Hydrogen-containing glass-based articles with high indentation cracking threshold

Abstract

A glass substrate includes a hydrogen-containing layer extending from one surface of the article to a depth thereof. The hydrogen-containing layer includes a hydrogen concentration ranging from a maximum hydrogen concentration to a decreasing hydrogen concentration at the depth of the layer. The glass substrate exhibits a high Vickers indentation cracking threshold. A glass composition selected to promote the formation of the hydrogen-containing layer and a method of forming the glass substrate are also provided.

Description

Hydrogen-containing glass substrate article having a high indentation cracking threshold Related applications This application claims the benefit of priority to U.S. Provisional Application No. 62 / 587,872, filed November 17, 2017, the content of which is relied upon and incorporated herein by reference in its entirety, and to NL Application No. 2020896, filed May 8, 2018, the content of which is relied upon and incorporated herein by reference in its entirety. The present disclosure relates to hydrogen-containing glass substrate articles, glass compositions for forming such glass substrate articles, and methods of forming such glass substrate articles. Portable electronic components such as smart phones, tablet computers, and wearable elements (such as watches and fitness trackers) continue to become smaller and more complex. Accordingly, the materials conventionally used on at least one outer surface of such portable electronic components also continue to become more complex. For example, as portable electronic components become smaller and thinner to meet consumer demands, the display covers and outer shells used in such portable electronic components also become smaller and thinner, resulting in higher performance requirements for the materials used to form such components. Accordingly, there is a need for materials that exhibit higher performance (such as damage resistance) for use in portable electronic components. In aspect (1), a glass substrate article is provided. The glass substrate article comprises: SiO 2 , Al 2 O 3 and P 2 O 5 ; and a hydrogen-containing layer extending from one surface of the glass substrate article to a layer depth. The hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the layer depth, and the layer depth is greater than 5 μm. In aspect (2), the glass substrate article of aspect (1) is provided, wherein the glass substrate article has a Vickers cracking initiation threshold of greater than or equal to 1 kgf. In aspect (3), the glass substrate article of aspect (1) or (2) is provided, wherein the layer depth is greater than or equal to 10 μm. In aspect (4), the glass substrate article of any one of aspects (1) to (3) is provided, wherein the maximum hydrogen concentration is at the surface of the glass substrate article. In aspect (5), the glass substrate article of any one of aspects (1) to (4) is provided, further comprising Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 at least one of O. In aspect (6), there is provided a glass substrate article of any one of aspects (1) to (5), further comprising K 2 O. In aspect (7), there is provided a glass substrate article of any one of aspects (1) to (6), wherein the center of the glass substrate article comprises: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P of greater than or equal to 6 mol% to less than or equal to 15 mol% 2 O 5 ; and K of greater than or equal to 6 mol% to less than or equal to 25 mol% 2 O. In aspect (8), there is provided a glass substrate article of any one of aspects (1) to (6), wherein the center of the glass substrate article comprises: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P of greater than or equal to 4 mol% to less than or equal to 15 mol% 2 O 5 ; and K of greater than or equal to 11 mol% to less than or equal to 25 mol% 2 O. In aspect (9), there is provided a glass substrate article of any one of aspects (1) to (6), wherein the center of the glass substrate article comprises: SiO of greater than or equal to 55 mol% to less than or equal to 69 mol% 2; Al of greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P of greater than or equal to 6 mol% to less than or equal to 10 mol% 2 O 5 ; and K of greater than or equal to 10 mol% to less than or equal to 20 mol%. 2 O. In aspect (10), there is provided a glass substrate article of any one of aspects (7) to (9), wherein the center of the glass substrate article comprises: Cs of greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O; and Rb of greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O. In aspect (11), there is provided a glass substrate article of any one of aspects (1) to (10), wherein the glass substrate article is substantially free of at least one of lithium and sodium. In aspect (12), there is provided a glass substrate article of any one of aspects (1) to (11), further comprising a compressive stress layer extending from one surface of the glass substrate article into the glass substrate article to a compressive depth. In aspect (13), there is provided the glass substrate article of aspect (12), wherein the compressive stress layer comprises a compressive stress of at least about 100 MPa, and the compressive depth is at least about 75 μm. In aspect (14), there is provided a consumer electronic product. The consumer electronic product comprises: a housing comprising a front surface, a rear surface and side surfaces; electrical components at least partially within the housing, the electrical components comprising at least one controller, a memory and a display, the display being at or adjacent to the front surface of the housing; and a cover substrate disposed on the display. At least a part of at least one of the housing or the cover substrate comprises a glass substrate article of any one of aspects (1) to (13). In aspect (15), there is provided a glass. The glass comprises: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3; P of greater than or equal to 6 mol% to less than or equal to 15 mol% 2 O 5 ; and K of greater than or equal to 6 mol% to less than or equal to 25 mol% 2 O. In aspect (16), there is provided the glass of aspect (15), comprising: SiO of greater than or equal to 55 mol% to less than or equal to 69 mol% 2 ; Al of greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P of greater than or equal to 6 mol% to less than or equal to 10 mol% 2 O 5 ; and K of greater than or equal to 10 mol% to less than or equal to 20 mol% 2 O. In aspect (17), there is provided the glass of aspect (15) or (16), further comprising: Cs of greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O; and Rb of greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O. In aspect (18), there is provided the glass of any one of aspects (15) to (17), wherein the glass is substantially free of lithium. In aspect (19), there is provided the glass of any one of aspects (15) to (18), wherein the glass is substantially free of sodium. In aspect (20), there is provided the glass of any one of aspects (15) to (19), comprising: SiO of greater than or equal to 58 mol% to less than or equal to 63 mol% 2 ; Al of greater than or equal to 7 mol% to less than or equal to 14 mol% 2 O 3 ; P of greater than or equal to 7 mol% to less than or equal to 10 mol% 2 O 5 ; and K of greater than or equal to 15 mol% to less than or equal to 20 mol% 2 O. In aspect (21), there is provided the glass of any one of aspects (15) to (20), wherein the glass has a Vickers crack initiation threshold value of greater than or equal to 5 kgf. In aspect (22), there is provided the glass of any one of aspects (15) to (21), further comprising Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O of at least one. In aspect (23), there is provided a glass. The glass comprises: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P of greater than or equal to 4 mol% to less than or equal to 15 mol% 2 O 5 ; and K of greater than or equal to 11 mol% to less than or equal to 25 mol% 2 O. In aspect (24), there is provided the glass of aspect (23), comprising: SiO of greater than or equal to 55 mol% to less than or equal to 69 mol% 2 ; Al of greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P of greater than or equal to 5 mol% to less than or equal to 10 mol% 2 O 5 ; and K of greater than or equal to 11 mol% to less than or equal to 20 mol% 2 O. In aspect (25), there is provided the glass of aspect (23) or (24), further comprising: Cs of greater than or equal to 0 mol% to less than or equal to 10 mol% 2O; and Rb in an amount greater than or equal to 0 mole % and less than or equal to 10 mole % 2 O. In aspect (26), there is provided a glass according to any one of aspects (23) to (25), wherein the glass is substantially free of lithium. In aspect (27), there is provided a glass according to any one of aspects (23) to (26), wherein the glass is substantially free of sodium. In aspect (28), there is provided a glass according to any one of aspects (23) to (27), comprising: SiO in an amount greater than or equal to 58 mole % and less than or equal to 63 mole % 2 ; Al in an amount greater than or equal to 7 mole % and less than or equal to 14 mole % 2 O 3 ; P in an amount greater than or equal to 7 mole % and less than or equal to 10 mole % 2 O 5 ; and K in an amount greater than or equal to 15 mole % and less than or equal to 20 mole % 2 O. In aspect (29), there is provided a glass according to any one of aspects (23) to (28), wherein the glass has a Vickers cracking initial threshold value of greater than or equal to 5 kgf. In aspect (30), there is provided a glass according to any one of aspects (23) to (29), further comprising at least one of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O. In aspect (31), there is provided a method. The method comprises: exposing a glass substrate to an environment having a relative humidity of greater than or equal to 75% to form a glass substrate article having a hydrogen-containing layer, the hydrogen-containing layer extending from a surface of the glass substrate article to a layer depth. The glass substrate comprises SiO 2 、Al 2 O 3 and P 2O 5 The hydrogen concentration in the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of the layer, and the depth of the layer is greater