-based article according to any one of embodiments (1) to (5), further comprising K2O.

[0012] Embodiment (7) provides a glass-based article according to any one of embodiments (1) to (6), wherein the core of the glass-based article contains 45 mol% to 75 mol% of SiO2; 3 mol% to 20 mol% of Al2O3; 6 mol% to 15 mol% of P2O5; and 6 mol% to 25 mol% of K2O.

[0013] Embodiment (8) provides a glass-based article according to any one of embodiments (1) to (6), wherein the core of the glass-based article contains 45 mol% to 75 mol% of SiO2; 3 mol% to 20 mol% of Al2O3; 4 mol% to 15 mol% of P2O5; and 11 mol% to 25 mol% of K2O.

[0014] Embodiment (9) provides a glass-based article according to any one of embodiments (1) to (6), wherein the core of the glass-based article contains 55 mol% to 69 mol% of SiO2; 5 mol% to 15 mol% of Al2O3; 6 mol% to 10 mol% of P2O5; and 10 mol% to 20 mol% of K2O.

[0015] Embodiment (10) provides a glass-based article according to any one of embodiments (7) to (9), wherein the core of the glass-based article contains 0 mol% to 10 mol% of Cs2O and 0 mol% to 10 mol% of Rb2O.

[0016] Embodiment (11) provides a glass-based article according to any one of embodiments (1) to (10), wherein the glass-based article substantially does not contain at least one of lithium and sodium.

[0017] Embodiment (12) provides a glass-based article according to any one of embodiments (1) to (11), further comprising a compressive stress layer extending from the surface of the glass-based article to the compressive depth within the glass-based article.

[0018] Embodiment (13) provides a glass-based article according to Embodiment (12), wherein the compressive stress layer contains a compressive stress of at least about 100 MPa and has a compression depth of at least about 75 μm.

[0019] In aspect (14), a household electronic product is provided. The household electronic product includes a housing including a front surface, a back surface, and side surfaces; electrical components at least partially within the housing, including at least a controller, a memory, and a display, and the display is provided on 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 according to any one of aspects (1) to (13).

[0020] In aspect (15), glass is provided. The glass includes 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less of Al2O3; 6 mol% or more and 15 mol% or less of P2O5; and 6 mol% or more and 25 mol% or less of K2O.

[0021] In aspect (16), the glass according to aspect (15) is provided, including 55 mol% or more and 69 mol% or less of SiO2; 5 mol% or more and 15 mol% or less of Al2O3; 6 mol% or more and 10 mol% or less of P2O5; and 10 mol% or more and 20 mol% or less of K2O.

[0022] In aspect (17), the glass according to aspect (15) or (16) is provided, further including 0 mol% or more and 10 mol% or less of Cs2O; and 0 mol% or more and 10 mol% or less of Rb2O.

[0023] In aspect (18), the glass according to any one of aspects (15) to (17) is provided, and the glass substantially does not contain lithium.

[0024] In aspect (19), the glass according to any one of aspects (15) to (18) is provided, and the glass substantially does not contain sodium.

[0025] In aspect (20), there is provided a glass according to any one of aspects (15) to (19), comprising 58 mol% or more and 63 mol% or less of SiO2; 7 mol% or more and 14 mol% or less of Al2O3; 7 mol% or more and 10 mol% or less of P2O5; and 15 mol% or more and 20 mol% or less of K2O.

[0026] In aspect (21), there is provided a glass according to any one of aspects (15) to (20), having a Vickers crack initiation threshold of 5 kgf (about 49 N) or more.

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

[0028] In aspect (23), there is provided a glass. The glass comprises 45 mol% or more and 75 mol% or less of SiO2; 3 mol% or more and 20 mol% or less of Al2O3; 4 mol% or more and 15 mol% or less of P2O5; and 11 mol% or more and 25 mol% or less of K2O.

[0029] In aspect (24), there is provided a glass according to aspect (23), comprising 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.

[0030] In aspect (25), there is provided a glass according to aspect (23) or (24), further comprising 0 mol% or more and 10 mol% or less of Cs2O; and 0 mol% or more and 10 mol% or less of Rb2O.

[0031] In aspect (26), there is provided a glass according to any one of aspects (23) to (25), substantially free of lithium.

[0032] In aspect (27), there is provided a glass according to any one of aspects (23) to (26), substantially free of sodium.

[0033] Embodiment (28) provides a glass according to any one of embodiments (23) to (27), comprising 58 mol% to 63 mol% of SiO2; 7 mol% to 14 mol% of Al2O3; 7 mol% to 10 mol% of P2O5; and 15 mol% to 20 mol% of K2O.

[0034] Embodiment (29) provides a glass according to any one of embodiments (23) to (28), wherein the glass has a Vickers crack initiation threshold of 5 kgf (approximately 49 N) or more.

[0035] Embodiment (30) provides a glass according to any one of embodiments (23) to (29), further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0036] Embodiment (31) provides a method, which includes the step of exposing a glass substrate to an environment with a relative humidity of 75% or higher to form a glass article having a hydrogen-containing layer extending from the surface of the glass article to a layer depth. The glass substrate comprises SiO2, Al2O3, and P2O5. The hydrogen concentration in the hydrogen-containing layer decreases from the maximum hydrogen concentration towards the layer depth, and the layer depth is greater than 5 μm.

[0037] Embodiment (32) provides the method described in Embodiment (31), wherein the glass substrate has a composition comprising 55 mol% to 69 mol% of SiO2; 5 mol% to 15 mol% of Al2O3; 6 mol% to 10 mol% of P2O5; and 10 mol% to 20 mol% of K2O.

[0038] Embodiment (33) provides the method described in Embodiment (31), wherein the glass substrate has a composition comprising 45 mol% to 75 mol% of SiO2; 3 mol% to 20 mol% of Al2O3; 4 mol% to 15 mol% of P2O5; and 11 mol% to 25 mol% of K2O.

[0039] Embodiment (34) provides the method described in Embodiment (31), wherein the glass substrate has a composition comprising 45 mol% to 75 mol% of SiO2; 3 mol% to 20 mol% of Al2O3; 6 mol% to 15 mol% of P2O5; and 6 mol% to 25 mol% of K2O.

