TW201930219A - Hydrogen-containing glass-based articles with high indentation cracking threshold - Google Patents

Abstract

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

Description

Hydrogen-containing glass substrate with high dent cracking threshold

Related application

The present application claims priority to US Provisional Application No. 62/587,872, filed on Nov. 17, the entire disclosure of which is hereby incorporated by reference inco The priority of NL Application No. 2020 896, the content of which is hereby incorporated by reference in its entirety in its entirety herein in

The present disclosure is directed to glass substrate articles containing hydrogen, glass compositions for forming such glass substrate articles, and methods of forming such glass substrate articles.

Portable electronic components such as smart phones, tablets and wearable components such as watches and fitness trackers continue to become smaller and more complex. Thus, materials conventionally used on at least one outer surface of such portable electronic components continue to become more complex. For example, when portable electronic components become smaller and thinner to meet consumer demand, display covers and housings used in such portable electronic components have also become smaller and thinner, resulting in To achieve higher performance requirements for the materials of these components.

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

In the 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 a surface of the glass substrate article to a depth. The hydrogen concentration of one of the hydrogen-containing layers decreases from a maximum hydrogen concentration to the depth of the layer, and the layer depth is greater than 5 μm.

In aspect (2), a glass substrate article of aspect (1) is provided, wherein the glass substrate article has an initial threshold of one of Vickers cracking greater than or equal to 1 kgf.

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

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

In the aspect (5), the glass substrate article of any one of the aspects (1) to (4), further comprising Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, and Rb ₂ O At least one.

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

In the aspect (7), the glass substrate article of any one of the aspects (1) to (6), wherein the center of the glass substrate article comprises: greater than or equal to 45 mol% to less than or equal to 75 m % SiO ₂ ; greater than or equal to 3 mole % to less than or equal to 20 mole % of Al ₂ O ₃ ; greater than or equal to 6 mole % to less than or equal to 15 mole % of P ₂ O ₅ ; Equal to 6 mol% to less than or equal to 25 mol% of K ₂ O.

The glass substrate article of any one of the aspects (1) to (6), wherein the center of the glass substrate article comprises: greater than or equal to 45 mol% to less than or equal to 75 mo SiO _{2 of the} ear; greater than or equal to 3 mol % to less than or equal to 20 mol % of Al ₂ O ₃ ; greater than or equal to 4 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; Or equal to 11 mol% to less than or equal to 25 mol% of K ₂ O.

In the aspect (9), the glass substrate article of any one of the aspects (1) to (6), wherein the center of the glass substrate article comprises: greater than or equal to 55 mol% to less than or equal to 69 mo SiO _{2 of the} ear; greater than or equal to 5 mol% to less than or equal to 15 mol% of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 10 mol % of P ₂ O ₅ ; Or equal to 10 mol% to less than or equal to 20 mol% of K ₂ O.

In the aspect (10), the glass substrate article of any one of the aspects (7) to (9), wherein the center of the glass substrate article comprises: greater than or equal to 0% by mole to less than or equal to 10% Cs ₂ O of the ear %; and Rb ₂ O greater than or equal to 0 mol% to less than or equal to 10 mol%.

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

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

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

In aspect (14), a consumer electronics product is provided. The consumer electronic product includes: a housing including a front surface, a rear surface, and a side surface; an electrical component at least partially within the housing, the electrical component including at least one controller, a memory, and a display, A display is at or adjacent the front surface of the outer casing; and a cover substrate is disposed on the display. At least a portion of at least one of the outer casing or the cover substrate comprises the glass substrate article of any of the aspects (1) to (13).

In the aspect (15), a glass is provided. The glass comprises: greater than or equal to 45 mole% to less than or equal to 75 mole% of SiO _2; greater than or equal to 3 mole% to less than or equal to 20 mole% of Al ₂ O _3; greater than or equal to 6 molar % to less than or equal to 15 mol% of P ₂ O ₅ ; and greater than or equal to 6 mol % to less than or equal to 25 mol % of K ₂ O.

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

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

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

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

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

In the aspect (21), the glass of any one of aspects (15) to (20), wherein the glass has an initial threshold of Vickers cracking greater than or equal to 5 kgf.

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

In the aspect (23), a glass is provided. The glass comprises: greater than or equal to 45 mole% to less than or equal to 75 mole% of SiO _2; greater than or equal to 3 mole% to less than or equal to 20 mole% of Al ₂ O _3; greater than or equal to 4 molar % to less than or equal to 15 mol% of P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 25 mol % of K ₂ O.

In the aspect (24), there is provided aspects (23) of glass, comprising: greater than or equal to 55 mole% to less than or equal to 69 mole% of SiO _2; greater than or equal to 5 mole% to less than or equal to 15 Mo ₂ % Al ₂ O ₃ ; greater than or equal to 5 mol % to less than or equal to 10 mol % P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 20 mol % K ₂ O .

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

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

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

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

In the aspect (29), the glass of any one of aspects (23) to (28), wherein the glass has an initial threshold of Vickers cracking greater than or equal to 5 kgf.

In the aspect (30), the glass of any one of the 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 By.

In the aspect (31), a method is provided. The method includes 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 extending from a surface of the glass substrate to One layer of depth. The glass base substrate includes SiO ₂ , Al ₂ O _{3 ,} and P ₂ O ₅ . The hydrogen concentration of one of the hydrogen-containing layers decreases from a maximum hydrogen concentration to the depth of the layer, and the layer depth is greater than 5 μm.