than 5 μm. In aspect (32), there is provided the method of aspect (31), wherein the glass substrate has a composition comprising one of the following: SiO of greater than or equal to 55 mol% to less than or equal to 69 mol% 2 ; Al of greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P of greater than or equal to 6 mol% to less than or equal to 10 mol% 2 O 5 ; and K of greater than or equal to 10 mol% to less than or equal to 20 mol% 2 O. In aspect (33), there is provided the method of aspect (31), wherein the glass substrate has a composition comprising one of the following: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P of greater than or equal to 4 mol% to less than or equal to 15 mol% 2 O 5 ; and K of greater than or equal to 11 mol% to less than or equal to 25 mol% 2 O. In aspect (34), there is provided the method of aspect (31), wherein the glass substrate has a composition comprising one of the following: SiO of greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al of greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P of greater than or equal to 6 mol% to less than or equal to 15 mol% 2 O 5; and K in an amount greater than or equal to 6 mol% and less than or equal to 25 mol% 2 O. In aspect (35), there is provided a method according to any one of aspects (31) to (34), wherein the glass substrate further comprises: Cs in an amount greater than or equal to 0 mol% and less than or equal to 10 mol% 2 O; and Rb in an amount greater than or equal to 0 mol% and less than or equal to 10 mol% 2 O. In aspect (36), there is provided a method according to any one of aspects (31) to (35), further comprising at least one of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O. In aspect (37), there is provided a method according to any one of aspects (31) to (36), wherein the glass substrate is substantially free of at least one of lithium and sodium. In aspect (38), there is provided a method according to any one of aspects (31) to (37), wherein the exposure occurs at a temperature greater than or equal to 70 °C. In aspect (39), there is provided a method according to any one of aspects (31) to (38), wherein the glass substrate has a Vickers crack initiation threshold of greater than or equal to 1 kgf. These and other aspects, advantages, and salient features will become apparent from the following detailed description, the drawings, and the appended claims. In the following description, throughout several views shown in the drawings, like reference characters represent like or corresponding parts. It should also be understood that terms such as "top", "bottom", "outward", "inward", and the like are for convenience only and should not be construed as limiting terms. Unless otherwise specified, a range of values when recited includes the upper and lower limits of the range, and any sub-ranges 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 should also be understood that the various features disclosed in the specification and the drawings can be used in any and all combinations. As used herein, the term "glass substrate" is used in its broadest sense to include any object made entirely or in part of glass, including glass ceramics (which include a crystalline phase and a residual amorphous glass phase). Unless otherwise specified, all compositions of the glasses described herein are expressed in mole percentages (mol %), and the components are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in degrees Celsius (°C). Note that the terms "substantially" and "about" may be used herein to indicate an inherent degree of uncertainty that may be attributable to any quantitative comparison, value, measurement, or other representation. These terms are also used herein to indicate the degree to which a quantitative representation can vary from the stated reference without resulting in a change in the basic function of the subject matter being discussed. For example, a glass that is "substantially free of K 2 O" is a glass in which K 2 O has not been actively added or batch-fed into the glass and may be present as a contaminant in trace amounts (such as in amounts 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 "greater than or equal to about 10 mol %". Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying examples and drawings. The glass substrate article includes a hydrogen-containing layer that extends from one surface of the article to a layer depth. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration of the glass substrate article to the layer depth. In some embodiments, the maximum hydrogen concentration may be located at the surface of the glass substrate article. The glass substrate article exhibits a high Vickers indentation cracking threshold (e.g., greater than or equal to 1 kgf) without using conventional strengthening methods (e.g., ion exchange of a pair of alkali ions or thermal tempering). The high Vickers indentation cracking threshold exhibited by the glass substrate article indicates high damage resistance. The glass substrate article can be formed by exposing a glass substrate wafer to an environment containing water vapor, thereby allowing hydrogen species to penetrate the glass substrate wafer and form a glass substrate article having a hydrogen-containing layer. As used herein, hydrogen species include molecular water, hydroxyl groups, hydrogen ions, and hydronium ions. The composition of the glass substrate wafers can be selected to facilitate the mutual diffusion of hydrogen species into the glass. As used herein, the term "glass substrate wafer" refers to the precursor before exposure to the water vapor environment for forming a glass substrate article including a hydrogen-containing layer. Similarly, the term "glass substrate article" refers to the exposed article after including a hydrogen-containing layer. A representative cross-section of a glass substrate article 100 according to some embodiments is depicted in FIG. 1. The glass substrate article 100 has a thickness t that extends between a first surface 110 and a second surface 112. A 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 that is measured from the first surface 110 into the glass substrate article 100. A 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 that is measured from the second surface 112 into the glass substrate article 100. A hydrogen-free material region 130 is present between the first layer depth and the second layer depth. The hydrogen-containing layer of the glass substrate article can have a layer depth (DOL) greater than 5 μm. In some embodiments, the layer depth can be greater than or equal to 10 μm, such as greater than or equal to 15 μm, greater than or equal to 20 μm, greater than or equal to 25 μm, greater than or equal to 30 μm, greater than or equal to 35 μm, greater than or equal to 40 μm, greater than or equal to 45 μm, greater than or equal to 50 μm, greater than or equal to 55 μm, greater than or equal to 60 μm, greater than or equal to 65 μm, greater than or equal to 70 μm, greater than or equal to 75 μm, greater than or equal to 80 μm, greater than or equal to 85 μm, greater than or equal to 90 μm, greater than or equal to 95 μm, greater than or equal to 100 μm, greater than or equal to 105 μm, greater than or equal to 110 μm, greater than or equal to 115 μm, greater than or equal to 120 μm, greater than or equal to 125 μm, greater than or equal to 130 μm, greater than or equal to 135 μm, greater than or equal to 140 μm, greater than or equal to 145 μm, greater than or equal to 150 μm, greater than or equal to 155 μm, greater than or equal to 160 μm, greater than or equal to 165 μm, greater than or equal to 170 μm, greater than or equal to 175 μm, greater than or equal to 180 μm, greater than or equal to 185 μm, greater than or equal to 190 μm, greater than or equal to 195 μm, greater than or equal to 200 μm or greater.In some embodiments, the layer depth can be greater than 5 μm and less than or equal to 205 μm, such as, greater than or equal to 10 μm and less than or equal to 200 μm, greater than or equal to 15 μm and less than or equal to 200 μm, greater than or equal to 20 μm and less than or equal to 195 μm, greater than or equal to 25 μm and less than or equal to 190 μm, greater than or equal to 30 μm and less than or equal to 185 μm, greater than or equal to 35 μm and less than or equal to 180 μm, greater than or equal to 40 μm and less than or equal to 175 μm, greater than or equal to 45 μm and less than or equal to 170 μm, greater than or equal to 50 μm and less than or equal to 165 μm, greater than or equal to 55 μm and less than or equal to 160 μm, greater than or equal to 60 μm and less than or equal to 155 μm, greater than or equal to 65 μm and less than or equal to 150 μm, greater than or equal to 70 μm and less than or equal to 145 μm, greater than or equal to 75 μm and less than or equal to 140 μm, greater than or equal to 80 μm and less than or equal to 135 μm, greater than or equal to 85 μm and less than or equal to 130 μm, greater than or equal to 90 μm and less than or equal to 125 μm, greater than or equal to 95 μm and less than or equal to 120 μm, greater than or equal to 100 μm and less than or equal to 115 μm, greater than or equal to 105 μm and less than or equal to 110 μm, or any sub-range formed by any of these endpoints. Generally, the layer depth exhibited by the glass substrate object is greater than the layer depth that can be generated by exposure to the surrounding environment. The hydrogen-containing layer of the glass substrate object can have a layer depth (depth of layer; DOL) greater than 0.005 t, where t is the thickness of the glass substrate object. In some embodiments, the layer depth can be greater than or equal to 0.010 t, such as, greater than or equal to 0.015 t, greater than or equal to 0.020 t, greater than or equal to 0.025 t, greater than or equal to 0.030 t, greater than or equal to 0.035 t, greater than or equal to 0.040 t, greater than or equal to 0.045 t, greater than or equal to 0.050 t, greater than or equal to 0.055 t, greater than or equal to 0.060 t, greater than or equal to 0.065 t is greater than or equal to 0.070 t is greater than or equal to 0.075 t is greater than or equal to 0.080 t is greater than or equal to 0.085 t is greater than or equal to 0.090 t is greater