[0040] Embodiment (35) provides a method according to any one of embodiments (31) to (34), wherein the glass substrate further comprises 0 mol% to 10 mol% of Cs2O and 0 mol% to 10 mol% of Rb2O.

[0041] Embodiment (36) provides the method according to any one of embodiments (31) to (35), further comprising at least one of Li2O, Na2O, Cs2O, and Rb2O.

[0042] Embodiment (37) provides a method according to any one of embodiments (31) to (36) in which the glass article substantially does not contain at least one of lithium and sodium.

[0043] Embodiment (38) provides a method according to any one of embodiments (31) to (37), wherein the exposure is carried out at a temperature of 70°C or higher.

[0044] Embodiment (39) provides a method according to any one of embodiments (31) to (38), wherein the glass-based article has a Vickers crack initiation threshold of 1 kgf (approximately 9.8 N) or more.

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

[0046] [Figure 1] This is a cross-sectional view of a glass-based article according to one embodiment. [Figure 2A] This is a plan view of an exemplary electronic device incorporating one of the glass-based articles disclosed herein. [Figure 2B] Figure 2A is a perspective view of an exemplary electronic device. [Figure 3] This figure shows the measurement of hydrogen concentration as a function of depth below the surface of a glass-based article formed from a glass-based substrate having the composition of Example 1, using SIMS. [Figure 4] This figure shows a photograph of Vickers indentations at 5 kgf (approximately 49 N) on a glass substrate having the composition of Example 1, before exposure to a hydrated environment. [Figure 5] This figure shows a photograph of Vickers indentation at 10 kgf (approximately 98 N) on a glass substrate having the composition of Example 1, before exposure to a humid environment. [Figure 6] This figure shows a photograph of 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 hydrated environment. [Figure 7] This figure shows a photograph of 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 hydrated environment. [Figure 8] This figure shows a photograph of 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 hydrated environment. [Figure 9] This figure shows a plot of the hydroxyl (βOH) concentration of a 0.5 mm thick glass article as a function of depth from the surface after exposure to a hydrated environment, according to one embodiment. [Figure 10] This figure shows a plot of the hydroxyl (βOH) concentration of a 1.0 mm thick glass article as a function of depth from the surface after exposure to a hydrated environment, according to one embodiment. [Figure 11] This is a side view of a ring-on-ring test apparatus. [Modes for carrying out the invention]

[0047] In the following description, similar reference letters indicate similar or corresponding parts throughout the figure from several specified locations shown in the figure. It should also be understood that, unless otherwise specified, terms such as “upper,” “lower,” “external,” and “internal” are for convenience only and should not be interpreted as restrictive terms. Unless otherwise specified, ranges of values, where enumerated, include both the upper and lower limits of the range, as well as any sub-ranges between them. Where 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 should also be understood that the various features disclosed in the specification and drawings may be used in any combination.

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

[0049] The terms “substantially” and “about” may be used herein to express an inherent degree of uncertainty that may arise from any quantitative comparison, value, measurement, or other expression. These terms are also used herein to express the extent to which a quantitative expression may deviate from the criteria mentioned without altering the fundamental function of the subject matter in question. For example, “substantially K2O-free” glass means 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%. Where used herein, when the term “about” is used to make a partial change to a value, the exact value is also disclosed. For example, the term “greater than about 10 mol%” also discloses “10 mol% or more.”

[0050] Next, various embodiments will be referenced in detail, these examples being shown in the attached embodiments and drawings.

[0051] The glass-based articles disclosed herein include a hydrogen-containing layer extending from the surface of the article to the layer depth. The hydrogen-containing layer contains a hydrogen concentration that decreases from the maximum hydrogen concentration of the glass-based article towards the layer depth. 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 (approximately 9.8 N) or higher) without using conventional strengthening methods (e.g., ion exchange of a pair of alkali metal ions or thermal strengthening). The high Vickers indentation crack threshold exhibited by the glass-based articles indicates high damage resistance.

[0052] Glass-based articles can be formed by exposing a glass-based substrate to a water vapor-containing environment, thereby allowing hydrogen species to penetrate 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 the interdiffusion of hydrogen species into the glass. As used herein, the term “glass-based substrate” refers to a precursor before exposure to a water vapor-containing environment for forming a glass-based article containing a hydrogen-containing layer. Similarly, the term “glass-based article” refers to an article after exposure containing a hydrogen-containing layer.

[0053] Figure 1 shows a typical cross-section of a glass-based article 100 according to several embodiments. The glass-based article 100 has a thickness t extending 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, where the first layer depth has a depth d1 measured from the first surface 110 into the glass-based article 100. The second hydrogen-containing layer 122 extends from the second surface 112 to a second layer depth, where the second layer depth 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 layer depth and the second layer depth.

[0054] The hydrogen-containing layer of a glass-based article may have a layer depth (DOL) greater than 5 μm. In some embodiments, the layer depth is 10 μm or more, for example, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 45 μm or more, 50 μm or more, 55 μm or more, 60 μm or more, 65 μm or more, 70 μm or more, 75 μm or more, 80 μm or more, 85 μm or more, 90 μm or more, 95 μm or more, 100 μm or more, 105 μm or more, 110 μm or more. The depth may be greater than or equal to 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 195 μm, 200 μm or greater, or exceed 200 μm. In some embodiments, the layer depth is greater than 5 μm and 205 μm or less, for example, 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, 6 The depth can be 0 μm to 155 μm, 65 μm to 150 μm, 70 μm to 145 μm, 75 μm to 140 μm, 80 μm to 135 μm, 85 μm to 130 μm, 90 μm to 125 μm, 95 μm to 120 μm, 100 μm to 115 μm, 105 μm to 110 μm, or any sub-range formed by any of these endpoints. Generally, the layer depth exhibited by glass-based articles is greater than the layer depth that can be generated by exposure to the surrounding environment.