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

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

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

The method of any one of aspects (31) to (34), wherein the glass base substrate further comprises: Cs greater than or equal to 0% by mole to less than or equal to 10% by mole of Cs ₂ O; and Rb ₂ O greater than or equal to 0% by mole to less than or equal to 10% by mole.

In the aspect (36), the method of any one of the 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 By.

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

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

The method of any one of aspects (31) to (38), wherein the glass substrate article has an initial threshold of Vickers cracking greater than or equal to 1 kgf.

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

In the following description, like reference characters refer to the It should also be understood that terms such as "top", "bottom", "outward", "inward" and the like are used in a convenient term and should not be construed as limiting terms. Unless otherwise specified, the range of values includes the upper and lower limits of the range, and any sub-ranges therebetween. As used herein, the indefinite article "a", "the", "the" and "the" It should also be understood that the various features disclosed in the description and drawings may be used in any and all combinations.

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

Note that the terms "substantially" and "about" may be used herein to denote the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms are also used herein to indicate a quantitative representation of a change that can be made by a reference to a statement, without causing a change in the basic function of the subject matter under discussion. For example, a glass that is "substantially free of K ₂ O" is K ₂ O and is not actively added or batched into the glass and can be contaminated by a very small amount (such as less than about 0.01 mole %). The glass of matter. As used herein, when the term "about" is used to modify a value, the precise value is also disclosed. For example, the term "greater than about 10 mol%" also reveals "greater than or equal to about 10 mol%."

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

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

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

One generation representation of a glass substrate article 100 in accordance with some embodiments is depicted in cross section in FIG. The glass substrate article 100 has a thickness t that extends between a first surface 110 and a second surface 112. The first hydrogen containing layer 120 extends from the first surface 110 to a first layer depth, wherein the first layer depth has a depth d1 that is measured from the first surface 110 into the glass substrate article 100. The second hydrogen containing layer 122 extends from the second surface 112 to a second layer depth, wherein the second layer depth has a depth d2 that is measured from the second surface 112 into the glass substrate article 100. The no-added hydrogen species region 130 exists between the first layer depth and the second layer depth.

The hydrogen-containing layer of the glass substrate article may have a depth of layer (DOL) of greater than 5 μm. In some embodiments, the layer depth may be greater than or equal to 10 μιη, such as greater than or equal to 15 μιη, greater than or equal to 20 μιη, greater than or equal to 25 μιη, greater than or equal to 30 μιη, greater than or equal to 35 μιη, 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 m or more. In some embodiments, the layer depth may be from greater than 5 μm to less than or equal to 205 μm, such as from greater than or equal to 10 μm to less than or equal to 200 μm, from greater than or equal to 15 μm to less than or equal to 200 μm, from Greater than or equal to 20 μm to less than or equal to 195 μm, from greater than or equal to 25 μm to less than or equal to 190 μm, from greater than or equal to 30 μm to less than or equal to 185 μm, from greater than or equal to 35 μm to less than or equal to 180 μm From greater than or equal to 40 μm to less than or equal to 175 μm, from greater than or equal to 45 μm to less than or equal to 170 μm, from greater than or equal to 50 μm to less than or equal to 165 μm, from greater than or equal to 55 μm to less than or equal to 160 μm, from greater than or equal to 60 μm to less than or equal to 155 μm, from greater than or equal to 65 μm to less than or equal to 150 μm, from greater than or equal to 70 μm to less than or equal to 145 μm, from greater than or equal to 75 μm to less than Or equal to 140 μm, from greater than or equal to 80 μm to less than or equal to 135 μm, from greater than or equal to 85 μm to less than or equal to 130 μm, from greater than or equal to 90 μm to less than or equal to 125 μm, from greater than or equal to 95 μm Less than or equal to 120 μm, from greater than or equal to 100 μm to less than or equal to 115 μm, from greater than or equal to 105 μm to less than or equal to 110 μm or the like whereby the end points of any subrange any of those formed. In general, the depth of the layer exhibited by the glass substrate article is greater than the depth of the layer that can be created by exposure to the surrounding environment.

The hydrogen containing layer of the glass substrate article can have a depth of layer (DOL) greater than 0.005 t , where t is the thickness of the glass substrate article. In some embodiments, the layer depth may 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 , greater than or equal to 0.070 t , greater than or equal to 0.075 t , greater than or equal to 0.080 t , greater than or equal to 0.085 t , greater than or equal to 0.090 t , greater than or equal to 0.095 t , greater than or equal to 0.10 t , greater than or equal to 0.15 t , greater than or equal to 0.20 t or greater. In some embodiments, the DOL may be from greater than 0.005 t to less than or equal to 0.205 t , such as from greater than or equal to 0.010 t to less than or equal to 0.200 t , from greater than or equal to 0.015 t to less than or equal to 0.195 t , from greater than or Is equal to 0.020 t to less than or equal to 0.190 t , from greater than or equal to 0.025 t to less than or equal to 0.185 t , from greater than or equal to 0.030 t to less than or equal to 0.180 t , from greater than or equal to 0.035 t to less than or equal to 0.175 t , from Greater than or equal to 0.040 t to less than or equal to 0.170 t , from greater than or equal to 0.045 t to less than or equal to 0.165 t , from greater than or equal to 0.050 t to less than or equal to 0.160 t , from greater than or equal to 0.055 t to less than or equal to 0.155 t From greater than or equal to 0.060 t to less than or equal to 0.150 t , from greater than or equal to 0.065 t to less than or equal to 0.145 t , from greater than or equal to 0.070 t to less than or equal to 0.140 t , from greater than or equal to 0.075 t to less than or equal to 0.135 t, from greater than or equal to less than or equal to 0.080 t 0.130 t, from greater than or equal to less than or equal to 0.085 t 0.125 t, from greater than or equal to less than or equal to 0.090 t 0.120 t From greater than or equal to less than or equal to 0.095 t 0.115 t, from greater than or equal to less than or equal to 0.100 t 0.110 t or the like whereby the end points is formed by any of the subranges.