than or equal to 0.095 t is greater than or equal to 0.10 t is greater than or equal to 0.15 t is greater than or equal to 0.20 t or greater. In some embodiments, DOL can be greater than 0.005 t and less than or equal to 0.205 t, such as, greater than or equal to 0.010 t and less than or equal to 0.200 t, greater than or equal to 0.015 t and less than or equal to 0.195 t, greater than or equal to 0.020 t and less than or equal to 0.190 t, greater than or equal to 0.025 t and less than or equal to 0.185 t, greater than or equal to 0.030 t and less than or equal to 0.180 t, greater than or equal to 0.035 t and less than or equal to 0.175 t, greater than or equal to 0.040 t and less than or equal to 0.170 t, greater than or equal to 0.045 t and less than or equal to 0.165 t, greater than or equal to 0.050 t and less than or equal to 0.160 t, greater than or equal to 0.055 t and less than or equal to 0.155 t, greater than or equal to 0.060 t and less than or equal to 0.150 t, greater than or equal to 0.065 t and less than or equal to 0.145 t, greater than or equal to 0.070 t is less than or equal to 0.140 t, is greater than or equal to 0.075 t is less than or equal to 0.135 t, is greater than or equal to 0.080 t is less than or equal to 0.130 t, is greater than or equal to 0.085 t is less than or equal to 0.125 t, is greater than or equal to 0.090 t is less than or equal to 0.120 t, is greater than or equal to 0.095 t is less than or equal to 0.115 t, is greater than or equal to 0.100 t is less than or equal to 0.110 t or any sub-range formed by any of these endpoints. The layer depth and hydrogen concentration are measured by secondary ion mass spectrometry (SIMS) techniques known in the art. SIMS techniques can measure the hydrogen concentration at a given depth, but cannot distinguish the hydrogen species present in the glass substrate object. For this reason, all hydrogen species contribute to the hydrogen concentration measured by SIMS. As used herein, the depth of layer (DOL) refers to the first depth below the surface of the glass substrate object at which the hydrogen concentration is equal to the hydrogen concentration at the center of the glass substrate object. This definition describes the hydrogen concentration of the glass substrate substrate prior to processing, such that the layer concentration refers to the depth of hydrogen added by the processing process. In practice, the hydrogen concentration at the center of the glass substrate object can be estimated by the hydrogen concentration at a depth from the surface of the glass substrate object at which the hydrogen concentration becomes substantially constant, since it is expected that the hydrogen concentration does not change between this depth and the center of the glass substrate object. This estimate allows the determination of the DOL without measuring the hydrogen concentration throughout the entire depth of the glass substrate object. In some embodiments, all of the thickness of the glass substrate article can be part of a hydrogen-containing layer. This glass substrate article can be produced when the treatment of the glass substrate is extended for a sufficient time under conditions sufficient for hydrogen species to diffuse from each exposed surface to the center of the glass substrate article. In some embodiments, with the surfaces of the glass substrate article exposed to the same treatment conditions, the minimum hydrogen concentration can be at half the thickness of the glass substrate article such that the hydrogen-containing layers meet at the center of the glass substrate article. In such embodiments, the DOL can be at half the thickness of the glass substrate article. In some embodiments, the glass substrate articles can not include a region free of added hydrogen species. In some embodiments, the glass substrate article can be treated in a wet environment such that the concentration of the added hydrogen species is uniform throughout the glass substrate article and the hydrogen concentration does not vary with depth below the surface of the glass substrate article. A glass substrate article according to such embodiments will not exhibit a DOL as defined herein because the hydrogen concentration at the center of the glass substrate article will be equivalent to the hydrogen concentration at all other depths. These glass substrate articles are highly resistant to Vickers indentation cracking. High resistance to Vickers indentation cracking confers high damage resistance to the glass substrate articles. Without wishing to be bound by any theory of the features, the water content of the glass substrate article can reduce the local viscosity of the hydrogen-containing layer such that local flow rather than cracking occurs. The Vickers indentation cracking threshold of the glass substrate article is achieved without using conventional strengthening techniques such as ion exchange of large alkali ions for smaller alkali ions in the glass, thermal tempering, or lamination of glass layers having a mismatch in thermal expansion coefficients. The glass substrate article exhibits a Vickers indentation cracking threshold of greater than or equal to 1 kgf, such as greater than or equal to 2 kgf, greater than or equal to 3 kgf, greater than or equal to 4 kgf, greater than or equal to 5 kgf, greater than or equal to 6 kgf, greater than or equal to 7 kgf, greater than or equal to 8 kgf, greater than or equal to 9 kgf, greater than or equal to 10 kgf, greater than or equal to 11 kgf, greater than or equal to 12 kgf, greater than or equal to 13 kgf, greater than or equal to 14 kgf, greater than or equal to 15 kgf, greater than or equal to 16 kgf, greater than or equal to 17 kgf, greater than or equal to 18 kgf, greater than or equal to 19 kgf, greater than or equal to 20 kgf, greater than or equal to 21 kgf, greater than or equal to 22 kgf, greater than or equal to 23 kgf, greater than or equal to 24 kgf, greater than or equal to 25 kgf, greater than or equal to 26 kgf, greater than or equal to 27 kgf, greater than or equal to 28 kgf, greater than or equal to 29 kgf, greater than or equal to 30 kgf or greater. In some embodiments, the glass substrate article exhibits a Vickers indentation cracking threshold from greater than or equal to 1 kgf to less than or equal to 30 kgf, such as from greater than or equal to 2 kgf to less than or equal to 29 kgf, from greater than or equal to 3 kgf to less than or equal to 28 kgf, from greater than or equal to 4 kgf to less than or equal to 27 kgf, from greater than or equal to 5 kgf to less than or equal to 26 kgf, from greater than or equal to 6 kgf to less than or equal to 25 kgf, from greater than or equal to 7 kgf to less than or equal to 24 kgf, from greater than or equal to 8 kgf to less than or equal to 23 kgf, from greater than or equal to 9 kgf to less than or equal to 22 kgf, from greater than or equal to 10 kgf to less than or equal to 21 kgf, from greater than or equal to 11 kgf to less than or equal to 20 kgf, from greater than or equal to 12 kgf to less than or equal to 19 kgf, from greater than or equal to 13 kgf to less than or equal to 18 kgf, from greater than or equal to 14 kgf to less than or equal to 17 kgf, from greater than or equal to 15 kgf to less than or equal to 16 kgf, or any sub-range formed by any of these endpoints. The Vickers initiation threshold (or indentation fracture threshold) is measured by a Vickers indenter. The Vickers initiation threshold is a measure of the indentation damage resistance of the glass. The test involves using a square-based pyramidal diamond indenter with an angle of 136° between the faces, called a Vickers indenter. The Vickers indenter is the same as the indenter used in standard microhardness tests (such as described in ASTM-E384-11). Select at least five specimens to represent the glass type and / or sample of interest. For each specimen, multiple sets of five indentations are introduced onto the specimen surface. Each set of five indentations is introduced at a given load, where each individual indentation is separated by at least 5 mm and no less than 5 mm from a specimen edge. For test loads ≥ 2 kg, use an indenter loading / unloading rate of 50 kg / min. For test loads < 2 kg, use a rate of 5 kg / min. Use a dwell (i.e., hold) time of 10 seconds at the target load. The machine maintains load control during the dwell period. After a period of at least 12 hours, the indentations are examined in reflected light using a compound microscope at 500X magnification. Then, for each indentation, the presence or absence of median / radial cracking (cracking extending from the indentation along a plane perpendicular to the main plane of the object) or specimen fracture is noted. Note that the formation of lateral cracking (cracking extending along a plane parallel to the main plane of the object) is not considered indicative of threshold behavior, as the formation of median / radial cracking or specimen fracture is of interest for this test. Define the specimen threshold as the midpoint of the lowest continuous indentation load (which includes more than 50% of the individual indentations that meet the threshold). For example, if within an individual specimen, 2 / 5 (40%) of the indentations induced at a 5 kg load have exceeded the threshold and 3 / 5 (60%) of the indentations induced at a 6 kg load have exceeded the threshold, then the specimen threshold will be defined as greater than 5 kg. The range (lowest value to highest value) of all specimen midpoints can also be reported for each sample. Control the pre-test, test, and post-test environments to 23 ± 2 °C and 50 ± 5% Rh to minimize variations in the fatigue (stress corrosion) behavior of the specimens. Without wishing to be bound by any particular theory, the hydrogen-containing layer of the glass substrate object can be the result of the mutual diffusion of hydrogenous substances for the ions contained in the composition of the glass substrate. Monovalent hydrogenous substances (such as, H 3 O + and / or H + ) can replace the alkali ions contained in the glass substrate composition to form the glass substrate object. The size of the alkali ions replaced by the hydrogenous substances affects the diffusivity of the hydrogenous substances in the glass substrate, because larger