Platinum-compatible glass compositions that can be fusion-formed and steam-strengthened

Abstract

A glass-based article having a compressive stress layer extending from the surface of the glass-based article to a compression depth is formed by exposing a glass-based substrate to a water vapor-containing environment. The composition of the glass-based substrate is selected to be fusion-formable and steam-strengthenable without introducing platinum defects during the forming process. The method of forming the glass-based article can include exposing the glass-based substrate to a water vapor-containing environment at elevated pressures and / or multiple times.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Patent Application No. 63 / 023,518, filed May 12, 2020, the entire disclosure of which is incorporated herein by reference. [Technical Field]

[0002] The present disclosure relates to steam-treated strengthened glass-based articles, glass compositions used to form glass-based articles, and steam-treatment methods for strengthening glass-based articles. [Background technology]

[0003] Portable electronic devices, such as smartphones, tablets, and wearable devices (e.g., wristwatches, fitness trackers, etc.), are becoming smaller and more complex. This, in turn, has led to an increase in the complexity of the materials traditionally used to form at least one of the exterior surfaces of such devices. For example, as portable electronic devices become smaller and thinner to meet consumer needs, the display covers and housings used in such devices are also becoming smaller and thinner, resulting in increased performance requirements for the materials used to form these components. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a demand for materials for use in portable electronic devices that have high performance such as damage resistance, and that can be manufactured at low cost and easily. [Means for solving the problem]

[0005] In aspect (1), a glass-based article is provided. The glass-based article has a compressive stress layer extending from the surface of the glass-based article to a compression depth, a hydrogen-containing layer extending from the surface of the glass-based article to a layer depth, and a composition of a center portion of the glass-based article, the composition of the center portion of the glass-based article including SiO2, Al2O3, KO, and, where the total amount of monovalent metal oxides is R2O, an R2O / Al2O3 ratio of 1.4 or less, 3.5 mol% to 6.0 mol% of P2O5, and 2.0 mol% to 5.0 mol% of Li2O. The compressive stress layer has a compressive stress of 25 MPa or more, and the hydrogen concentration of the hydrogen-containing layer decreases from the maximum hydrogen concentration toward the layer depth, and the layer depth exceeds 5 μm.

[0006] In embodiment (2), there is provided the glass-based article of embodiment (1), further comprising a fusion line.

[0007] In aspect (3), there is provided the glass-based article according to aspect (1) or (2), wherein the glass-based article contains less than one platinum bead-and-chain defect per pound (about 0.45 kg).

[0008] In an aspect (4), there is provided the glass-based article of aspect (1) or (2), wherein the glass-based article does not exhibit substantially phase separation.

[0009] In an embodiment (5), there is provided the glass-based article according to any one of embodiments (1) to (4), wherein the composition of the center part of the glass-based article further comprises B2O3.

[0010] In an embodiment (6), there is provided the glass-based article according to any one of embodiments (1) to (5), wherein the composition of the center part of the glass-based article further comprises Na2O.

[0011] In an embodiment (7), there is provided the glass-based article according to any one of embodiments (1) to (6), wherein the composition of the center part of the glass-based article further comprises SnO2.

[0012] In an embodiment (8), there is provided a glass-based article according to any one of embodiments (1) to (7), wherein the composition of the center portion of the glass-based article has an average alkali modifier field strength of 0.18 or less.

[0013] In an embodiment (9), there is provided the glass-based article according to any one of embodiments (1) to (8), wherein the composition of the center of the glass-based article comprises 55.0 mol% to 65.0 mol% of SiO2, 10.0 mol% to 15.0 mol% of Al2O3, 0 mol% to 10.0 mol% of B2O3, and 6.0 mol% to 15.0 mol% of K2O.

[0014] In an aspect (10), there is provided a glass-based article according to any one of aspects (1) to (9), wherein the composition of the center part of the glass-based article comprises 4.5 mol % or more and 5.5 mol % or less of P2O5.