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

[0056] The layer depth and hydrogen concentration are measured by secondary ion mass spectrometry (SIMS) techniques known in the art. While SIMS can measure the hydrogen concentration at a given depth, it cannot distinguish between different hydrogen species present in the glass-based article. Therefore, all hydrogen species affect the hydrogen concentration measured by SIMS. As used herein, layer depth (DOL) refers to the initial depth below the surface of the glass-based article, where the hydrogen concentration is equal to that at the center of the glass-based article. Because this definition takes into account the hydrogen concentration of the glass-based substrate before treatment, the layer depth refers to the depth to which hydrogen has been 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, since it is expected that the hydrogen concentration will not change 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 over the entire depth of the glass-based article.

[0057] In some embodiments, the entire thickness of the glass article may be the portion of the hydrogen-containing layer. Such glass articles can be produced when the glass substrate is treated for a sufficient amount of time under conditions sufficient for hydrogen species to diffuse from each exposed surface to the center of the glass article. In some embodiments where the surface of the glass article is exposed to the same treatment conditions, the minimum hydrogen concentration may be located at half the thickness of the glass article, so the hydrogen-containing layer is in contact with the center of the glass article. In such embodiments, the DOL may be located at half the thickness of the glass article. In some embodiments, the glass article may not include any region that does not contain added hydrogen species. In some embodiments, the glass article may be treated in a humid environment such that the concentration of added hydrogen species is equilibrium throughout the glass article and the hydrogen concentration does not change at depths below the surface of the glass article. Since the hydrogen concentration at the center of the glass article is equivalent to the hydrogen concentration at all other depths, glass articles according to such embodiments do not exhibit the DOL as defined herein.

[0058] Glass-based articles are highly resistant to Vickers indentation cracks. High Vickers indentation crack resistance imparts high damage resistance to glass-based articles. While we do not wish to be bound by any particular theory, the water content of glass-based articles can reduce the local viscosity of the hydrogen-containing layer, causing local flow instead of cracking. The Vickers indentation crack threshold of glass-based articles is achieved without using conventional strengthening techniques, such as the replacement of large alkali metal ions in the glass with smaller alkali metal ions, thermal strengthening, or lamination of glass layers utilizing mismatches in thermal expansion coefficients. Glass-based articles must have a pressure of 1 kgf (approximately 9.8 N) or higher, for example, 2 kgf (approximately 19.6 N) or higher, 3 kgf (approximately 29.4 N) or higher, 4 kgf (approximately 39.2 N) or higher, 5 kgf (approximately 49 N) or higher, 6 kgf (approximately 58.8 N) or higher, 7 kgf (approximately 68.6 N) or higher, 8 kgf (approximately 78.4 N) or higher, 9 kgf (approximately 88.2 N) or higher, 10 kgf (approximately 98 N) or higher, 11 kgf (approximately 107.8 N) or higher, 12 kgf (approximately 117.6 N) or higher, 13 kgf (approximately 127.4 N) or higher, 14 kgf (approximately 137.2 N) or higher, 15 kgf (approximately 147 N) or higher, 16 kgf (approximately 156.8 N) or higher, 17 kgf This indicates a Vickers indentation crack threshold of approximately 166.6N or higher, 18kgf (approximately 176.4N) or higher, 19kgf (approximately 186.2N) or higher, 20kgf (approximately 196N) or higher, 21kgf (approximately 205.8N) or higher, 22kgf (approximately 215.6N) or higher, 23kgf (approximately 225.4N) or higher, 24kgf (approximately 235.2N) or higher, 25kgf (approximately 245N) or higher, 26kgf (approximately 254.8N) or higher, 27kgf (approximately 264.6N) or higher, 28kgf (approximately 274.4N) or higher, 29kgf (approximately 284.2N) or higher, 30kgf (approximately 294N) or higher, or greater than 30kgf (approximately 294N).In some embodiments, the glass-based article has a N-force of 1 kgf (approximately 9.8 N) to 30 kgf (approximately 294 N), for example, 2 kgf (approximately 19.6 N) to 29 kgf (approximately 284.2 N), 3 kgf (approximately 29.4 N) to 28 kgf (approximately 274.4 N), 4 kgf (approximately 39.2 N) to 27 kgf (approximately 264.6 N), 5 kgf (approximately 49 N) to 26 kgf (approximately 254.8 N), 6 kgf (approximately 58.8 N) to 25 kgf (approximately 245 N), 7 kgf (approximately 68.6 N) to 24 kgf (approximately 235.2 N), 8 kgf (approximately 78.4 N) to 23 kgf (approximately 225.4 N), and 9 kg This indicates the Vickers indentation crack thresholds for any subrange formed by the following endpoints: f (approx. 88.2 N) to 22 kgf (approx. 215.6 N), 10 kgf (approx. 98 N) to 21 kgf (approx. 205.8 N), 11 kgf (approx. 107.8 N) to 20 kgf (approx. 196 N), 12 kgf (approx. 117.6 N) to 19 kgf (approx. 186.2 N), 13 kgf (approx. 127.4 N) to 18 kgf (approx. 176.4 N), 14 kgf (approx. 137.2 N) to 17 kgf (approx. 166.6 N), 15 kgf (approx. 147 N) to 16 kgf (approx. 156.8 N), or any subrange formed by any of these endpoints.

[0059] The Vickers crack initiation threshold (or indentation failure threshold) was measured using 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 facet-to-face angle of 136°, known as a Vickers indenter. The Vickers indenter was the same as that used in standard microhardness tests (as described in ASTM-E384-11). A minimum of five specimens were selected to represent the type of glass and / or sample being tested. For each specimen, multiple sets of five indentations were introduced onto the specimen surface. Each set of five indentations was introduced under a given load, with each individual indentation spaced at least 5 mm apart and not closer than 5 mm from the edge of the specimen. For test loads of 2 kg or more, 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 residence (i.e., holding) time of 10 seconds at the target load was utilized. During the dwell time, the machine maintained load control. After at least 12 hours, the indentations were examined under reflected light at 500X magnification using a compound microscope. The presence or absence of central / radial cracks (cracks extending from the indentation along a plane perpendicular to the main plane of the article) or fracture of the specimen was then recorded for each indentation. Since this test focused on the formation of central / radial cracks or fracture of the specimen, the formation of lateral cracks (cracks extending along a plane parallel to the main plane of the article) was not considered an indicator of threshold behavior. The threshold value of a specimen is defined as the midpoint value of the minimum load of consecutive indentations, grouping together more than 50% of the individual indentations that satisfy the threshold. For example, if, within an individual specimen, two out of five indentations (40%) induced by a 5kg load exceed the threshold, and three out of five indentations (60%) induced by a 6kg load exceed the threshold, the threshold value of the specimen is defined as greater than 5kg. The midpoint range (from minimum to maximum) for all specimens may also be reported for each sample. The environment before, during, and after testing was controlled to 23±2°C and 50±5%RH to minimize variations in the fatigue (stress corrosion) behavior of the specimens.