alkali ions create larger void spaces that facilitate the mutual diffusion mechanism. For example, hydronium ions (H 3 O + ) having an ionic radius that is close to that of potassium and much larger than that of lithium. It has been observed that when the glass substrate contains potassium, the diffusivity of the hydrogen-containing substance in the glass substrate is significantly two orders of magnitude higher than when the glass substrate contains lithium. This observed behavior may also indicate that the hydrated hydrogen ion is the main monovalent hydrogen-containing substance diffusing into the glass substrate. The ionic radii for the alkali ions and the hydrated hydrogen ion are reported in Table I below. As shown in Table I, rubidium and cesium have ionic radii significantly larger than that of the hydrated hydrogen ion, which can result in a higher hydrogen diffusivity than that observed for potassium. In some embodiments, the replacement of alkali ions in a glass substrate having hydrogen ions can create a compressive stress layer extending from the surface of the glass substrate object into the glass substrate object to a compressive depth. As used herein, the depth of layer (DOC) means the depth at which the stress in the glass substrate object changes from compressive to tensile. Thus, the glass substrate object also contains a tensile stress region having a maximum central tension (CT) such that the forces are balanced within the glass substrate object. Without wishing to be bound by any theory, the compressive stress region may be the result of the exchange of hydrogen ions having an ionic radius greater than that of the ion being replaced. In some embodiments, the compressive stress layer can include a compressive stress of greater than or equal to 100 MPa, such as greater than or equal to 105 MPa, greater than or equal to 110 MPa, greater than or equal to 115 MPa, greater than or equal to 120 MPa, greater than or equal to 125 MPa, greater than or equal to 130 MPa, greater than or equal to 135 MPa or greater. In some embodiments, the compressive stress layer can include a compressive stress from greater than or equal to 100 MPa to less than or equal to 150 MPa, such as from greater than or equal to 105 MPa to less than or equal to 145 MPa, from greater than or equal to 110 MPa to less than or equal to 140 MPa, from greater than or equal to 115 MPa to less than or equal to 135 MPa, from greater than or equal to 120 MPa to less than or equal to 130 MPa, 125 MPa or any sub-range formed from any of these endpoints. In some embodiments, the DOC of the compressive stress layer can be greater than or equal to 75 MPa, such as, greater than or equal to 80 MPa, greater than or equal to 85 MPa, greater than or equal to 90 MPa, greater than or equal to 95 MPa, greater than or equal to 100 MPa or greater. In some embodiments, the DOC of the compressive stress layer can be from greater than or equal to 75 μm to less than or equal to 115 μm, such as, from greater than or equal to 80 μm to less than or equal to 110 μm, from greater than or equal to 85 μm to less than or equal to 105 μm, from greater than or equal to 90 μm to less than or equal to 100 μm, 95 μm or any sub-range that can be formed from any of these endpoints. In some embodiments, the glass substrate object can have a DOC greater than or equal to 0.05 of t, where t is the thickness of the glass substrate object, such as, greater than or equal to 0.06 of t, greater than or equal to 0.07 of t, greater than or equal to 0.08 of t, greater than or equal to 0.09 of t, greater than or equal to 0.10 of t, greater than or equal to 0.11 of t, greater than or equal to 0.12 of t or greater. In some embodiments, the glass substrate object can have a DOC from greater than or equal to 0.05 of t to less than or equal to 0.20 of t, such as, from greater than or equal to 0.06 of t to less than or equal to 0.19 of t, from greater than or equal to 0.07 of t to less than or equal to 0.18 of t, from greater than or equal to 0.08 of t to less than or equal to 0.17 of t, from greater than or equal to 0.09 of t to less than or equal to 0.16 of t, from greater than or equal to 0.10 of t to less than or equal to 0.15 of t, from greater than or equal to 0.11 of t to less than or equal to 0.14 of t, from greater than or equal to 0.12 of t to less than or equal to 0.13 of t or any sub-range that can be formed from any of these endpoints. In some embodiments, the CT of the glass substrate article can be greater than or equal to 10 Mpa, such as greater than or equal to 11 MPa, greater than or equal to 12 MPa, greater than or equal to 13 MPa, greater than or equal to 14 MPa, greater than or equal to 15 MPa, greater than or equal to 16 MPa, greater than or equal to 17 MPa, greater than or equal to 18 MPa, greater than or equal to 19 MPa, greater than or equal to 20 MPa, greater than or equal to 22 MPa, greater than or equal to 24 MPa, greater than or equal to 26 MPa, greater than or equal to 28 MPa, greater than or equal to 30 MPa, greater than or equal to 32 MPa or greater. In some embodiments, the CT of the glass substrate article can be from greater than or equal to 10 Mpa to less than or equal to 35 MPa, such as from greater than or equal to 11 Mpa to less than or equal to 34 MPa, from greater than or equal to 12 Mpa to less than or equal to 33 MPa, from greater than or equal to 13 Mpa to less than or equal to 32 MPa, from greater than or equal to 14 Mpa to less than or equal to 32 MPa, from greater than or equal to 15 Mpa to less than or equal to 31 MPa, from greater than or equal to 16 Mpa to less than or equal to 30 MPa, from greater than or equal to 17 Mpa to less than or equal to 28 MPa, from greater than or equal to 18 Mpa to less than or equal to 26 MPa, from greater than or equal to 19 Mpa to less than or equal to 24 MPa, from greater than or equal to 20 Mpa to less than or equal to 22 MPa or any sub-range formed from any of these endpoints. The compressive stress (including surface CS) is measured by a surface stress meter using a commercially available instrument such as the FSM-6000 (FSM) manufactured by Orihara Industrial Co., Ltd. (Japan). The surface stress measurement result depends on the accurate measurement of the stress optical coefficient (SOC) related to the birefringence of the glass. The SOC is measured according to Procedure C (glass disc method) described in ASTM standard C770-16 entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the content of which is incorporated herein by reference in its entirety. The DOC is measured by the FSM. The maximum central tension (CT) value is measured using a scattered light polariscope (SCALP) known in the art. The glass substrate article can be formed from a glass substrate having any suitable composition. The composition of the glass substrate can be specifically selected to facilitate the diffusion of hydrogen-containing substances, such that a glass substrate article including a hydrogen-containing layer can be efficiently formed. In some embodiments, the glass substrate can have a composition including SiO 2 、Al 2 O 3 and P 2 O 5 In some embodiments, the glass substrate can additionally include an alkali metal oxide, such as, Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O. In some embodiments, the glass substrate can be substantially free or free of at least one of lithium and sodium. In some embodiments, after the diffusion of the hydrogen-containing substance into the glass substrate, the glass substrate article can have an overall composition that is substantially the same as the composition of the glass substrate. In some embodiments, the hydrogen substance may not diffuse to the center of the glass substrate article. In other words, the center of the glass substrate article is the region least affected by the water vapor treatment. For this reason, before treatment in a water-containing environment, the center of the glass substrate article can have a composition that is substantially the same as or the same as the composition of the glass substrate. The glass substrate can include any suitable amount of SiO 2 . SiO 2 is the largest component, and thus, SiO 2 is the main component of the glass network formed from the glass composition. If the concentration of SiO 2 in the glass composition is too high, the formability of the glass composition can be reduced because the higher concentration of SiO 2 increases the difficulty of melting the glass, which in turn adversely affects the formability of the glass. In some embodiments, the glass substrate can include an amount of SiO 2 from greater than or equal to 45 mole % to less than or equal to 75 mole %, such as, from greater than or equal to 46 mol% to less than or equal to 74 mol%, from greater than or equal to 47 mol% to less than or equal to 73 mol%, from greater than or equal to 48 mol% to less than or equal to 72 mol%, from greater than or equal to 49 mol% to less than or equal to 71 mol%, from greater than or equal to 50 mol% to less than or equal to 70 mol%, from greater than or equal to 51 mol% to less than or equal to 69 mol%, from greater than or equal to 52 mol% to less than or equal to 68 mol%, from greater than or equal to 53 mol% to less than or equal to 67 mol%, from greater than or equal to 54 mol% to less than or equal to 66 mol%, from greater than or equal to 55 mol% to less than or equal to 65 mol%, from greater than or equal to 56 mol% to less than or equal to 64 mol%, from greater than or equal to 57 mol% to less than or equal to 63 mol%, from greater than or equal to 58 mol% to less than or equal to 62 mol%, from greater than or equal to 59 mol% to less than or equal to 61 mol%, 60 mol%, or any sub-range formed from any of these endpoints. In some embodiments, the glass substrate may comprise an amount of SiO from greater than or equal to 55 mol% to less than or equal to 69 mol% 2 , such as, from greater than or equal to 58 mol% to less than or equal to 63 mol%, or any sub-range formed from any of these endpoints. The glass substrate may comprise any suitable amount of Al 2 O 3 . Al 2 O 3 can act as a glass network former, similar to SiO 2 . Al 2 O 3 Due to its tetrahedral coordination in the glass melt formed from the glass composition, it can increase the viscosity of the glass composition, so that when