[0015] In an embodiment (11), there is provided the glass-based article according to any one of embodiments (1) to (10), wherein the composition of the center portion of the glass-based article comprises more than 0 mol% and not more than 3.0 mol% of B2O3.

[0016] In aspect (12), there is provided a glass-based article according to any one of aspects (1) to (11), in which the zircon decomposition viscosity of glass having the same composition as that of the central part of the glass-based article is 35 kP or less.

[0017] In aspect (13), there is provided a glass-based article according to any one of aspects (1) to (12), in which the liquidus viscosity of glass having the same composition as that of the central part of the glass-based article is 100 kP or more.

[0018] In an aspect (14), there is provided a glass-based article according to any one of aspects (1) to (13), wherein the glass-based article has a substantially haze-free appearance.

[0019] In an embodiment (15), there is provided the glass-based article according to any one of embodiments (1) to (14), wherein the compression depth is greater than 5 μm.

[0020] In an embodiment (16), there is provided the glass-based article according to any one of embodiments (1) to (15), wherein the compressive stress layer has a compressive stress of 200 MPa or more.

[0021] In an aspect (17), there is provided a glass-based article according to any one of aspects (1) to (16), wherein the composition has a (R2O+P2O5) / Al2O3 ratio of 1.4<(R2O+P2O5) / Al2O3<1.9, where R2O is the total amount of monovalent metal oxides.

[0022] In aspect (18), a consumer electronics product is provided. The consumer electronics product includes a housing having a front surface, a back surface, and a side surface, electrical components at least partially housed inside the housing, the electrical components including at least a controller, a memory, and a display provided on the front surface of the housing or adjacent thereto, and a cover substrate disposed to cover the display. At least one of the housing and the cover substrate includes, at least in part, the glass-based article according to any one of aspects (1) to (17).

[0023] In a nineteenth aspect, a glass-based article is provided. The glass-based article has a compressive stress layer extending from the surface of the glass-based article to a compression depth, a hydrogen-containing layer extending from the surface of the glass-based article to a layer depth, and a composition at a center of the glass-based article, the composition including SiO, AlO, KO, (R2O + P2O5) / Al2O3, where R2O is the total amount of monovalent metal oxides, such that (R2O + P2O5) / Al2O3 is 1.4<(R2O + P2O5) / Al2O3<1.9, 3.5 mol% to 6.0 mol% P2O5, and 2.0 mol% to 5.0 mol% Li2O. The compressive stress layer has a compressive stress of 25 MPa or more, and the hydrogen concentration of the hydrogen-containing layer decreases from the maximum hydrogen concentration toward the layer depth, and the layer depth exceeds 5 μm.

[0024] In an embodiment (20), there is provided the glass-based article according to embodiment (19), wherein the glass-based article contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0025] In an aspect (21), there is provided the glass-based article of aspect (19) or (20), wherein the glass-based article does not exhibit substantially phase separation.

[0026] In a twenty-second embodiment, a glass-based article is provided. The glass-based article has a compressive stress layer extending from the surface of the glass-based article to a compression depth, a hydrogen-containing layer extending from the surface of the glass-based article to a layer depth, and a composition at a center of the glass-based article, the composition including SiO, AlO, KO, (R2O+PO5) / Al2O3, where 1.4<(R2O+PO5) / Al2O3<1.9, where R2O is the total amount of monovalent metal oxides, and 3.5 mol% to 6.0 mol% of PO5. The compressive stress layer has a compressive stress of 25 MPa or more, and the hydrogen concentration of the hydrogen-containing layer decreases from the maximum hydrogen concentration toward the layer depth, and the layer depth exceeds 5 μm.

[0027] In an embodiment (23), there is provided the glass-based article according to embodiment (22), wherein the glass-based article contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0028] In an aspect (24), there is provided the glass-based article of aspect (22) or (23), wherein the glass-based article does not exhibit substantially phase separation.