[0060] While we do not wish to be bound by any particular theory, the hydrogen-containing layer in glass-based articles may be the result of the interdiffusion of hydrogen species of ions contained in the composition of the glass-based substrate. H3O + and / or H + Monovalent hydrogen-containing species such as can replace alkali metal ions contained in glass-based substrate compositions to form glass-based articles. The size of the alkali metal ions replaced by the hydrogen-containing species contributes to the diffusivity of the hydrogen-containing species in the glass-based substrate because larger alkali metal ions create larger pore spaces that promote the interdiffusion mechanism. For example, hydronium ions (H3O + 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 substrates was observed to be two orders of magnitude higher when the glass substrate contained potassium than when the glass substrate contained lithium. This observed behavior may also indicate that hydronium ions are the main monovalent hydrogen-containing species that diffuse into glass substrates. 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 those of hydronium ions, which can result in higher hydrogen diffusion coefficients than those observed for potassium.

[0061] [Table 1]

[0062] In some embodiments, replacing alkali metal ions in a glassy substrate with hydrogen-containing ions can generate a compressive stress layer extending from the surface of the glassy article to the compressive depth within the article. As used herein, compressive depth (DOC) refers to the depth to which the stress in the glassy article changes from compressive to tensile. Thus, the glassy article also includes a tensile stress region with a maximum central tension (CT) such that the forces within the article are in equilibrium. While we do not wish to be bound by theory, the compressive stress region may be the result of replacement with hydrogen-containing ions having a larger ionic radius than the ions being replaced.

[0063] In some embodiments, the compressive stress layer may include compressive stresses of 100 MPa or more, for example, 105 MPa or more, 110 MPa or more, 115 MPa or more, 120 MPa or more, 125 MPa or more, 130 MPa or more, 135 MPa or more, or greater than 135 MPa. In some embodiments, the compressive stress layer may include compressive stresses of 100 MPa or more and 150 MPa or less, for example, 105 MPa or more and 145 MPa or less, 110 MPa or more and 140 MPa or less, 115 MPa or more and 135 MPa or less, 120 MPa or more and 130 MPa or less, 125 MPa or less, or any subrange formed from any of these endpoints.

[0064] In some embodiments, the DOC of the compressive stress layer may be 75 μm or more, for example 80 μm or more, 85 μm or more, 90 μm or more, 95 μm or more, 100 μm or more, or exceed 100 μm. In some embodiments, the DOC of the compressive stress layer may be 75 μm or more and 115 μm or less, for example 80 μm or more and 110 μm or less, 85 μm or more and 105 μm or less, 90 μm or more and 100 μm or less, 95 μm, or any partial range that can be formed from any of these endpoints.

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

[0066] In some embodiments, the CT of a glass-based article may be 10 MPa or more, for example, 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 exceed 32 MPa. In some embodiments, the CT of a glass-based article may be 10 MPa or more and 35 MPa or less, for example, 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 partial range formed from any of these endpoints.

[0067] Compressive stress (including surface CS) is measured using a surface stress meter with commercially available equipment such as the FSM-6000 (FSM) manufactured by Orihara Manufacturing Co., Ltd. (Japan). Surface stress measurement relies on the accurate measurement of the stress optical coefficient (SOC) 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 measuring the stress-optical coefficient of glass," the details of which are incorporated herein by reference in their entirety. DOC is measured with the FSM. Maximum central tension (CT) value is measured using the scattered light polarizer (SCALP) technique known in the art.

[0068] Glass articles can be formed from glass substrates having any suitable composition. The composition of the glass substrate can be specifically selected to promote the diffusion of hydrogen-containing species, so that glass articles containing a hydrogen-containing layer can be efficiently formed. In some embodiments, the glass substrate may have a composition comprising SiO2, Al2O3, and P2O5. In some embodiments, the glass substrate may further contain at least one of alkali metal oxides, such as Li2O, Na2O, K2O, Rb2O, and Cs2O. In some embodiments, the glass substrate may substantially not contain or not contain at least one of lithium and sodium. In some embodiments, after the diffusion of hydrogen-containing species into the glass substrate, the glass article may have a bulk composition that is substantially the same as the composition of the glass substrate. In some embodiments, the hydrogen species may not diffuse into the center of the glass article. In other words, the center of the glass article is the region least affected by steam treatment. For this reason, the center of the glass article may have a composition that is substantially the same as, or identical to, the composition of the glass substrate before treatment in a hydrated environment.

[0069] Glass substrates can contain any appropriate amount of SiO2. SiO2 is the largest component and, therefore, the main component of the glass network formed from the glass composition. If the concentration of SiO2 in the glass composition is too high, the moldability of the glass composition may decrease. This is because higher concentrations of SiO2 make it more difficult to melt the glass, which also negatively affects the moldability of the glass. In some embodiments, the glass substrate may contain SiO2 in an amount of 45 mol% to 75 mol%, for example 46 mol% to 74 mol%, 47 mol% to 73 mol%, 48 mol% to 72 mol%, 49 mol% to 71 mol%, 50 mol% to 70 mol%, 51 mol% to 69 mol%, 52 mol% to 68 mol%, 53 mol% to 67 mol%, 54 mol% to 66 mol%, 55 mol% to 65 mol%, 56 mol% to 64 mol%, 57 mol% to 63 mol%, 58 mol% to 62 mol%, 59 mol% to 61 mol%, 60 mol%, or any sub-range formed by any of these endpoints.