the amount of Al 2 O 3 is too high, it reduces the formability of the glass composition. However, when the concentration of Al 2 O 3 is balanced against the concentration of SiO 2 and the concentration of alkali oxides in the glass composition, Al 2 O 3 can lower the liquidus temperature of the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as fusion forming processes. Al in the glass substrate 2 O 3 in the glass substrate includes preventing phase separation and reducing the number of non-bridging oxygen (NBO) in the glass. Additionally, Al 2 O 3 can improve the effectiveness of ion exchange. In some embodiments, the glass substrate can include from greater than or equal to 3 mole % to less than or equal to 20 mole % of Al 2 O 3 , such as from greater than or equal to 4 mole % to less than or equal to 19 mole %, from greater than or equal to 5 mole % to less than or equal to 18 mole %, from greater than or equal to 6 mole % to less than or equal to 17 mole %, from greater than or equal to 7 mole % to less than or equal to 16 mole %, from greater than or equal to 8 mole % to less than or equal to 15 mole %, from greater than or equal to 9 mole % to less than or equal to 14 mole %, from greater than or equal to 10 mole % to less than or equal to 13 mole %, from greater than or equal to 11 mole % to less than or equal to 12 mole %, or any sub-range formed by any of these endpoints. In some embodiments, the glass substrate can include from greater than or equal to 5 mole % to less than or equal to 15 mole % of Al 2 O 3 , such as from greater than or equal to 7 mole % to less than or equal to 14 mole %, or any sub-range formed by any of these endpoints. The glass substrate can include any amount of P sufficient to produce the desired hydrogen diffusivity 2 O 5 . The inclusion of phosphorus in the glass substrate promotes faster interdiffusion, independent of the exchange ion pairs. Thus, a phosphorus-containing glass substrate allows for the efficient formation of a glass substrate article including a hydrogen-containing layer. P 2 O 5which also allows for the production of glass substrate articles having a deep layer depth (e.g., greater than about 10 μm) in a relatively short processing time. In some embodiments, the glass substrate may comprise from greater than or equal to 4 mol% to less than or equal to 15 mol% of P 2 O 5 , such as from greater than or equal to 5 mol% to less than or equal to 14 mol%, from greater than or equal to 6 mol% to less than or equal to 13 mol%, from greater than or equal to 7 mol% to less than or equal to 12 mol%, from greater than or equal to 8 mol% to less than or equal to 11 mol%, from greater than or equal to 9 mol% to less than or equal to 10 mol%, or any sub-range formed by any of these endpoints. In some embodiments, the glass substrate may comprise from greater than or equal to 5 mol% to less than or equal to 15 mol% of P 2 O 5 , such as from greater than or equal to 6 mol% to less than or equal to 15 mol%, from greater than or equal to 5 mol% to less than or equal to 10 mol%, from greater than or equal to 6 mol% to less than or equal to 10 mol%, from greater than or equal to 7 mol% to less than or equal to 10 mol%, or any sub-range formed by any of these endpoints. The glass substrate may comprise any suitable amount of alkali metal oxide. Alkali metal oxides facilitate ion exchange. The sum of the alkali metal oxides (e.g., Li 2 O, Na 2 O, and K 2 O, and other alkali metal oxides including Cs 2 O and Rb 2 O) in the glass composition may be referred to as "R 2 O", and R 2 O may be expressed in mol%. In some embodiments, the glass substrate may be substantially free or free of at least one of lithium and sodium. In some embodiments, the glass composition comprises greater than or equal to 6 mol% of R 2O, such as, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, greater than or equal to 10 mol%, greater than or equal to 11 mol%, greater than or equal to 12 mol%, greater than or equal to 13 mol%, greater than or equal to 14 mol%, greater than or equal to 15 mol%, greater than or equal to 16 mol%, greater than or equal to 17 mol%, greater than or equal to 18 mol%, greater than or equal to 19 mol%, greater than or equal to 20 mol%, greater than or equal to 21 mol%, greater than or equal to 22 mol%, greater than or equal to 23 mol% or greater than or equal to 24 mol%. In one or more embodiments, the glass composition comprises an amount of R less than or equal to 25 mol% 2 O, such as, less than or equal to 24 mol%, less than or equal to 23 mol%, less than or equal to 22 mol%, less than or equal to 21 mol%, less than or equal to 20 mol%, less than or equal to 19 mol%, less than or equal to 18 mol%, less than or equal to 17 mol%, less than or equal to 16 mol%, less than or equal to 15 mol%, less than or equal to 14 mol%, less than or equal to 13 mol%, less than or equal to 12 mol%, less than or equal to 11 mol%, less than or equal to 10 mol%, less than or equal to 9 mol%, less than or equal to 8 mol% or less than or equal to 7 mol%. It should be understood that in embodiments, any of the above ranges may be combined with any other range. In some embodiments, the glass composition comprises an amount of R from greater than or equal to 6.0 mol% to less than or equal to 25.0 mol% 2 O, such as, from greater than or equal to 7.0 mol% to less than or equal to 24.0 mol%, from greater than or equal to 8.0 mol% to less than or equal to 23.0 mol%, from greater than or equal to 9.0 mol% to less than or equal to 22.0 mol%, from greater than or equal to 10.0 mol% to less than or equal to 21.0 mol%, from greater than or equal to 11.0 mol% to less than or equal to 20.0 mol%, from greater than or equal to 12.0 mol% to less than or equal to 19.0 mol%, from greater than or equal to 13.0 mol% to less than or equal to 18.0 mol%, from greater than or equal to 14.0 mol% to less than or equal to 17.0 mol% or from greater than or equal to 15.0 mol% to less than or equal to 16.0 mol%, and all ranges and sub - ranges between the foregoing values. In some embodiments, the alkali metal oxide can be K 2 O. The inclusion of K 2 O allows for efficient exchange of hydrogen species into the glass substrate upon exposure to a hydrous environment. In some embodiments, the glass substrate can comprise an amount of K from greater than or equal to 6 mol% to less than or equal to 25 mol% 2 O, such as, greater than or equal to 7 mol% to less than or equal to 24 mol%, greater than or equal to 8 mol% to less than or equal to 23 mol%, greater than or equal to 9 mol% to less than or equal to 22 mol%, greater than or equal to 10 mol% to less than or equal to 21 mol%, greater than or equal to 11 mol% to less than or equal to 20 mol%, greater than or equal to 12 mol% to less than or equal to 19 mol%, greater than or equal to 13 mol% to less than or equal to 18 mol%, greater than or equal to 14 mol% to less than or equal to 17 mol%, or greater than or equal to 15 mol% to less than or equal to 16 mol%, or any sub-range formed from any of these endpoints. In some embodiments, the glass substrate may comprise an amount of K greater than or equal to 10 mol% to less than or equal to 25 mol% 2 O, such as, greater than or equal to 10 mol% to less than or equal to 20 mol%, greater than or equal to 11 mol% to less than or equal to 25 mol%, greater than or equal to 11 mol% to less than or equal to 20 mol%, greater than or equal to 15 mol% to less than or equal to 20 mol%, or any sub-range formed from any of these endpoints. The glass substrate may comprise any suitable amount of Rb 2 O. In some embodiments, the glass substrate may comprise an amount of Rb greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O, such as, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 8 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, 5 mol%, or any sub-range formed from any of these endpoints. The glass substrate may comprise any suitable amount of Cs 2 O. In some embodiments, the glass substrate may comprise an amount of Cs greater than or equal to 0 mol% to less than or equal to 10 mol% 2 O, such as, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 8 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, 5 mol%, or any sub-range formed from any of these endpoints. In some embodiments, the glass substrate may have a composition comprising one of the following: SiO greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al from greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P from greater than or equal to 6 mol% to less than or equal to 15 mol% 2 O 5 ; and K from greater than or equal to 6 mol% to less than or equal to 25 mol% 2 O. In some embodiments, the glass substrate may have a composition comprising one of the following: SiO from greater than or equal to 45 mol% to less than or equal to 75 mol% 2 ; Al from greater than or equal to 3 mol% to less than or equal to 20 mol% 2 O 3 ; P from greater than or equal to 4 mol% to less than or equal to 15 mol% 2 O 5 ; and K from greater than or equal to 11 mol% to less than or equal to 25 mol% 2 O. In some embodiments, the glass substrate may have a composition comprising one of the following: SiO from greater than or equal to 55 mol% to less than or equal to 69 mol% 2 ; Al from greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P from greater than or equal to 6 mol% to less than or equal to 10 mol% 2 O 5 ; and K from greater than or equal to 10 mol% to less than or equal to 20 mol% 2 O. In some embodiments, the glass substrate may have a composition comprising one of the following: SiO from greater than or equal to 55 mol% to less than or equal to 69 mol% 2 ; Al from greater than or equal to 5 mol% to less than or equal to 15 mol% 2 O 3 ; P ranging from greater than or equal to 5 mol% to less than or equal to 10 mol% 2 O 5 ; and K ranging from greater than or equal to 11 mol% to less than or equal to 20 mol% 2 O. In some embodiments, the glass substrate may have a composition comprising: SiO ranging from greater than or equal to 58 mol% to less than or equal to 63 mol% 2 ; Al ranging from greater than or equal to 7 mol% to less than or equal to 14 mol% 2 O 3 ; P ranging from greater than or equal to 7 mol% to less than or equal to 10 mol% 2 O 5 ; and K ranging from greater than or equal to 15 mol% to less than or equal to 20 mol% 2 O. In some embodiments, the glass substrate may exhibit a Vickers cracking initial threshold of greater than or equal to 5 kgf, such as greater than or equal to 6 kgf, greater than or equal to 7 kgf, greater than or equal to 8 kgf, greater than or equal to 9 kgf, greater than or equal to 10 kgf or greater. The glass substrate can have any suitable geometry. In some embodiments, the glass substrate may have a thickness of less than or equal to 2 mm, such as less than or equal to 1 mm, less than or equal to 900 μm, less than or equal to 800 μm, less than or equal to 700 μm, less than or equal to 600 μm, less than or equal to 500 μm, less than or equal to 400 μm, less than or equal to 300 μm or less. 