The layer depth and hydrogen concentration are measured by the secondary ion mass spectrometry (SIMS) technique known in the art. The SIMS technology is capable of measuring the hydrogen concentration at a given depth, but is unable to discern the hydrogen species present in the glass substrate. For this reason, all hydrogen species have an effect on the hydrogen concentration measured by SIMS. As used herein, a depth of layer (DOL) refers to a first depth below the surface of a glass substrate article at which the hydrogen concentration is equal to the hydrogen concentration at the center of the glass substrate article. This definition describes the hydrogen concentration of the glass substrate prior to processing such that the layer concentration refers to the depth of hydrogen added by the processing process. In fact, the concentration of hydrogen at the center of the glass substrate can be estimated by the hydrogen concentration at a depth from the surface of the glass substrate at which the hydrogen concentration becomes substantially constant, since it is expected to be at this depth with the glass substrate. The hydrogen concentration does not change between the centers. This estimation allows DOL to be determined without measuring the hydrogen concentration across the full depth of the glass substrate.

In some embodiments, all of the thickness of the glass substrate article can be part of a hydrogen containing layer. The glass substrate can be produced when the treatment of the glass substrate is extended for a sufficient time under sufficient conditions for the hydrogen species to diffuse from the exposed surface to the center of the glass substrate. In some embodiments, where the surface of the glass substrate article is exposed to the same processing conditions, the minimum hydrogen concentration can be located at one-half the thickness of the glass substrate article such that the hydrogen-containing layer meets at the center of the glass substrate article. In such embodiments, the DOL can be located at one-half of the thickness of the glass substrate article. In some embodiments, the glass substrate articles may not include a region of the unadded hydrogen species. In some embodiments, the glass substrate article can be treated in a wet environment such that the concentration of added hydrogen species is uniform across the glass substrate article and the hydrogen concentration does not vary with depth below the surface of the glass substrate article. The glass substrate article according to such embodiments will not exhibit a DOL as defined herein, as 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 objects are highly resistive to Vickers dent cracking. High Vickers dent crack resistance imparts high damage resistance to glass substrate articles. Without wishing to be bound by any feature theory, the water content of the glass substrate can reduce the local viscosity of the hydrogen containing layer such that localized flow occurs rather than cracking. The Vickers dent cracking threshold of glass substrate articles is laminated without the use of conventional strengthening techniques such as the exchange of large alkali ions for small alkali ions in glass, thermal tempering, or glass layers with mismatched thermal expansion coefficients. Under the circumstances. The glass substrate article exhibits a Vickers dent cracking threshold 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 24 kgf or more, 25 kgf or more, 26 kgf or more, 27 kgf or more, 28 kgf or more, 29 kgf or more, 30 kgf or more or more. In some embodiments, the glass substrate article exhibits a Vickers dent cracking threshold from greater than or equal to 1 kgf to less than or equal to 30 kgf, such as from greater than or equal to 2 kgf to less than or equal to 29 kgf, from greater than or equal to 3 Kgf to less than or equal to 28 kgf, from greater than or equal to 4 kgf to less than or equal to 27 kgf, from greater than or equal to 5 kgf to less than or equal to 26 kgf, from greater than or equal to 6 kgf to less than or equal to 25 kgf, from greater than or Equivalent 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 Any subrange that is formed from any greater than or equal to 15 kgf to less than or equal to 16 kgf or any of the endpoints.

The initial threshold of Vickers cracking (or the dent break threshold) is measured by dimensional dents. The initial threshold of Vickers cracking is the measure of the dent resistance of the glass. The test involves the use of a square-based pyramidal diamond dentometer with an angle of 136° between the faces, referred to as a Vickers dentometer. The Vickers dent meter is the same as the dent meter used in the standard microhardness test (as described in ASTM-E384-11). A minimum of five samples are selected to indicate the type of glass and/or sample of interest. For each sample, a plurality of five indent sets were introduced to the surface of the sample. Each of the five dent sets is introduced at a given load, with each individual dent separated by a minimum of 5 mm and not less than 5 mm near the edge of a sample. For a test load ≥ 2 kg, a loading/unloading rate of 50 kg/min dent is used. For test loads < 2 kg, use a rate of 5 kg/min. A 10 second pause (ie, hold) time at the target load is utilized. The machine maintains load control during the dwell period. After one cycle of at least 12 hours, the dent was examined under reflected light using a composite microscope at 500X magnification. The intermediate/radial cracking (cracking from a dent along a plane perpendicular to the principal plane of the object) or the presence or absence of sample rupture is then noted for each dent. Note that the formation of lateral cracking (cracking along a plane parallel to the principal plane of the object) is not considered indicative of exhibiting threshold behavior due to the formation of intermediate/radial cracking or sample fracture for this test. Stakes. The sample threshold is defined as the midpoint of the lowest continuous dent load (which includes more than 50% of individual dents that meet the threshold). For example, if in one sample, 2/5 (40%) of the dent induced at 5 kg load has exceeded the threshold and 3/5 (60%) of the depression induced at 6 kg load If the mark has exceeded the threshold, the sample threshold will be defined as greater than 5 kg. The range of the midpoints (lowest to highest) for all samples can also be reported for each sample. Pre-test, test, and post-test environments were controlled to 23 ± 2 ° C and 50 ± 5% Rh to minimize variations in fatigue (stress corrosion) behavior of the specimen.