[0029] In a 25th aspect, a method is provided. The method includes forming a glass-based article by exposing a glass-based substrate to a processing environment having a pressure of 0.1 MPa or more, a water partial pressure of 0.05 MPa or more, and a temperature greater than 85°C. The glass-based substrate includes SiO, AlO, KO, an R / AlO ratio of 1.4 or less, where R is the total amount of monovalent metal oxides, an P0 ratio of 3.5 mol% to 6.0 mol%, and an LiO ratio of 2.0 mol% to 5.0 mol%. The glass-based article includes: a compressive stress layer extending from a surface of the glass-based article to a compression depth, the compressive stress layer having a compressive stress of 25 MPa or more; and a hydrogen-containing layer extending from the surface of the glass-based article to a depth, the hydrogen concentration of the hydrogen-containing layer decreasing from a maximum hydrogen concentration toward the depth, the depth being greater than 5 μm.

[0030] In an embodiment (26), the method of embodiment (25) is provided, wherein the processing environment is a saturated steam environment.

[0031] In an embodiment (27), the method of embodiment (25) or (26) is provided, wherein the processing environment has a pressure of 1 MPa or more.

[0032] In an embodiment (28), there is provided the method of any one of embodiments (25) to (27), wherein the treatment environment has a temperature of 150° C. or greater.

[0033] In an embodiment (29), there is provided the method of any one of embodiments (25) to (28), further comprising manufacturing the glass-based substrate by a fusion molding process.

[0034] In an embodiment (30), there is provided the method according to any one of embodiments (25) to (29), wherein the glass-based substrate is not subjected to an ion exchange treatment using an alkali ion source.

[0035] In an embodiment (31), there is provided the method of any one of embodiments (25) to (30), wherein the glass-based substrate further comprises B2O3.

[0036] In an embodiment (32), there is provided the method of any one of embodiments (25) to (31), wherein the glass-based substrate further comprises Na2O.

[0037] In an embodiment (33), there is provided the method of any one of embodiments (25) to (32), wherein the glass-based substrate further comprises SnO2.

[0038] In an embodiment (34), there is provided the method of any one of embodiments (25) to (33), wherein the glass-based substrate has an average alkali modifier field strength of 0.18 or less.

[0039] In an embodiment (35), there is provided the method of any one of embodiments (25) to (34), wherein the glass-based substrate comprises 55.0 mol% to 65.0 mol% of SiO2, 10.0 mol% to 15.0 mol% of Al2O3, 0 mol% to 10.0 mol% of B2O3, and 6.0 mol% to 15.0 mol% of K2O.

[0040] In an embodiment (36), there is provided the method of any one of embodiments (25) to (35), wherein the glass-based substrate comprises 4.5 mol % or more and 5.5 mol % or less of P2O5.

[0041] In an embodiment (37), there is provided the method of any one of embodiments (25) to (36), wherein the glass-based substrate comprises more than 0 mol % and not more than 3.0 mol % B2O3.

[0042] In an embodiment (38), there is provided the method of any one of embodiments (25) to (37), wherein the glass-based substrate has a fusion line.

[0043] In an embodiment (39), there is provided the method of any one of embodiments (25) to (38), wherein the glass-based substrate contains less than one platinum ball-and-chain defect per pound (about 0.45 kg).

[0044] In an embodiment (40), there is provided the method of any one of embodiments (25) to (39), wherein the glass-based substrate has a zircon decomposition viscosity of 35 kP or less.

[0045] In an embodiment (41), there is provided the method of any one of embodiments (25) to (40), wherein the glass-based substrate has a liquidus viscosity of 100 kP or greater.

[0046] In an embodiment (42), there is provided the method of any one of embodiments (25) to (41), wherein the glass-based article has a substantially haze-free appearance.

[0047] In an embodiment (43), there is provided the method of any one of embodiments (25) to (42), wherein the compression depth is greater than 5 μm.

[0048] In an embodiment (44), there is provided the method of any one of embodiments (25) to (43), wherein the compressive stress layer has a compressive stress of 200 MPa or more.