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 a sheet-like object 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, "3D shape" refers to an object having first and second opposing major surfaces that are at least partially non-planar. Glass substrate articles can be produced from glass substrate wafers by exposure to water vapor under any suitable conditions. The exposure can be carried out in any suitable element, such as an oven with relative humidity control. In some embodiments, the glass substrate wafer can be exposed to an environment having a relative humidity greater than or equal to 75%, such as greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, greater than or equal to 95%, greater than or equal to 99% or greater. In some embodiments, the glass substrate wafer can be exposed to an environment having 100% relative humidity. In some embodiments, the glass substrate wafer can be exposed to an environment at a temperature greater than or equal to 70°C, such as greater than or equal to 75°C, greater than or equal to 80°C, greater than or equal to 85°C, greater than or equal to 90°C, greater than or equal to 95°C, greater than or equal to 100°C, greater than or equal to 105°C, greater than or equal to 110°C, greater than or equal to 115°C, greater than or equal to 120°C, greater than or equal to 125°C, greater than or equal to 130°C, greater than or equal to 135°C, greater than or equal to 140°C, greater than or equal to 145°C, greater than or equal to 150°C, greater than or equal to 155°C, greater than or equal to 160°C, greater than or equal to 160°C, greater than or equal to 165°C, greater than or equal to 170°C, greater than or equal to 175°C, greater than or equal to 180°C, greater than or equal to 185°C, greater than or equal to 190°C, greater than or equal to 195°C, greater than or equal to 200°C or greater. In some embodiments, the glass substrate wafer can be exposed to an environment at a temperature from greater than or equal to 70°C to less than or equal to 210°C, such as from greater than or equal to 75°C to less than or equal to 205°C, from greater than or equal to 80°C to less than or equal to 200°C, from greater than or equal to 85°C to less than or equal to 195°C, from greater than or equal to 90°C to less than or equal to 190°C, from greater than or equal to 90°C to less than or equal to 185°C, from greater than or equal to 100°C to less than or equal to 180°C, from greater than or equal to 105°C to less than or equal to 175°C, from greater than or equal to 110°C to less than or equal to 170°C, from greater than or equal to 115°C to less than or equal to 165°C, from greater than or equal to 120°C to less than or equal to 160°C, from greater than or equal to 125°C to less than or equal to 155°C, from greater than or equal to 130°C to less than or equal to 150°C, from greater than or equal to 135°C to less than or equal to 145°C, 140°C or any sub-range formed from these endpoints. In some embodiments, the glass substrate may be exposed to an environment containing water vapor for a time period sufficient to produce a desired degree of hydrogen-containing material diffusion and a desired layer depth. In some embodiments, the glass substrate may be exposed to an environment containing water vapor for greater than or equal to 1 day, such as greater than or equal to 2 days, greater than or equal to 3 days, greater than or equal to 4 days, greater than or equal to 5 days, greater than or equal to 6 days, greater than or equal to 7 days, greater than or equal to 8 days, greater than or equal to 9 days, greater than or equal to 10 days, greater than or equal to 15 days, greater than or equal to 20 days, greater than or equal to 25 days, greater than or equal to 30 days, greater than or equal to 35 days, greater than or equal to 40 days, greater than or equal to 45 days, greater than or equal to 50 days, greater than or equal to 55 days, greater than or equal to 60 days, greater than or equal to 65 days or more. In some embodiments, the glass substrate may be exposed to an environment containing water vapor for a time period greater than or equal to 1 day to less than or equal to 70 days, such as from greater than or equal to 2 days to less than or equal to 65 days, from greater than or equal to 3 days to less than or equal to 60 days, from greater than or equal to 4 days to less than or equal to 55 days, from greater than or equal to 5 days to less than or equal to 45 days, from greater than or equal to 6 days to less than or equal to 40 days, from greater than or equal to 7 days to less than or equal to 35 days, from greater than or equal to 8 days to less than or equal to 30 days, from greater than or equal to 9 days to less than or equal to 25 days, from greater than or equal to 10 days to less than or equal to 20 days, 15 days or any sub-range formed from any of these endpoints. The exposure conditions can be modified to reduce the time necessary to produce the desired amount of hydrogen-containing material diffusion into the glass substrate. For example, the temperature and / or relative humidity can be increased to reduce the time required to achieve the desired degree of hydrogen-containing material diffusion and layer depth into the glass substrate. The glass substrate articles disclosed herein can be incorporated into another article, such as an article having a display (or display article) (e.g., consumer electronics, including mobile phones, tablet computers, computers, navigation systems, wearable elements (e.g., watches), and the like), a building article, a transportation article (e.g., cars, trains, airplanes, ships, etc.), an electrical article, or any article that requires a certain transparency, scratch resistance, wear resistance, or a combination thereof. An exemplary article incorporating any of the glass substrate articles disclosed herein is shown in FIGS. 2A and 2B. Specifically, FIGS. 2A and 2B show a consumer electronics component 200 that includes: a housing 202 having a front portion 204, a rear portion 206, and side surfaces 208; electrical components (not shown) that are at least partially or entirely inside the housing and include at least one controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or on the front surface of the housing such that it is over the display. In some embodiments, at least a portion of one of the cover substrate 212 and the housing 202 may include any of the glass substrate articles disclosed herein. Exemplary embodiments A glass composition particularly suitable for forming the glass substrate articles herein is formed into a glass substrate. The compositions of Examples 1 to 6 are described in Table II below. The density is determined using the buoyancy method of ASTM C693-93(2013). The coefficient of linear thermal expansion (CTE) over the temperature range of 25 °C to 300 °C is expressed in 10 -7 / °C and is determined using a push rod dilatometer according to ASTM E228-11. The strain point and annealing point are determined using the beam bending viscosity method of ASTM C598-93(2013). The softening point is determined using the parallel plate viscosity method of ASTM C1351M-96(2012). According to ASTM C965-96(2012) entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point", the temperatures at which the glass has a viscosity of 200 P, 35,000 P, and 200,000 P are measured for the resulting composition. A glass substrate having the composition of Example 1 and a thickness of 1 mm is exposed to an environment of 85% relative humidity for 65 days to form a glass substrate article including a hydrogen-containing layer of the type described herein. Before and after exposure, the depth of the hydrogen-containing layer was measured by SIMS. The results of the SIMS hydrogen concentration measurement are shown in Figure 3, where the hydrogen concentration curve 301 of the as-received glass substrate has a layer depth of about 5 μm, and the hydrogen concentration curve 302 of the glass substrate object has a layer depth of about 30 μm. The glass substrate object after exposure was measured to a depth of about 25 μm, and the extrapolated curve 303 was used to determine the layer depth. Based on the measured values, the hydrogen diffusivity (D) was calculated using the general formula DOL = sqrt(D•time). Before and after exposure to an environment containing water vapor, the Vickers indentation cracking threshold was measured. After indentation at 5 kgf and 10 kgf respectively, the results of the Vickers indentation of the as-received glass substrate are shown in Figures 4 and 5. As shown in Figures 4 and 5, the glass substrate has an initial Vickers cracking threshold higher than 5 kgf but lower than 10 kgf. After indentation at 5 kgf, 10 kgf, and 20 kgf respectively, the results of the Vickers indentation of the exposed glass substrate object are shown in Figures 6, 7, and 8. As demonstrated by Figures 6, 7, and 8, the Vickers indentation cracking threshold of the glass substrate object is greater than 20 kgf. Glass substrates having the compositions of Comparative Examples 1 to 3 and 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 to 3 are reported in Table III below. Before and after exposure to an environment containing water vapor, the Vickers indentation cracking threshold was measured, and after exposure, the depth of the hydrogen-containing layer was measured by SIMS. The hydrogen diffusivity was calculated based on the measured values. As shown in Table III, the glass composition of Example 1 exhibited a hydrogen diffusivity two orders of magnitude higher than that of the glass composition of Comparative