Without wishing to be bound by any particular theory, the hydrogen-containing layer of the glass substrate may be the result of interdiffusion of the hydrogen species with respect to ions contained in the composition of the glass substrate. The monovalent hydrogen-containing substance (such as H ₃ O ⁺ and/or H ⁺ ) may replace the alkali ions contained in the glass base substrate composition to form a glass substrate article. The size of the alkali ion replaced by the hydrogen-containing substance has an influence on the diffusibility of the hydrogen-containing substance in the glass base substrate because the larger alkali ion generates a large void space which contributes to the mutual diffusion mechanism. For example, hydronium ions (H ₃ O ⁺ ) have an ionic radius that is close to the ionic radius of potassium and much larger than the ionic radius of lithium. It was observed that when the glass base substrate contains potassium, the diffusibility of the hydrogen-containing substance in the glass base substrate is significantly two orders of magnitude higher than when the glass base substrate contains lithium. This observed behavior may also indicate that the hydronium ion is a major monovalent hydrogen-containing species that diffuses into the glass substrate. The ionic radii for the alkali ions and hydronium ions are reported in Table I below. As shown in Table I, ruthenium and osmium have significantly larger ionic radii than hydronium ions, which can result in higher hydrogen diffusivity than hydrogen observed for potassium.

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

In some embodiments, the compressive stress layer can include one or more compressive stresses 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 may comprise a compressive stress from one of 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 the endpoints.

In some embodiments, the compressive stress layer may have a DOC 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 Bigger. 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 article may be one of greater than or equal 0.05 t DOC, where t is the thickness of the glass substrate article, such as greater than or equal to 0.06 t, 0.07 t is greater than, or equal to, greater than or equal to 0.08 t, greater than Or equal to 0.09 t , greater than or equal to 0.10 t , greater than or equal to 0.11 t , greater than or equal to 0.12 t or greater. In some embodiments, the glass substrate article can have a DOC from greater than or equal to 0.05 t to less than or equal to 0.20 t , such as from greater than or equal to 0.06 t to less than or equal to 0.19 t , from greater than or equal to 0.07 t to less than Or equal to 0.18 t , from greater than or equal to 0.08 t to less than or equal to 0.17 t , from greater than or equal to 0.09 t to less than or equal to 0.16 t , from greater than or equal to 0.10 t to less than or equal to 0.15 t , from greater than or equal to 0.11 t Up to or less than 0.14 t , from greater than or equal to 0.12 t to less than or equal to 0.13 t or any subrange formed from any of the 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 any subrange that is less than or equal to 22 MPa or any of these endpoints.

The compressive stress (including the surface CS) was measured by a surface stress meter using a commercially available instrument such as FSM-6000 (FSM) manufactured by Orihara Industrial Co., Ltd. (Japan). The surface stress measurement results depend on an accurate measurement of the stress optical coefficient (SOC) associated with the birefringence of the glass. The SOC is further measured according to the procedure C (glass dish method) described in ASTM Standard C770-16 entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the contents of which are incorporated by reference. Into this article. The DOC is measured by FSM. The maximum central tension (CT) value is measured using a scattered light polarizer (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 base substrate can be specifically selected to promote diffusion of the hydrogen-containing substance, so that the glass substrate article including a hydrogen-containing layer can be efficiently formed. In some embodiments, the glass base substrate may have a composition including one of SiO ₂ , Al ₂ O _{3 ,} and P ₂ O ₅ . In some embodiments, the glass base substrate may additionally include an alkali metal oxide such as at least one of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O. In some embodiments, the glass base substrate can be substantially free or free of at least one of lithium and sodium. In some embodiments, after diffusion of the hydrogen-containing material into the glass substrate, the glass substrate article can have a total composition that is substantially the same as the composition of the glass substrate. In some embodiments, the hydrogen species may not diffuse to the center of the glass substrate article. In other words, the center of the glass substrate is the area that is least affected by the steam treatment. For this reason, the center of the glass substrate article may have substantially the same or the same composition as the composition of the glass substrate before processing in an aqueous environment.

The glass substrate can include any suitable amount of SiO ₂ . SiO ₂ is the largest component, and thus, SiO ₂ is a 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 adversely affects the formability of the glass. In some embodiments, the glass base substrate can include SiO ₂ in an amount 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 mole % to less than or equal to 74 moles %, from greater than or equal to 47% by mole to less than or equal to 73% by mole, from greater than or equal to 48% by mole to less than or equal to 72% by mole, from greater than or equal to 49% by mole to less than or equal to 71% Ear %, from greater than or equal to 50 mole % to less than or equal to 70 mole %, from greater than or equal to 51 mole % to less than or equal to 69 mole %, from greater than or equal to 52 mole % to less than or equal to 68 Molar%, from greater than or equal to 53% by mole to less than or equal to 67% by mole, from greater than or equal to 54% by mole to less than or equal to 66% by mole, from greater than or equal to 55% by mole 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 Equivalent to 62 mole %, from greater than or equal to 59 mole % to less than or equal to 61 mole %, 60 mole % or any subrange formed by any of the endpoints. In some embodiments, the glass base substrate can include SiO ₂ in an amount from greater than or equal to 55 mole % to less than or equal to 69 mole %, such as from greater than or equal to 58 mole % to less than or equal to 63 moles % or any sub-range formed from any of these endpoints.