[0049] In embodiment (45), a glass is provided that includes 55.0 mol% to 65.0 mol% SiO, 10.0 mol% to 15.0 mol% AlO, 0 mol% to 10.0 mol% BO, 6.0 mol% to 15.0 mol% KO, 3.5 mol% to 6.0 mol% PO, 2.0 mol% to 5.0 mol% LiO, and (R0+P0) / AlO such that, where R0 is the total amount of monovalent metal oxides, 1.4<(R0+P0) / AlO<1.9.

[0050] In an embodiment (46), the glass of embodiment (45) is provided, having an average alkali modifier field strength of 0.18 or less.

[0051] In an embodiment (47), there is provided the glass of embodiment (45) or (46), comprising 4.5 mol % or more and 5.5 mol % or less of P2O5.

[0052] In an embodiment (48), there is provided the glass of any one of embodiments (45) to (47), further comprising B2O3.

[0053] In an embodiment (49), there is provided the glass of any one of embodiments (45) to (48), further comprising greater than 0 mol % and not greater than 3 mol % of B2O3.

[0054] In an embodiment (50), there is provided the glass according to any one of embodiments (45) to (49), further comprising Na2O.

[0055] In an embodiment (51), there is provided the glass according to any one of embodiments (45) to (50), further comprising at least 0 mol % and at most 11 mol % Na2O.

[0056] In an embodiment (52), there is provided the glass according to any one of embodiments (45) to (51), further comprising SnO2.

[0057] In an embodiment (53), there is provided the glass according to any one of embodiments (45) to (52), having a zircon decomposition viscosity of 35 kP or less.

[0058] In an embodiment (54), there is provided the glass according to any one of embodiments (45) to (53), which has a liquidus viscosity of 100 kP or more.

[0059] These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims. [Brief explanation of the drawings]

[0060] [Figure 1] FIG. 1 shows a representative cross section of a glass-based article according to one embodiment. [Figure 2A] FIG. 1 is a plan view illustrating an exemplary electronic device incorporating any of the glass-based articles disclosed herein. [Figure 2B] FIG. 2B is a perspective view of the exemplary electronic device shown in FIG. 2A. [Figure 3] Plot showing water saturation conditions as a function of pressure and temperature [Figure 4] Plot showing the number of platinum bead-and-chain defects per pound of glass as a function of phosphorus content. [Figure 5] Microscope image showing platinum bead-chain defects in glass [Figure 6A] Diffuse scattering transmittance versus wavelength plot for a glass composition according to an embodiment of the present disclosure and a comparative glass composition. [Figure 6B] Scattering ratio versus wavelength plot for a glass composition according to an embodiment of the present disclosure and comparative glass compositions. [Figure 7A] Scanning electron microscope (SEM) images of comparative glass compositions showing evidence of phase separation [Figure 7B] Scanning electron microscope (SEM) images of comparative glass compositions showing evidence of phase separation DETAILED DESCRIPTION OF THE INVENTION

[0061] In the following description, like or corresponding parts throughout the figures shown in the drawings will be designated by like reference numerals. It is also understood that, unless otherwise noted, terms such as "top," "bottom," "outward," and "inward" are for convenience only and should not be construed as limiting terms. Unless otherwise noted, when a range of values ​​is described, the range is inclusive of both the upper and lower limits, as well as any subranges therebetween. Furthermore, unless otherwise noted, the indefinite articles "a," "an," and their corresponding definite article "the" used herein mean "at least one" or "one or more." It is also understood that the various features disclosed in this specification and the drawings can be used in any and all combinations.

[0062] As used herein, the term "glass-based" is used broadly to include any object made entirely or partially of glass, such as a glass-ceramic (containing a crystalline phase and a residual amorphous glass phase). Unless otherwise noted, all glass compositions described herein are expressed in mole percent (mol%), and the components are expressed on an oxide basis. Additionally, all temperatures are expressed in degrees Celsius (°C) unless otherwise noted.