[0070] Glass substrates may contain any appropriate amount of Al2O3. Al2O3, like SiO2, can function as a glass network-forming agent. Al2O3 increases the viscosity of the glass composition due to its tetrahedral coordination in the glass melt formed from it; if the amount of Al2O3 is too high, the moldability of the glass composition decreases. However, when the concentration of Al2O3 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 with certain molding processes, such as melt molding. Including Al2O3 in glass substrates inhibits phase separation and reduces the number of non-crosslinked oxygen atoms (NBOs) in the glass. Furthermore, Al2O3 can improve the effect of ion exchange. In some embodiments, the glass substrate may contain Al2O3 in amounts of 3 mol% to 20 mol%, for example 4 mol% to 19 mol%, 5 mol% to 18 mol%, 6 mol% to 17 mol%, 7 mol% to 16 mol%, 8 mol% to 15 mol%, 9 mol% to 14 mol%, 10 mol% to 13 mol%, 11 mol% to 12 mol%, or any sub-range formed by any of these endpoints. In some embodiments, the glass substrate may contain Al2O3 in amounts of 5 mol% to 15 mol%, for example 7 mol% to 14 mol%, or any sub-range formed by any of these endpoints.

[0071] The glass substrate may contain any amount of P2O5 sufficient to yield the desired hydrogen diffusion coefficient. The inclusion of phosphorus in the glass substrate promotes faster interdiffusion regardless of the ion pairs being exchanged. Therefore, phosphorus-containing glass substrates enable the efficient formation of glass articles containing hydrogen-containing layers. The inclusion of P2O5 also allows for the production of glass articles with deep layers (e.g., more than approximately 10 μm) in relatively short processing times. In some embodiments, the glass substrate may contain P2O5 in amounts 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 sub-range formed by any of these endpoints. In some embodiments, the glass substrate may contain P2O5 in an amount of 5 mol% to 15 mol%, for example, 6 mol% to 15 mol%, 5 mol% to 10 mol%, 6 mol% to 10 mol%, 7 mol% to 10 mol%, or any sub-range formed by any of these endpoints.

[0072] The glass substrate may contain any appropriate amount of alkali metal oxide. Alkali metal oxides promote ion exchange. Alkali metal oxides in the glass composition (e.g., Li2O, Na2O and K2O, as well as other alkali metal oxides including Cs2O and Rb2O) may be collectively referred to as "R2O", and R2O can be expressed in mol%. In some embodiments, the glass substrate may substantially not contain or contain at least one of lithium and sodium. In embodiments, the glass composition contains 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 contains R2O in an amount of 25 mol% or less, for example, 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. In embodiments, it should be understood that any of the above ranges may be combined with any of the other ranges. In some embodiments, the glass composition contains R2O in amounts of 6.0 mol% to 25.0 mol%, for example, 7.0 mol% to 24.0 mol%, 8.0 mol% to 23.0 mol%, 9.0 mol% to 22.0 mol%, 10.0 mol% to 21.0 mol%, 11.0 mol% to 20.0 mol%, 12.0 mol% to 19.0 mol%, 13.0 mol% to 18.0 mol%, 14.0 mol% to 17.0 mol%, or 15.0 mol% to 16.0 mol%, and all and partial ranges between the aforementioned values.

[0073] In some embodiments, the alkali metal oxide may be K2O. The inclusion of K2O enables efficient exchange of hydrogen species into the glass substrate when exposed to a hydrated environment. In embodiments, the glass substrate may contain K2O in amounts of 6 mol% to 25 mol%, for example, 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 sub-range formed from any of these endpoints. In some embodiments, the glass substrate may contain K2O in amounts of 10 mol% to 25 mol%, for example, 10 mol% to 20 mol%, 11 mol% to 25 mol%, 11 mol% to 20 mol%, 15 mol% to 20 mol%, or any sub-range formed from any of these endpoints.

[0074] The glass substrate may contain Rb2O in any suitable amount. In some embodiments, the glass substrate may contain Rb2O in amounts of 0 mol% to 10 mol%, for example, 1 mol% to 9 mol%, 2 mol% to 8 mol%, 3 mol% to 7 mol%, 4 mol% to 6 mol%, 5 mol%, or any sub-range formed from any of these endpoints.

[0075] The glass substrate may contain Cs2O in any suitable amount. In some embodiments, the glass substrate may contain Cs2O in amounts of 0 mol% to 10 mol%, for example, 1 mol% to 9 mol%, 2 mol% to 8 mol%, 3 mol% to 7 mol%, 4 mol% to 6 mol%, 5 mol%, or any sub-range formed from any of these endpoints.

[0076] In some embodiments, the glass substrate may have a composition containing 45 mol% to 75 mol% of SiO2, 3 mol% to 20 mol% of Al2O3, 6 mol% to 15 mol% of P2O5, and 6 mol% to 25 mol% of K2O.

[0077] In some embodiments, the glass substrate may have a composition containing 45 mol% to 75 mol% of SiO2, 3 mol% to 20 mol% of Al2O3, 4 mol% to 15 mol% of P2O5, and 11 mol% to 25 mol% of K2O.

[0078] In some embodiments, the glass substrate may have a composition containing 55 mol% to 69 mol% of SiO2, 5 mol% to 15 mol% of Al2O3, 6 mol% to 10 mol% of P2O5, and 10 mol% to 20 mol% of K2O.

[0079] In some embodiments, the glass substrate may have a composition containing 55 mol% to 69 mol% of SiO2, 5 mol% to 15 mol% of Al2O3, 5 mol% to 10 mol% of P2O5, and 11 mol% to 20 mol% of K2O.

[0080] In some embodiments, the glass substrate may have a composition containing 58 mol% to 63 mol% of SiO2, 7 mol% to 14 mol% of Al2O3, 7 mol% to 10 mol% of P2O5, and 15 mol% to 20 mol% of K2O.