The glass substrate can include any suitable amount of Al ₂ O ₃ . Al ₂ O ₃ acts as a glass network former, similar to SiO ₂ . Al ₂ O ₃ can increase the viscosity of the glass composition due to its tetrahedral coordination in the glass melt formed from the glass composition, thereby lowering the glass composition when the amount of Al ₂ O ₃ is too high Formability. However, when the concentration of Al ₂ O ₃ is balanced against the concentration of SiO _{2 and} the concentration of the alkali oxide 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. The Al ₂ O ₃ in the glass base substrate includes preventing phase separation and reducing the number of non-bridging oxygen (NBO) in the glass. In addition, Al ₂ O ₃ can improve the effectiveness of ion exchange. In some embodiments, the glass base substrate can include Al ₂ O _{3 in an} amount from greater than or equal to 3 mole % to less than or equal to 20 mole %, such as from greater than or equal to 4 mole % to less than or equal to 19 Molar%, from greater than or equal to 5 mol% to less than or equal to 18 mol%, from greater than or equal to 6 mol% to less than or equal to 17 mol%, from greater than or equal to 7 mol% to less than or equal to 16 mol%, from greater than or equal to 8 mol% to less than or equal to 15 mol%, from greater than or equal to 9 mol% to less than or equal to 14 mol%, from greater than or equal to 10 mol% 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 subrange formed by any of the endpoints. In some embodiments, the glass base substrate can include Al ₂ O _{3 in an} amount from greater than or equal to 5 mole % to less than or equal to 15 mole %, such as from greater than or equal to 7 mole % to less than or equal to 14 Mol% or any sub-range formed from any of these endpoints.

The glass substrate can include any amount of P ₂ O ₅ sufficient to produce the desired hydrogen diffusivity. The inclusion of phosphorus in the glass-based substrate promotes faster interdiffusion, independent of the exchange of ion pairs. Therefore, the phosphorus-containing glass base substrate allows efficient formation of a glass substrate article including a hydrogen-containing layer. The inclusion of P ₂ O ₅ also allows for the creation of glass substrate articles having a deep layer depth (e.g., greater than about 10 μm) in relatively short processing times. In some embodiments, the glass base substrate can include P ₂ O _{5 in an} amount from greater than or equal to 4 mole % to less than or equal to 15 mole %, such as from greater than or equal to 5 mole % to less than or equal to 14 Molar%, 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 mole %, from greater than or equal to 9 mole % to less than or equal to 10 mole % or any sub-range formed by any of the endpoints. In some embodiments, the glass base substrate can include P ₂ O _{5 in an} amount from greater than or equal to 5 mole % to less than or equal to 15 mole %, such as from greater than or equal to 6 mole % to less than or equal to 15 Molar%, 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 Any of the sub-ranges formed by any of the 10% or any of the endpoints.

The glass substrate can comprise any suitable amount of alkali metal oxide. The alkali metal oxide promotes ion exchange. The sum of alkali metal oxides (for example, 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 can be expressed in % by mole. In some embodiments, the glass base substrate can be substantially free or free of at least one of lithium and sodium. In some embodiments, the glass composition comprises R ₂ O in an amount greater than or equal to 6 mole %, such as greater than or equal to 7 mole %, greater than or equal to 8 mole %, greater than or equal to 9 mole %, 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% by mole, greater than or equal to 17% by mole, greater than or equal to 18% by mole, greater than or equal to 19% by mole, greater than or equal to 20% by mole, greater than or equal to 21% by mole, greater than or equal to 22 Mole%, greater than or equal to 23 mol% or greater than or equal to 24 mol%. In one or more embodiments, the glass composition comprises R ₂ O in an amount less than or equal to 25 mole %, such as less than or equal to 24 mole %, less than or equal to 23 mole %, less than or equal to 22 moles Ear %, less than or equal to 21 mole %, less than or equal to 20 mole %, less than or equal to 19 mole %, less than or equal to 18 mole %, less than or equal to 17 mole %, less than or equal to 16 mole % Less than or equal to 15% by mole, less than or equal to 14% by mole, less than or equal to 13% by mole, less than or equal to 12% by mole, less than or equal to 11% by mole, less than or equal to 10% by mole, less than Or equal to 9 mole %, less than or equal to 8 mole % or less than or equal to 7 mole %. It should be understood that in the embodiments, any of the above ranges may be combined with any other range. In some embodiments, the glass composition comprises R ₂ O in an amount from greater than or equal to 6.0 mole % to less than or equal to 25.0 mole %, such as from greater than or equal to 7.0 mole % to less than or equal to 24.0 moles %, 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 m Ear %, 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 Molar%, 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 subranges between the foregoing values .