[0063] It should be noted that the terms "substantially" and "about" used herein may express the inherent degree of uncertainty that may arise in any quantitative comparison, value, measurement, or other expression. The terms "substantially" and "about" are also used herein to express the degree to which a quantitative expression can vary from a stated reference value without changing the basic function of the subject matter. For example, a glass that is "substantially free of K2O" is a glass in which K2O is not actively added or batched into the glass, but may be present as an impurity in very small amounts, e.g., less than about 0.01 mol%. Furthermore, when a value is modified with the term "about" herein, the exact value itself is also disclosed. For example, the term "greater than about 10 mol%" also discloses "10 mol% or greater."

[0064] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying examples and drawings.

[0065] The glass-based articles disclosed herein are formed by vapor treating a glass-based substrate to create a compressive stress layer that extends from the surface of the article to a depth of compression (DOC). The composition of the glass-based substrate is selected to make the glass-based substrate fusion-formable and platinum-compatible, so that the glass-based substrate can be fusion-formed and does not introduce platinum defects during the forming process. Furthermore, the composition of the glass-based substrate and the processing method are selected to prevent the formation of haze on the surface of the glass-based article. The compressive stress layer has a stress that decreases from the maximum stress toward the compression depth. In some embodiments, the location of the maximum compressive stress can be the surface of the glass-based article. As used herein, depth of compression (DOC) refers to the depth at which the stress within the glass-based article changes from compressive to tensile. That is, the glass-based article also has a tensile stress region with a maximum central tension (CT), thereby balancing the forces within the glass-based article.

[0066] The glass-based article also includes a hydrogen-containing layer extending from the surface of the article to a depth thereof. The hydrogen-containing layer has a hydrogen concentration that decreases from a maximum hydrogen concentration in the glass-based article to a depth thereof. In some embodiments, the location of the maximum hydrogen concentration can be the surface of the glass-based article.

[0067] Glass-based articles can be formed by exposing a glass-based substrate to an environment containing water vapor, which allows hydrogen species to penetrate the glass-based substrate and form a glass-based article having a hydrogen-containing layer and / or a compressive stress layer. As used herein, the term "hydrogen species" encompasses water molecules, hydroxyls, hydrogen ions, and hydronium. The composition of the glass-based substrate is selected to promote the interdiffusion of hydrogen species into the glass. As used herein, the term "glass-based substrate" refers to the precursor prior to exposure to a water vapor-containing environment to form a glass-based article having a hydrogen-containing layer and / or a compressive stress layer. Similarly, the term "glass-based article" refers to the article having a hydrogen-containing layer and / or a compressive stress layer after exposure.

[0068] The glass-based articles disclosed herein can produce compressive stress layers without traditional ion exchange, heat tempering, or lamination processes. Ion exchange processes generate a large amount of waste in the form of spent molten salt baths, which can be costly to dispose of, and they are only applicable to certain glass compositions. Regarding heat tempering, heat tempering thin sheets requires thick glass samples because the small air gap during the quenching process makes them prone to scratches, reducing performance and yield. Furthermore, when heat tempering thin glass sheets, it can be difficult to achieve uniform compressive stress throughout the entire surface and edge. Furthermore, lamination processes can expose tensile stress regions when cutting large sheets to usable sizes.

[0069] On the other hand, when glass-based articles are formed using steam treatment, molten salts are not used, which reduces waste and costs compared to ion exchange treatment. Steam treatment also allows for the strengthening of thin (<2 mm) glass that is not suitable for thermal tempering. Furthermore, steam treatment can be performed at the component level, avoiding the exposure of tensile stress regions that is problematic in lamination processes. In other words, the glass-based articles disclosed herein can be manufactured at low cost with reduced thickness while still exhibiting high compressive stress and deep compression depth.