Example 3, which also included potassium but did not include phosphorus. These results indicate that the presence of phosphorus in the glass composition shows an increase in hydrogen diffusivity. Similarly, the glass composition of Comparative Example 3 exhibited a hydrogen diffusivity two orders of magnitude higher than those of Comparative Examples 1 and 2, which included lithium and sodium respectively. The difference in hydrogen diffusivity between the potassium-containing glass composition and the lithium- and sodium-containing glass compositions indicates that alkali ions with larger ionic radii allow faster hydrogen diffusivity. A glass substrate comprising the glass composition of Example 6 was produced with thicknesses of 0.5 mm and 1.0 mm. The glass substrate was exposed to a 100% relative humidity environment at 200 °C for a period of 7 days to produce glass substrate articles of the type described herein. These glass substrate articles exhibit a compressive stress region extending from the surface to a compressive depth. The maximum compressive stress measured for the 0.5 mm glass substrate article was 124 Mpa, and the maximum compressive stress measured for the 1.0 mm glass substrate article was 137 Mpa. The maximum central tension measured for the 0.5 mm glass substrate article was 32 Mpa, and the maximum compressive stress measured for the 1.0 mm glass substrate article was 15 Mpa. The compressive depth of the 0.5 mm glass substrate article was 101 μm, and the compressive depth of the 1.0 mm glass substrate article was 99 μm. After exposure to a 100% relative humidity environment at 200 °C for 7 days, center cut samples of 0.5 mm and 1.0 mm thick glass substrate articles formed from a glass substrate also freely comprising the glass composition of Example 6 were also formed. 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 cm -1 resolution, 10 μm aperture and 10 μm step. The scan originated from the surface of the sample and continued to approximately the midpoint of the thickness. Spectra were generated relative to "dry" silica, and the 3900 cm -1 max and 3550 cm -1 min parameters were used to calculate the hydroxyl (βOH) concentration. Due to the multi-component nature of the glass substrate articles, it was not possible to distinguish between bound hydroxyl and molecular hydroxyl, so the curve reports the concentration of the total hydroxyl content. The measured hydroxyl concentrations for the 0.5 mm thick and 1.0 mm thick samples are shown in Figures 9 and 10, respectively. As shown in Figures 9 and 10, the measured hydroxyl content becomes substantially constant and the concentration within the sample equivalent to the hydroxyl content at the center of the article (indicating the background hydroxyl content of the precursor glass substrate article) is approximately 200 μm, as measured by FTIR. The appearance of the buried hydroxyl concentration peaks in Figures 9 and 10 is an artifact of the measurement method. Prepare square samples having the composition of Example 1, with a thickness of 1 mm and sides of 50 mm. Five of these samples were then processed in an environment of 100% relative humidity at 200 °C for 121 hours. The resulting compressive stress (CS) and depth of compression (DOC) of the processed samples were then measured by FSM, resulting in a CS of 167 MPa and a DOC of 73 μm. Five steam-treated samples and three control samples not exposed to steam treatment were subjected to an abraded ring-on-ring (AROR) test. The strength and peak load of the samples for each test were reported in Table IV. As shown in Table IV, the steam-treated samples exhibited significantly increased peak loads and strengths compared to the untreated control samples. The AROR test is a surface strength measurement for testing flat glass specimens, and ASTM C1499-09(2013) entitled "Standard Test Method for Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperature" serves as the basis for the AROR test method utilized herein. The content of ASTM C1499-09 is hereby incorporated by reference in its entirety. Using the method and apparatus described in Appendix 2 entitled "abrasion Procedures" of ASTM C158-02(2012) entitled "Standard Test Methods for Strength of Glass by Flexure (Determination of Modulus of Rupture)", the glass specimens were abraded with 90 coarse sand silicon carbide (SiC) particles delivered to the glass samples prior to the ring-on-ring test. The content of ASTM C158-02 and the content of Appendix 2 are hereby incorporated by reference in their entirety. Prior to the ring-on-ring test, the surface of the glass substrate object sample was abraded as described in ASTM C158-02, Appendix 2, to normalize and / or control the surface defect condition of the sample using the apparatus shown in Figure A2.1 of ASTM C158-02. The abrasive material was sandblasted onto the surface of the glass substrate object at an air pressure of 5 psi. After establishing an air flow, 1 cm 3 of the abrasive material was poured into the furnace and the sample was sandblasted. For the AROR test, a glass substrate object having at least one ground surface, as shown in Figure 11, is placed between two concentric rings of different sizes to determine the equi-biaxial flexural strength (i.e., the maximum stress that the material can support when subjected to flexure between two concentric rings). In the AROR configuration 400, the ground glass substrate object 410 is supported by a support ring 420 having a diameter D2. A force F is applied by a loading ring 430 having a diameter D1 to the surface of the glass substrate object by a dynamometer (not shown). The diameter ratio D1 / D2 of the loading ring to the support ring can be in a range from 0.2 to 0.5. In some embodiments, D1 / D2 is 0.5. The loading ring 430 and the support ring 420 should be concentrically aligned within 0.5% of the support ring diameter D2. At any load within the selected range, the dynamometer used for the test should be accurate within ±1%. The test is conducted at a temperature of 23 ± 2 °C and a relative humidity of 40 ± 10%. For the fixture design, the radius r of the protruding surface of the loading ring 430 is in the range of h / 2 ≤ r ≤ 3h / 2, where h is the thickness of the glass substrate object 410. The loading ring 430 and the support ring 420 are made of hardened steel having a hardness HRc > 40. The AROR fixture is commercially available. The intended failure mechanism for the AROR test is to observe the fracture of the glass substrate object 410 originating from the surface 430a within the loading ring 430. Failures occurring outside this area (i.e., between the loading ring 430 and the support ring 420) are ignored during data analysis. However, due to the thinness and high strength of the glass substrate object 410, sometimes deflections exceeding the specimen thickness h are observed. Therefore, it is not uncommon to observe a high percentage of failures originating under the loading ring 430. Without knowing the stress development inside and under the ring (collected via strain gauge analysis) and the source of failure in each specimen, the stress cannot be accurately calculated. As a response to the measurement, the AROR test thus focuses on the peak load at the failure point. Although the typical embodiments have been described for illustrative purposes, the foregoing description should not be regarded as a limitation on the scope of the present disclosure or the appended claims. Thus, various modifications, adaptations, and alternatives can be envisioned by those skilled in the art without departing from the spirit and scope of the present disclosure or the appended claims. 100: Glass substrate object 110: First surface 112: Second surface 120: First hydrogen-containing layer 122: Second hydrogen-containing layer 130: Hydrogen-free substance region 200: Consumer electronic component 202: Housing 204: Front portion 206: Rear portion 208: Side surface 210: Display 212: Cover substrate 301: As-received glass substrate hydrogen concentration curve 302: Glass substrate object hydrogen concentration curve 303: Extrapolated curve 400: AROR configuration 410: Ground glass substrate object 420: Support ring 430: Loading ring 430a: Surface d1: Depth d2: Depth t: Thickness D1: Loading ring diameter D2: Support ring diameter F: Force FIG. 1 is a representation of a cross-section of a glass substrate object according to an embodiment. FIG. 2A is a plan view of an exemplary electronic component incorporating any of the glass substrate objects disclosed herein. FIG. 2B is a perspective view of the exemplary electronic component of FIG. 2A. FIG. 3 is a measurement of the hydrogen concentration as a function of depth below the surface generated by SIMS for a glass substrate object formed from a glass substrate having the composition of Example 1. FIG. 4 is a photograph of a Vickers indent at 5 kgf in a glass substrate having the composition of Example 1 before exposure to an aqueous environment. FIG. 5 is a photograph of a Vickers indent at 10 kgf in a glass substrate having the composition of Example 1 before exposure to an aqueous environment. FIG. 6 is a photograph of a Vickers indent at 5 kgf in a glass substrate object formed by exposing a glass substrate having the composition of Example 1 to an aqueous environment. FIG. 7 is a photograph of a Vickers indent at 10 kgf in a glass substrate object formed by exposing a glass substrate having the composition of Example 1 to an aqueous environment. FIG. 8 is a photograph of a Vickers indent at 20 kgf in a glass substrate object formed by exposing a glass substrate having the composition of Example 1 to an aqueous environment. FIG. 9 is a graph of the hydroxyl (BOH) concentration as a function of depth from the surface for a 0.5 mm thick glass object after exposure to an aqueous environment according to an embodiment. FIG. 10 is a graph of the hydroxyl (BOH) concentration as a function of depth from the surface for a 1.0 mm thick glass object after exposure to an aqueous environment according to an embodiment. FIG. 11 is a side view of a ring-on-ring test apparatus. Domestic deposit information (Please note in the order of deposit institution, date, number) None Foreign deposit information (Please note in the order of country, institution, date, and number) None