In some embodiments, the alkali metal oxide can be K ₂ O. The K ₂ O includes an efficient exchange of hydrogen species into the glass substrate after exposure to an aqueous environment. In some embodiments, the glass base substrate can include K ₂ O in an amount from greater than or equal to 6 mole % to less than or equal to 25 mole %, such as from greater than or equal to 7 mole % to less than or equal to 24 moles Ear %, from greater than or equal to 8 mole % to less than or equal to 23 mole %, from greater than or equal to 9 mole % to less than or equal to 22 mole %, from greater than or equal to 10 mole % to less than or equal to 21 Molar%, from greater than or equal to 11 mol% to less than or equal to 20 mol%, from greater than or equal to 12 mol% to less than or equal to 19 mol%, from greater than or equal to 13 mol% to less than or equal to 18 mol%, from greater than or equal to 14 mol% to less than or equal to 17 mol% or from greater than or equal to 15 mol% to less than or equal to 16 mol%, or form from any of these endpoints Any subrange. In some embodiments, the glass base substrate can include K ₂ O in an amount from greater than or equal to 10 mole % to less than or equal to 25 mole %, such as from greater than or equal to 10 mole % to less than or equal to 20 moles Ear %, from greater than or equal to 11 mole % to less than or equal to 25 mole %, from greater than or equal to 11 mole % to less than or equal to 20 mole %, from greater than or equal to 15 mole % to less than or equal to 20 Mol% or any sub-range formed from any of these endpoints.

The glass substrate can include any suitable amount of Rb ₂ O. In some embodiments, the glass base substrate can include Rb ₂ O in an amount from greater than or equal to 0 mole % to less than or equal to 10 mole %, such as from greater than or equal to 1 mole % to less than or equal to 9 moles Ear %, from greater than or equal to 2 mole % to less than or equal to 8 mole %, from greater than or equal to 3 mole % to less than or equal to 7 mole %, from greater than or equal to 4 mole % to less than or equal to 6 Mole %, 5 mol % or any sub-range formed from any of these endpoints.

The glass substrate can include any suitable amount of Cs ₂ O. In some embodiments, the glass base substrate can include Cs ₂ O in an amount from greater than or equal to 0 mole % to less than or equal to 10 mole %, such as from greater than or equal to 1 mole % to less than or equal to 9 moles Ear %, from greater than or equal to 2 mole % to less than or equal to 8 mole %, from greater than or equal to 3 mole % to less than or equal to 7 mole %, from greater than or equal to 4 mole % to less than or equal to 6 Mole %, 5 mol % or any sub-range formed from any of these endpoints.

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

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

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

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

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

In some embodiments, the glass base substrate can exhibit an initial threshold of one or more of 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 more.

The glass substrate can have any suitable geometry. In some embodiments, the glass base substrate may have a thickness 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 base substrate may have been in the form of a sheet or a sheet. In some other embodiments, the glass base substrate can have a 2.5D or 3D shape. As used herein, "2.5D shape" refers to a sheet-like article having at least one major surface that is at least partially uneven, and substantially one of the second major surfaces. As used herein, "3D shape" refers to an article having first and second opposing major surfaces that are at least partially uneven.

The glass substrate article can be produced from a glass substrate by exposure to water vapor under any suitable conditions. Exposure can be performed in any suitable component, such as a furnace with relative humidity control. In some embodiments, the glass base substrate can be exposed to an environment having a relative humidity of 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 base substrate can be exposed to an environment having a relative humidity of 100%.

In some embodiments, the glass base substrate 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 base substrate can be exposed to an environment at a temperature from one 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 Equivalent 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 such endpoints.

In some embodiments, the glass substrate can be exposed to an aqueous vapor environment for a period of time sufficient to produce a desired degree of diffusion of the hydrogen-containing material and a desired layer depth. In some embodiments, the glass substrate can be exposed to an aqueous vapor environment 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 can be exposed to an aqueous vapor environment for a period of time 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 by any of these endpoints. These exposure conditions can be modified to reduce the time necessary to produce the desired amount of diffusion of the hydrogen-containing material into the glass substrate. For example, the temperature and/or relative humidity can be increased to reduce the time required to achieve a desired degree of hydrogen species diffusion and layer depth into the glass substrate.

The glass substrate article disclosed herein can be incorporated into another article, such as an item (or display item) having a display (eg, consumer electronic components, including mobile phones, tablets, computers, navigation systems, wearable Components (eg, watches) and the like), building parts, traffic items (eg, cars, trains, airplanes, sea wheels, etc.), electrical items, or require some transparency, scratch resistance, wear resistance, or a combination thereof Any object. An exemplary article of any of the glass substrate articles disclosed herein is shown in Figures 2A and 2B. In particular, Figures 2A and 2B show a consumer electronic component 200 comprising: a housing 202 having a front portion 204, a rear portion 206 and a side surface 208; an electrical component (not shown) at least partially in the housing Internal or wholly within the housing and including at least one controller, a memory and a display 210 at or adjacent the front surface of the housing; and a cover substrate 212 at or above the front surface of the housing such that it is on the display on. In some embodiments, at least a portion of one of the lid substrate 212 and the outer shell 202 can comprise any of the glass substrate articles disclosed herein.
Illustrative embodiment

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

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

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

The Vickers dent cracking threshold was measured before and after exposure to an aqueous vapor environment. The results of the Vickers dents of the pre-exposed glass substrate after exposure at 5 kgf and 10 kgf, respectively, are shown in Figures 4 and 5. As shown in Figures 4 and 5, the glass base substrate has an initial threshold of Vickers cracking above 5 kgf but below 10 kgf. The results of the Vickers dents of the exposed glass substrate were shown in Figures 6, 7, and 8 after indentations at 5 kgf and 10 kgf and 20 kgf, respectively. As shown in Figures 6, 7, and 8, the Vickers dent cracking threshold for glass substrate articles is greater than 20 kgf.