[0070] FIG. 1 illustrates a representative cross-section of a glass-based article 100 according to some embodiments. The glass-based article 100 has a thickness t extending between a first surface 110 and a second surface 112. A first compressive stress layer 120 extends from the first surface 110 to a first compressed depth. The first compressed depth has a depth d1 measured from the first surface 110 toward the interior of the glass-based article 100. A second compressive stress layer 122 extends from the second surface 112 to a second compressed depth. The second compressed depth has a depth d2 measured from the second surface 112 toward the interior of the glass-based article 100. A tensile stress region 130 exists between the first compressed depth and the second compressed depth. In embodiments, the first compressed depth d1 can be substantially equal to or equal to the second compressed depth d2.

[0071] In some embodiments, the compressive stress layer of the glass-based article can have a compressive stress of 25 MPa or greater, for example, 30 MPa or greater, 40 MPa or greater, 50 MPa or greater, 60 MPa or greater, 70 MPa or greater, 80 MPa or greater, 90 MPa or greater, 100 MPa or greater, 110 MPa or greater, 120 MPa or greater, 130 MPa or greater, 140 MPa or greater, 145 MPa or greater, 150 MPa or greater, 160 MPa or greater, 170 MPa or greater, 180 MPa or greater, 190 MPa or greater, 200 MPa or greater, 210 MPa or greater, MPa or greater, 220 MPa or greater, 230 MPa or greater, 240 MPa or greater, 250 MPa or greater, 260 MPa or greater, 270 MPa or greater, 280 MPa or greater, 290 MPa or greater, 300 MPa or greater, 310 MPa or greater, 320 MPa or greater, 330 MPa or greater, 340 MPa or greater, 350 MPa or greater, 360 MPa or greater, 370 MPa or greater, 380 MPa or greater, 390 MPa or greater, 400 MPa or greater, 410 MPa or greater, 420 MPa or greater, or greater than 420 MPa. In some embodiments, the compressive stress layer can have a compressive stress of 25 MPa or more and 450 MPa or less, for example, 30 MPa or more and 440 MPa or less, 40 MPa or more and 430 MPa or less, 50 MPa or more and 420 MPa or less, 60 MPa or more and 410 MPa or less, 70 MPa or more and 400 MPa or less, 80 MPa or more and 390 MPa or less, 90 MPa or more and 380 MPa or less, 100 MPa or more and 370 MPa or less, 110 MPa or more and 360 MPa or less, 120 MPa or more and 350 MPa or less, 130 MPa or more and 140 MPa or less. The compressive stress may be 340 MPa or less, 140 MPa to 330 MPa, 150 MPa to 320 MPa, 160 MPa to 310 MPa, 170 MPa to 300 MPa, 180 MPa to 290 MPa, 190 MPa to 280 MPa, 200 MPa to 270 MPa, 210 MPa to 260 MPa, 220 MPa to 250 MPa, 220 MPa to 240 MPa, or any subrange formed from the endpoints of any of these ranges.

[0072] In some embodiments, the compression depth of the compressive stress layer can be 5 μm or greater, such as 7 μm or greater, 10 μm or greater, 15 μm or greater, 20 μm or greater, 25 μm or greater, 30 μm or greater, or greater than 30 μm. In some embodiments, the compression depth of the compressive stress layer can be 5 μm or greater to 100 μm or less, such as 7 μm or greater to 90 μm, 10 μm or greater to 80 μm, 15 μm or greater to 70 μm, 20 μm or greater to 60 μm, 25 μm or greater to 50 μm, 30 μm or greater to 40 μm, 30 μm or greater to 35 μm, or any subrange formable from either endpoint of these ranges.

[0073] In some embodiments, the glass-based article can have a high compression depth and a high compressive stress. For example, the glass-based article can have a combination of any of the compression depths and any of the compressive stresses described herein.

[0074] In some embodiments, where t is the thickness of the glass-based article, the glass-based article may have a compression depth of 0.05t or greater, such as 0.06t or greater, 0.07t or greater, 0.08t or greater, 0.09t or greater, 0.10t or greater, 0.11t or greater, 0.12t or greater, 0.13t or greater, 0.14t or greater, 0.15t or greater, 0.16t or greater, 0.17t or greater, 0.18t or greater, 0.19t or greater, or greater than 0.19t. In some embodiments, the glass-based article may have a compression depth of from 0.05t to 0.20t, for example, from 0.06t to 0.19t, from 0.07t to 0.18t, from 0.08t to 0.17t, from 0.09t to 0.16t, from 0.10t to 0.15t, from 0.11t to 0.14t, from 0.12t to 0.13t, or any subrange formed from the endpoints of either of these ranges.