[0081] In some embodiments, the glass substrate may exhibit a Vickers crack initiation threshold of 5 kgf (approximately 49 N) or higher, for example, 6 kgf (approximately 58.8 N) or higher, 7 kgf (approximately 68.6 N) or higher, 8 kgf (approximately 78.4 N) or higher, 9 kgf (approximately 88.2 N) or higher, 10 kgf (approximately 98 N) or higher, or exceeding 10 kgf (approximately 98 N).

[0082] The glass substrate may have any suitable shape. In some embodiments, the glass substrate may have a thickness of 2 mm or less, for example, 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 substrate may be in the form of a plate or a sheet. In some other embodiments, the glass substrate may have a 2.5D or 3D shape. As used herein, “2.5D shape” refers to an article in the form of a sheet in which at least one principal surface is at least partially non-planar and the second principal surface is substantially planar. As used herein, “3D shape” refers to an article having first and second opposing principal surfaces that are at least partially non-planar.

[0083] Glass-based articles can be manufactured by exposing a glass-based substrate to water vapor under any suitable conditions. Exposure can be carried out in any suitable apparatus, such as a furnace with relative humidity control. In some embodiments, the glass-based substrate may be exposed to an environment with a relative humidity of 75% or more, for example, 80% or more, 85% or more, 90% or more, 95% or more, 99% or more, or above 99%. In some embodiments, the glass-based substrate may be exposed to an environment with a relative humidity of 100%.

[0084] In some embodiments, the glass substrate may be exposed to the environment at temperatures of 70°C or higher, for example, 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, 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 above 200°C. In some embodiments, the glass substrate may be exposed to the environment at temperatures between 70°C and 210°C, for example, 75°C and 205°C, 80°C and 200°C, 85°C and 195°C, 90°C and 190°C, 95°C and 185°C, 100°C and 180°C, 105°C and 175°C, 110°C and 170°C, 115°C and 165°C, 120°C and 160°C, 125°C and 155°C, 130°C and 150°C, 135°C and 145°C, 140°C, or any partial range of temperatures formed from these endpoints.

[0085] In some embodiments, the glass substrate may be exposed to a water vapor-containing environment for a time sufficient to allow for the diffusion of hydrogen-containing species to a desired degree and the desired layer depth. In some embodiments, the glass substrate may be exposed to a water vapor-containing environment for one day or more, for example, two days or more, three days or more, four days or more, five days or more, six days or more, seven days or more, eight days or more, nine days or more, ten days or more, fifteen days or more, twenty days or more, twenty-five days or more, thirty days or more, thirty days or more, thirty-five days or more, forty days or more, forty-five days or more, fifty days or more, fifty days or more, fifty days or more, sixty days or more, sixty days or more, or more than sixty days. In some embodiments, the glass substrate may be exposed to a water vapor-containing environment for a period of time of 1 to 70 days, for example, 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 partial range formed from any of these endpoints. The exposure conditions can be partially modified to shorten the time required to bring about a desired amount of diffusion of hydrogen-containing species into the glass 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 layer depth of hydrogen-containing species into the glass substrate.

[0086] The glass articles disclosed herein may be incorporated into other articles such as articles with displays (or display articles) (e.g., consumer electronic products including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches)), building articles, transport articles (e.g., automobiles, trains, aircraft, ships, etc.), instrument articles for specific purposes, or any articles requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. An exemplary article incorporating any of the glass articles disclosed herein is shown in Figures 2A and 2B. Specifically, Figures 2A and 2B show a housing 202 having a front 204, a rear 206, and sides 208; electrical components (not shown) at least partially inside or throughout the housing and including at least a controller, memory, and a display 210 provided on or adjacent to the front of the housing; and a cover substrate 212 provided on or covering the front of the housing to cover the display. In some embodiments, at least a portion of one of the cover substrate 212 and housing 202 may include any of the glass-based articles disclosed herein.

[0087] Exemplary Embodiments Glass compositions particularly suitable for forming the glass-based articles described herein were formed on glass-based substrates. The compositions of Examples 1 to 6 are listed in Table II below. Density was determined using the buoyancy method according to 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 was expressed in units of / °C and determined using a pushrod dilatometer in accordance with ASTM E228-11. The strain point and annealing point were determined using the beam bending viscosity method of ASTM C598-93 (2013). The softening point was determined using the parallel plate viscosity method of ASTM C1351M-96 (2012). The temperatures at which the glass viscosity reached 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 Glass Above the Softening Point."

[0088] [Table 2]

[0089] A glass-based substrate containing the composition of Example 1 and having a thickness of 1 mm was exposed to an environment with a relative humidity of 85% for 65 days to form a glass-based article containing a hydrogen-containing layer of the type described herein.

[0090] The hydrogen-containing layer depth was measured using SIMS before and after exposure. The results of the SIMS hydrogen concentration measurements are shown in Figure 3. Here, the hydrogen concentration curve 301 for the untreated glass substrate has a layer depth of approximately 5 μm, and the hydrogen concentration curve 302 for the glass article has a layer depth of approximately 30 μm. For the exposed glass article, measurements were taken 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 measured values ​​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. Figures 4 and 5 show the Vickers indentation results for glass substrates before exposure, and after indentation at 5 kgf (approximately 49 N) and 10 kgf (approximately 98 N), respectively. As shown in Figures 4 and 5, the glass substrates had a Vickers crack initiation threshold higher than 5 kgf (approximately 49 N) but lower than 10 kgf (approximately 98 N). Figures 6, 7, and 8 show the Vickers indentation results for exposed glass articles, after indentation at 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 for glass articles exceeded 20 kgf (approximately 196 N).

[0092] Glass substrates containing the compositions of Comparative Examples 1-3 and having a thickness of 1 mm were also prepared and exposed to an environment with a relative humidity of 85% 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 a 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 the glass composition 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 Comparative Examples 1 and 2, which contained lithium and sodium, respectively. The difference in hydrogen diffusion coefficients between the potassium-containing glass composition and the lithium and sodium-containing glass compositions indicates that alkali metal ions with larger ionic radii allow for faster hydrogen diffusion.