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

As shown in Table III, the glass composition of Example 1 exhibited two orders of magnitude higher hydrogen diffusion for the glass composition of Comparative Example 3, and Comparative Example 3 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 diffusion of two orders of magnitude higher than Comparative Examples 1 and 2, respectively, including lithium and sodium. The difference in hydrogen diffusivity between the potassium-containing glass composition and the lithium-containing and soda glass compositions indicates that alkali ions having a larger ionic radius allow for faster hydrogen diffusivity.

A glass base substrate comprising the glass composition of Example 6 was produced having a thickness of 0.5 mm and 1.0 mm. The glass substrate was exposed to a 100% relative humidity environment at a temperature of 200 ° C for a period of 7 days to produce a glass substrate article of the type described herein. The glass substrate articles exhibit a region of compressive stress extending from the surface to a compression depth. The maximum compressive stress measured for a 0.5 mm glass substrate object is 124 Mpa, and the maximum compressive stress measured for a 1.0 mm glass substrate object is 137 Mpa. The maximum central stretch for a 0.5 mm glass substrate is 32 Mpa and the maximum compressive stress for a 1.0 mm glass substrate is 15 Mpa. The 0.5 mm glass substrate has a compression depth of 101 μm and a 1.0 mm glass substrate with a compression depth of 99 μm.

A centrally cut sample of 0.5 mm and 1.0 mm thick glass substrate articles formed from a glass substrate comprising the glass composition of Example 6 was also exposed after exposure to a 100% relative humidity environment at 200 °C for 7 days. The sample was then polished to a width of 0.5 mm and subjected to Fourier-transform infrared spectroscopy (FTIR) analysis. FTIR analysis was performed by the following conditions: CaF/InSb, 64 scans, 16 cm ^-1 resolution, 10 μm aperture and 10 μm steps. The scan originates from the surface of the sample and continues to approximately the midpoint of the thickness. The spectra were generated relative to the "dry" vermiculite, and the hydroxyl (βOH) concentration was calculated using the 3900 cm ^-1 max and 3550 cm ^-1 min parameters. Due to the multi-component nature of the glass substrate article, it is not possible to distinguish between the bound hydroxyl group and the molecular hydroxyl group, so the curve reports the concentration of the total hydroxyl content. The hydroxyl concentration of the 0.5 mm thick and 1.0 mm thick samples is shown in Figures 9 and 10, respectively. As shown in Figures 9 and 10, the measured hydroxyl content becomes substantially constant and is equivalent to the hydroxyl content at the center of the article (indicating the background hydroxyl content of the precursor glass substrate article). The concentration is approximately 200 μm as measured by FTIR. The appearance of the peak value of the buried hydroxyl concentration in Figs. 9 and 10 is an artifact of the measurement method.

A square sample having the composition of Example 1 was prepared with a thickness of 1 mm and 50 mm sides. Five of these samples were then processed in a 100% relative humidity environment at 200 °C for 121 hours. Then, the resulting compressive stress (CS) and depth of compression (DOC) of the treated sample were measured by FSM to obtain CS of 167 MPa and 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 intensity and peak load of each test sample are reported in Table IV. As shown in Table IV, the steam treated samples exhibited greatly increased peak load and strength compared to untreated control samples.

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

Prior to the ring-to-loop test, the surface of the glass substrate article sample is ground as described in ASTM C158-02, Appendix 2, to be normalized using the device shown in Figure A2.1 of ASTM C158-02. Or control the surface defect condition of the sample. The abrasive material was blasted onto the surface of the glass substrate article under an air pressure of 5 psi. After the air flow was established, 1 cm ³ of the abrasive material was poured into the furnace and the sample was sandblasted.

For the AROR test, a glass substrate article having at least one abrasive surface as shown in FIG. 11 is placed between two concentric rings of different sizes to determine the isoaxial flexural strength (ie, when subjected to two concentricities) The maximum stress that the material can support when flexing between the rings). In the AROR configuration 400, the ground glass substrate article 410 is supported by a support ring 420 having a diameter D2. By loading the ring 430 with one of the diameters D1, the force F is applied to the surface of the glass substrate article by a dynamometer (not shown).

The diameter ratio D1/D2 of the loading ring to the support ring may 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 diameter D2 of the support ring. The dynamometer used for testing should be accurate to within ±1% at any load within the selected range. The test was carried out 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 article 410. The loading ring 430 and the support ring 420 are made of hardened steel having a hardness of HRc > 40. AROR fixtures are commercially available.

The intended failure mechanism for the AROR test is to observe the breakage of the glass substrate article 410 originating from the surface 430a within the loading ring 430. Failures outside the region (i.e., between the load ring 430 and the support ring 420) are ignored in the data analysis. However, due to the thinness and high strength of the glass substrate article 410, a large deflection exceeding the thickness h of the sample is sometimes observed. Therefore, it is not uncommon to observe that a high percentage of faults originating from the load ring 430. The stress cannot be accurately calculated without knowing the stress development inside and below the ring (collected via strain gauge analysis) and the source of the fault in each sample. In response to the measurement, the AROR test therefore focuses on the peak load at the fault.