[0075] Compressive stress (including surface compressive stress) is measured with a surface stress meter (FSM) using commercially available equipment, such as the FSM-6000 manufactured by Orihara Seisakusho Co., Ltd. (Japan). Measuring surface stress requires accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. The SOC is measured according to Procedure C (glass disk method) described in ASTM Standard C770-16, "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the entire contents of which are incorporated herein by reference. Compression depth is measured with the surface stress meter. All maximum central tension (CT) values ​​are measured using the scattered light polariscope (SCALP) technique, which is well known in the art.

[0076] The hydrogen-containing layer of the glass-based article can have a depth of layer (DOL) of greater than 5 μm. In some embodiments, the DOL can be 10 μm or greater, such as 15 μm or greater, 20 μm or greater, 25 μm or greater, 30 μm or greater, 35 μm or greater, 40 μm or greater, 45 μm or greater, 50 μm or greater, 55 μm or greater, 60 μm or greater, 65 μm or greater, 70 μm or greater, 75 μm or greater, 80 μm or greater, 85 μm or greater, 90 μm or greater, 95 μm or greater, or greater than 95 μm. In some embodiments, the depth of layer can be greater than 5 μm and less than or equal to 100 μm, such as 10 μm to 95 μm, 15 μm to 90 μm, 20 μm to 85 μm, 25 μm to 80 μm, 30 μm to 75 μm, 35 μm to 70 μm, 40 μm to 65 μm, 45 μm to 60 μm, 50 μm to 55 μm, or any subrange formed by any endpoint of these ranges. This hydrogen depth of layer is equal to or greater than the compression depth measured using the surface stress meter technique described above. Generally, the glass-based article will exhibit a depth of layer greater than that which can be produced by exposure to the ambient environment.

[0077] The hydrogen-containing layer of the glass-based article can have a depth of layer (DOL) of greater than 0.005t, where t is the thickness of the glass-based article. In some embodiments, the depth of layer can be 0.010t or greater, such as 0.015t or greater, 0.020t or greater, 0.025t or greater, 0.030t or greater, 0.035t or greater, 0.040t or greater, 0.045t or greater, 0.050t or greater, 0.055t or greater, 0.060t or greater, 0.065t or greater, 0.070t or greater, 0.075t or greater, 0.080t or greater, 0.085t or greater, 0.090t or greater, 0.095t or greater, 0.10t or greater, 0.15t or greater, or greater than 0.20t, or greater than 0.20t. In some embodiments, the depth of layer can be greater than 0.005t and less than or equal to 0.205t, for example, 0.010t or greater and less than or equal to 0.200t, 0.015t or greater and less than or equal to 0.195t, 0.020t or greater and less than or equal to 0.190t, 0.025t or greater and less than or equal to 0.185t, 0.030t or greater and less than or equal to 0.180t, 0.035t or greater and less than or equal to 0.175t, 0.040t or greater and less than or equal to 0.170t, 0.045t or greater and less than or equal to 0.165t, 0.050t or greater and less than or equal to 0.160t, 0.05 ...55t or greater and less than or equal to 0.185t, 0.055t or greater and less than or equal to 0.185t, 0.055t or greater and less than or equal to 0.185t, 0.055t or greater and less than or equal to 0.185t, 0.055t or greater and less than or equal to The layer depth may be 0.155t or less, 0.060t or more and 0.150t or less, 0.065t or more and 0.145t or more, 0.070t or more and 0.140t or less, 0.075t or more and 0.135t or less, 0.080t or more and 0.130t or more, 0.085t or more and 0.125t or less, 0.090t or more and 0.120t or less, 0.095t or more and 0.115t or more, 0.100t or more and 0.110t or less, or any subrange formed by the endpoints of any of these ranges.