[0095] Glass substrates containing the glass composition of Example 6 were manufactured with thicknesses of 0.5 mm and 1.0 mm. The glass substrates were exposed to a 100% relative humidity environment at a temperature of 200°C for 7 days to produce glass articles of the type described herein. The glass articles exhibited a compressive stress region extending from the surface to the compression depth. The measured maximum compressive stress of the 0.5 mm glass article was 124 MPa, and the measured maximum compressive stress of the 1.0 mm glass article was 137 MPa. The measured maximum central tension of the 0.5 mm glass article was 32 MPa, and the measured maximum central tension of the 1.0 mm glass article was 15 MPa. The compression depth of the 0.5 mm glass article was 101 μm, and the compression depth of the 1.0 mm glass article was 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 articles formed from glass 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. The FTIR analysis was performed under the following conditions: CaF / InSb, 64 scans, 16 cm². -1 The scan was performed with a resolution of 10 μm, an aperture of 10 μm, and steps of 10 μm. The scan started at the surface of the sample and continued to approximately the midpoint of its thickness. Spectra were prepared for "dry" silica with a hydroxyl (βOH) concentration of 3900 cm⁻¹. -1 (Maximum) and 3550cm -1 The calculations were performed using the (minimum) parameters. Due to the multi-component nature of the glass-based articles, it was not possible to distinguish between bound hydroxyls and molecular hydroxyls; therefore, the plots report the concentration of total hydroxyl content. The measured hydroxyl concentration profiles of samples with thicknesses of 0.5 mm and 1.0 mm are shown in Figures 9 and 10, respectively. As shown in Figures 9 and 10, the depth in the sample at which the measured hydroxyl content becomes substantially constant and is equivalent to the hydroxyl content at the center of the article indicates the background hydroxyl content of the precursor glass-based substrate, which was approximately 200 μm as measured by FTIR. The appearance of embedded hydroxyl concentration peaks in Figures 9 and 10 is an artifact of the measurement method.

[0097] Square samples with 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 CS being 167 MPa and DOC being 73 μm. The five steam-treated samples and three control samples that were not exposed to steam treatment were then subjected to an abrasive ring-on-ring (AROR) test. The strength and peak load of each tested sample are shown in Table IV. As shown in Table IV, the steam-treated samples showed 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 plate glass specimens, and the AROR test method used herein is based on ASTM C1499-09 (2013), entitled "Standard Test Method for Equibiaxial Bending Strength of Advanced Ceramics at Ambient Temperature." The contents of ASTM C1499-09 are incorporated herein by reference in their entirety. Before the ring-on-ring test, the glass specimens are polished with 90-grit silicon carbide (SiC) particles delivered to the glass samples using the method and apparatus described in Appendix A2 entitled "Polishing Procedure" in ASTM C158-02 (2012), entitled "Standard Test Method for Bending Strength of Glass (Measurement of Breaking Factor)." The contents of ASTM C158-02 and in particular Appendix 2 are incorporated herein by reference in their entirety.

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

[0101] In the AROR test, as shown in Figure 11, a glass-based article having at least one abrasion surface is placed between two concentric rings of different sizes to measure the equibiaxial bending strength (i.e., the maximum stress the material can withstand when bent between two concentric rings). In the AROR configuration 400, the 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 cell (not shown) through a load ring 430 having a diameter D1.

[0102] The ratio of the diameters of the load ring to the support ring, D1 / D2, can be in the range of 0.2 to 0.5. In some embodiments, D1 / D2 is 0.5. It is desirable that the load ring 430 and the support ring 420 be arranged concentrically within 0.5% of the support ring diameter D2. The load cell used for the test is desirable to have an accuracy of within ±1% at any load within the selected range. The test is performed at a temperature of 23±2°C and a relative humidity of 40±10%.

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

[0104] The intended fracture mechanism of the AROR test is to observe the fracture of the glass-based article 410 originating from surface 430a within the load ring 430. Fractures occurring outside this region, i.e., between the load 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 thickness h of the specimen are sometimes observed. Therefore, it is not uncommon for a high proportion of fractures to originate from the underside of the load ring 430. Without knowing the stress generation (collected by strain gauge analysis) both inside and under the ring and the fracture origin of each specimen, it is impossible to accurately calculate the stress. Therefore, the AROR test focuses on the peak load at fracture as the measured response.

[0105] While typical embodiments have been described for illustrative purposes, the foregoing description should not be considered to limit the scope of the claims of this disclosure or the appended claims. Therefore, a variety of modifications, adaptations, and alternatives can be found without departing from the spirit and scope of the claims of this disclosure or the appended claims.

[0106] Preferred embodiments of the present invention are described below in separate sections.

[0107] Embodiment 1 Glass-based articles, SiO2, Al2O3 and P2O5; and A hydrogen-containing layer extending from the surface to the depth of the glass-based article. Includes, The hydrogen concentration in the hydrogen-containing layer decreases from the maximum hydrogen concentration towards the layer depth, A glass-based article having a layer depth greater than 5 μm.

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

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

[0110] Embodiment 4 A glass-based article according to any one of Embodiments 1 to 3, wherein the maximum hydrogen concentration is located on the surface of the glass-based article.

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

[0112] Embodiment 6 A glass-based article according to any one of Embodiments 1 to 5, further comprising K2O.

[0113] Embodiment 7 The center of the glass-based article is SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 6 mol% to 15 mol%; and K2O 6 mol% to 25 mol% A glass-based article according to any one of Embodiments 1 to 6, including the above.

[0114] Embodiment 8 The center of the glass-based article is SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 4 mol% to 15 mol%; and K2O 11 mol% to 25 mol% A glass-based article according to any one of Embodiments 1 to 6, including the above.

[0115] Embodiment 9 The center of the glass-based article is SiO2 in an amount of 55 mol% to 69 mol%; Al2O3 in an amount of 5 mol% to 15 mol%; P2O5 in amounts of 6 mol% to 10 mol%; and K2O 10 mol% to 20 mol% A glass-based article according to any one of Embodiments 1 to 6, including the above.