Claims

1. A glass article formed by steam treatment, comprising: greater than or equal to 11 moles to less than or equal to 25 moles of K₂O; a hydrogen-containing layer on a surface of the glass article extending from the surface to a depth, wherein the depth refers to a first depth below the surface, wherein a hydrogen concentration at the first depth is equal to a hydrogen concentration at a center of the glass article; and a compressive stress layer extending from the surface of the glass article to a compressive depth, wherein the compressive depth refers to the depth at which stress in the glass article changes from compression to tension; wherein the depth from the surface is greater than 5 μm; and wherein the compressive stress layer contains a compressive stress of at least 100 MPa.

2. The glass object as claimed in claim 1 further includes a tensile stress region containing a maximum central tension of 10 MPa or greater.

3. The glass object as claimed in claim 1, wherein a maximum hydrogen concentration is located on the surface of the glass object, and wherein the hydrogen concentration of the hydrogen-containing layer decreases from the maximum hydrogen concentration to the depth of the layer.

4. The glass article as claimed in claim 1, wherein the hydrogen substance comprises one or more of molecular water, hydroxyl groups, hydrogen ions, and hydrated hydrogen ions.

5. The glass object as claimed in claim 1, wherein the surface is a first surface of the glass object, and the glass object further includes a second surface and a thickness extending between the first surface and the second surface, wherein the depth of the layer is greater than 0.005 times the thickness of the glass object.

6. The glass article as claimed in claim 1, wherein the surface is a first surface of the glass article, and the glass article further includes a second surface and a thickness extending between the first surface and the second surface, wherein the thickness is less than or equal to 2 mm.

7. The glass article as claimed in claim 1, wherein the surface is a first surface of the glass article, and the glass article further includes a second surface and a thickness extending between the first surface and the second surface, wherein the hydrogen-containing layer is a first hydrogen-containing layer with a depth of a first layer depth, and the glass article further includes a second hydrogen-containing layer extending from the second surface to the glass article to a second layer depth; and wherein the glass article further includes a region between the first layer depth and the second layer depth, wherein the hydrogen concentration in the region is substantially constant between the first layer depth and the second layer depth.

8. The glass article as claimed in claim 1, wherein the surface is a first surface of the glass article, and the glass article further includes a second surface and a thickness extending between the first surface and the second surface, wherein the glass article can be shaped into a sheet such that the first surface and the second surface are its opposing principal surfaces.

9. The glass object as claimed in claim 8, wherein the glass object has a 3D shape such that the first surface and the second surface are at least partially uneven.

10. The glass object as described in claim 8, having at least some degree of transparency.

11. A transportation object comprising a glass object formed by steam treatment as described in claim 1, therein. The transportation object is a car.

12. A consumer electronic component comprising: a plurality of electrical components including a display; and a cover covering the display, wherein at least a portion of the cover comprises a glass object formed by steam treatment as described in claim 1.

13. A glass article formed by steam treatment, comprising: greater than or equal to 11 moles to less than or equal to 25 moles of K2O; a compressive stress layer on a surface of the glass article extending from the surface of the glass article to a compression depth, wherein the compression depth refers to the depth at which stress in the glass article changes from compression to tension; and wherein the compressive stress layer contains a compressive stress of at least 100 MPa.

14. The glass article as claimed in claim 13, wherein the surface is a first surface of the glass article, and the glass article further includes a second surface and a thickness (t) extending between the first surface and the second surface, wherein the compression depth is greater than or equal to 0.05 t.

15. The glass article as claimed in claim 13, wherein the surface is a first surface of the glass article, and the glass article further includes a second surface and a thickness extending between the first surface and the second surface, wherein the thickness is less than or equal to 2 mm.

16. The glass article as claimed in claim 13 further includes a tensile stress region containing a maximum central tension of 10 MPa or greater.

17. The glass object as described in claim 13, having at least some degree of transparency.

18. The glass object as described in claim 13, wherein the compression depth is less than or equal to 115 μm.

19. The glass object as claimed in claim 13, wherein the compression depth is greater than or equal to 75 μm.

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