Although the exemplary embodiments have been described for purposes of illustration, the foregoing description should not be construed as limiting the scope of the disclosure or the scope of the appended claims. Accordingly, various modifications, adaptations and substitutions are conceivable to those skilled in the art without departing from the spirit and scope of the disclosure.

100‧‧‧Glass base objects

110‧‧‧ first surface

112‧‧‧ second surface

120‧‧‧First hydrogen-containing layer

122‧‧‧Second hydrogen containing layer

130‧‧‧No added hydrogen substance area

200‧‧‧ Consumer Electronic Components

202‧‧‧Shell

204‧‧‧ front

206‧‧‧ Rear

208‧‧‧ side surface

210‧‧‧ display

212‧‧‧Cover substrate

301‧‧‧The original hydrogen concentration curve of the glass substrate

302‧‧‧Glass base material hydrogen concentration curve

303‧‧‧Extrapolation curve

400‧‧‧AROR configuration

410‧‧‧Grinding glass substrate

420‧‧‧Support ring

430‧‧‧Loading ring

430a‧‧‧ surface

D1‧‧ depth

D2‧‧ depth

T‧‧‧thickness

D1‧‧‧ loading ring diameter

D2‧‧‧ support ring diameter

F‧‧‧ force

Figure 1 is a representation of a cross section of a glass substrate article in accordance with an embodiment.

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

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

Figure 3 is a measurement of the concentration of hydrogen produced by SIMS on a glass substrate formed from a glass substrate having the composition of Example 1 as a function of depth below the surface.

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

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

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

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

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

Figure 9 is a graph of hydroxyl (BOH) concentration of a 0.5 mm thick glass article as a function of depth from the surface after exposure to an aqueous environment, in accordance with an embodiment.

Figure 10 is a graph of hydroxyl (BOH) concentration of a 1.0 mm thick glass article as a function of depth from the surface after exposure to an aqueous environment, in accordance with an embodiment.

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

Domestic deposit information (please note in the order of the depository, date, number)
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Foreign deposit information (please note in the order of country, organization, date, number)
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Claims (10)

A glass substrate article comprising: SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ ; and a hydrogen-containing layer extending from a surface of the glass substrate to a depth, wherein: a hydrogen concentration of the hydrogen-containing layer The depth decreases from a maximum hydrogen concentration to the depth of the layer; and the depth of the layer is greater than 5 μm. The glass substrate article of claim 1, wherein the glass substrate article is characterized by at least one of the following: An initial threshold of at least 1 kgf of Vickers cracking, or a depth of the layer of at least about 10 μm. The glass substrate article of claim 1 or 2, wherein the center of the glass substrate article comprises at least one of the following composition: I. greater than or equal to 45 mol% to less than or equal to 75 mol% of SiO ₂ ; Greater than or equal to 3 mol% to less than or equal to 20 mol% of Al ₂ O ₃ ; greater than or equal to 6 mol % to less than or equal to 15 mol % of P ₂ O ₅ ; and greater than or equal to 6 mol % to less than or equal to 25 mole% of K ₂ O, II or greater than or equal to 45 mole% to less than or equal to 75 mole% of SiO _2;. greater than or equal to 3 mole% to less than or equal to 20 mole% Al ₂ O ₃ ; greater than or equal to 4 mol% to less than or equal to 15 mol% of P ₂ O ₅ ; and greater than or equal to 11 mol % to less than or equal to 25 mol % of K ₂ O. The glass substrate article of claim 1 or 2, wherein the glass substrate article is substantially free of at least one of lithium and sodium. The glass substrate article of claim 1 or 2, further comprising a compressive stress layer extending from a surface of the glass substrate member to the glass substrate member to a compression depth, wherein the compressive stress layer comprises greater than or equal to 100 One of the Mpa compresses the stress, and the compression depth is greater than or equal to 75 μm. A consumer electronics product that includes: An outer casing comprising a front surface, a rear surface and a side surface; an electrical component at least partially within the outer casing, the electrical component comprising at least one controller, a memory and a display, the display being at or adjacent to the outer casing The front surface; and a cover substrate disposed on the display, wherein at least a portion of the at least one of the outer casing or the cover substrate comprises the glass substrate article of claim 1 or 2. A glass comprising: SiO ₂ greater than or equal to 45 mol% to less than or equal to 75 mol%; greater than or equal to 3 mol% to less than or equal to 20 mol% of Al ₂ O ₃ ; greater than or equal to 6 mo Ear % to less than or equal to 15 mole % P ₂ O ₅ ; and greater than or equal to 6 mole % to less than or equal to 25 mole % K ₂ O. A glass comprising: SiO ₂ greater than or equal to 45 mol% to less than or equal to 75 mol%; greater than or equal to 3 mol% to less than or equal to 20 mol% of Al ₂ O ₃ ; greater than or equal to 4 mo Ear % to less than or equal to 15 mole % P ₂ O ₅ ; and greater than or equal to 11 mole % to less than or equal to 25 mole % K ₂ O. The glass of claim 7 or 8, wherein the glass is characterized by at least one of the following: There is substantially no one of lithium and sodium, or one of greater than or equal to 5 kgf of the initial threshold of Vickers cracking. A method comprising the steps of: 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 from the glass substrate a surface extending to a depth, wherein: the glass base substrate comprises SiO ₂ , Al ₂ O ₃ and P ₂ O ₅ ; a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to a depth of the layer; and the layer depth Greater than or equal to 5 μm.