[0116] Embodiment 10 The center of the glass-based article is Cs2O in amounts of 0 mol% to 10 mol%; and Rb2O 0 mol% to 10 mol% A glass-based article according to any one of embodiments 7 to 9, including the above.

[0117] Embodiment 11 A glass-based article according to any one of Embodiments 1 to 10, wherein the glass-based article substantially does not contain at least one of lithium and sodium.

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

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

[0120] Embodiment 14 Household electronic products, Enclosure including the front, back, and sides; Electrical components located at least partially within the housing, including at least a controller, memory, and a display, wherein the display is located on or adjacent to the front of the housing; and Cover substrate placed on the display A household electronic product comprising, wherein at least one part of the housing or the cover substrate contains a glass-based article according to any one of embodiments 1 to 13.

[0121] Embodiment 15 It is made of glass, SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 6 mol% to 15 mol%; and K2O 6 mol% to 25 mol% Glass, including.

[0122] Embodiment 16 SiO2 in an amount of 55 mol% to 69 mol%; Al2O3 in an amount of 5 mol% to 15 mol%; P2O5 in amounts of 6 mol% to 10 mol%; and K2O 10 mol% to 20 mol% The glass according to Embodiment 15, including the glass described above.

[0123] Embodiment 17 Cs2O in amounts of 0 mol% to 10 mol%; and Rb2O 0 mol% to 10 mol% The glass according to embodiment 15 or 16, further comprising:

[0124] Embodiment 18 The glass according to any one of embodiments 15 to 17, wherein the glass substantially does not contain lithium.

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

[0126] Embodiment 20 SiO2 in an amount of 58 mol% to 63 mol%; Al2O3 in an amount of 7 mol% to 14 mol%; P2O5 in amounts of 7 mol% to 10 mol%; and K2O 15 mol% to 20 mol% A glass according to any one of embodiments 15 to 19, including the glass described above.

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

[0128] Embodiment 22 A glass according to 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 made of glass, SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 4 mol% to 15 mol%; and K2O 11 mol% to 25 mol% Glass, including.

[0130] Embodiment 24 SiO2 in an amount of 55 mol% to 69 mol%; Al2O3 in an amount of 5 mol% to 15 mol%; P2O5 in amounts of 5 mol% to 10 mol%; and K2O 11 mol% to 20 mol% Glass according to Embodiment 23, including the glass described above.

[0131] Embodiment 25 Cs2O in amounts of 0 mol% to 10 mol%; and Rb2O 0 mol% to 10 mol% The glass according to embodiment 23 or 24, further comprising:

[0132] Embodiment 26 The glass according to any one of embodiments 23 to 25, wherein the glass substantially does not contain lithium.

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

[0134] Embodiment 28 SiO2 in an amount of 58 mol% to 63 mol%; Al2O3 in an amount of 7 mol% to 14 mol%; P2O5 in amounts of 7 mol% to 10 mol%; and K2O 15 mol% to 20 mol% A glass according to any one of embodiments 23 to 27, including the glass described above.

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

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

[0137] Embodiment 31 It is a method, The step of exposing a glass-based substrate to an environment with a relative humidity of 75% or higher to form a glass-based article having a hydrogen-containing layer extending from the surface of the glass-based article to the layer depth. Includes, The glass-based substrate comprises SiO2, Al2O3, and P2O5. The hydrogen concentration in the hydrogen-containing layer decreases from the maximum hydrogen concentration towards the layer depth, The method wherein the layer depth is 5 μm or more.

[0138] Embodiment 32 The glass-based substrate is SiO2 in an amount of 55 mol% to 69 mol%; Al2O3 in an amount of 5 mol% to 15 mol%; P2O5 in amounts of 6 mol% to 10 mol%; and K2O 10 mol% to 20 mol% The method according to Embodiment 31, having a composition including the following.

[0139] Embodiment 33 The glass-based substrate is SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 4 mol% to 15 mol%; and K2O 11 mol% to 25 mol% The method according to Embodiment 31, having a composition including the following.

[0140] Embodiment 34 The glass-based substrate is SiO2 in an amount of 45 mol% to 75 mol%; Al2O3 in an amount of 3 mol% to 20 mol%; P2O5 in amounts of 6 mol% to 15 mol%; and K2O 6 mol% to 25 mol% The method according to Embodiment 31, having a composition including the following.

[0141] Embodiment 35 The glass-based substrate is Cs2O in amounts of 0 mol% to 10 mol%; and Rb2O 0 mol% to 10 mol% The method according to any one of embodiments 31 to 34, further including the above.

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

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

[0144] Embodiment 38 The method according to any one of embodiments 31 to 37, wherein the exposure is carried out at a temperature of 70°C or higher.

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

Claims

1. Glass articles strengthened by water treatment, The main component is SiO ２ and Al ２ O ３ , P 15 mol% or less ２ O ５ , and K at a concentration of 11 mol% to 25 mol% ２ O, The glass article includes, The surface of the glass article, A hydrogen-containing layer extending from the surface of the glass article to a layer depth within the glass article, and A compressive stress layer comprising hydrogen species, the compressive stress layer extending from the surface of the glass article to the compression depth within the glass article, Includes, The layer depth is a first depth below the surface where the hydrogen concentration matches that of the center of the glass article, and the compression depth is the depth at which the stress in the glass article changes from compressive stress to tensile stress. The aforementioned layer depth is greater than 5 μm from the surface. The compressive stress layer has a compressive stress of at least 100 MPa. Glassware.

2. The glass article according to claim 1, wherein the maximum hydrogen concentration is located on the surface of the glass article, the hydrogen concentration of the hydrogen-containing layer decreases from the maximum hydrogen concentration to the layer depth, and the hydrogen species includes one or more of molecular water, hydroxyl, hydrogen ions, and hydronium.

3. The glass article according to claim 1, further comprising a tensile stress region having a maximum central tension of 10 MPa or more.

4. The glass article according to claim 1, wherein the surface is a first surface of the glass article, and the glass article further has a second surface and a thickness between the first surface and the second surface, the layer depth is greater than 0.005 times the thickness of the glass article, and the thickness is 2 mm or less.

5. Electrical components including displays, and A cover that covers the display, 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.

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