[0078] The depth of layer and hydrogen concentration are measured using secondary ion mass spectrometry (SIMS) techniques known in the art. While SIMS techniques can measure hydrogen concentration at a certain depth, they cannot distinguish between hydrogen species present in a glass-based article. Therefore, the hydrogen concentration measured by SIMS represents the concentration of all hydrogen species. As used herein, depth of layer (DOL) refers to the depth below the surface of a glass-based article at which a hydrogen concentration equal to the hydrogen concentration at the center of the glass-based article first appears. This definition is based on the hydrogen concentration in the glass-based substrate before treatment, and is determined so that the depth of hydrogen introduced during the treatment process is the depth of layer. However, in practice, the hydrogen concentration at the center of a glass-based article can be approximated by the hydrogen concentration at a depth from the surface of the glass-based article where the hydrogen concentration is substantially constant. This is because the hydrogen concentration at that depth is expected to remain constant between that depth and the center of the glass-based article. This approximation allows the depth of layer to be determined without measuring the hydrogen concentration at the entire depth of the glass-based article. It can be seen that when a compressive stress layer is formed in the glass-based article by the steam treatment, a hydrogen-containing layer is produced.

[0079] Without wishing to be bound by any particular theory, it is believed that the hydrogen-containing layer of the glass-based article results from the interdiffusion of hydrogen ion species contained in the composition of the glass-based substrate. + , HO, and / or H + Glass-based articles can be formed by diffusing hydrogen-containing species, such as ammonium hydroxide, into a glass-based substrate. Water can form silanol groups and penetrate the glass-based substrate, destroying the network structure and causing a volumetric expansion of the glass. This volumetric expansion can then produce a compressive stress layer in the glass-based article. The compressive stress and compression depth of the compressive stress layer can vary depending on the composition of the glass-based substrate used to form the glass-based article and the water vapor treatment conditions (e.g., temperature, pressure, water content, treatment time, etc.). Glass-based articles produced by water vapor treatment can have a stress profile similar to that produced by a sodium-potassium ion exchange strengthening process.

[0080] The glass-based article having the compressive stress layer also exhibits an increase in mass compared to the glass-based substrate prior to the water vapor treatment process. This increase in mass of the glass-based article indicates the formation of a hydrogen-containing layer by the water vapor treatment. This increase in mass is directly related to the amount of hydrogen species incorporated into the glass-based article by the water vapor treatment process.

[0081] The glass-based articles disclosed herein can be incorporated into other articles. Such other articles include, for example, display-equipped articles (or display articles) (e.g., consumer electronics devices such as mobile phones, tablets, computers, navigation systems, and wearable devices (e.g., wristwatches)), as well as any article requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination thereof, such as architectural articles, transportation articles (e.g., automobiles, trains, aircraft, ships, etc.), and electrical appliances. Figures 2A and 2B illustrate exemplary articles incorporating any of the glass-based articles disclosed herein. Specifically, Figures 2A and 2B illustrate a consumer electronic device 200. The consumer electronic device 200 includes a housing 202 having a front surface 204, a back surface 206, and sides 208; electrical components (not shown) at least partially or entirely housed within the housing and including at least a controller, memory, and a display 210 located on or adjacent to the front surface of the housing; and a cover plate 212 located on or over the front surface of the housing to cover the display. In some embodiments, at least one of the cover plate 212 and the housing 202 can comprise, at least in part, any of the glass-based articles disclosed herein.

[0082] Glass-based articles can be formed from glass-based substrates having any suitable composition. The composition of the glass-based substrate can be specifically selected to promote the diffusion of hydrogen-containing species to efficiently form a glass-based article having a hydrogen-containing layer and a compressive stress layer, to enable fusion molding of the glass-based article, to avoid the generation of platinum defects during the manufacturing process, and to avoid the generation of haze due to the water vapor treatment process. In some embodiments, the glass-based substrate can have a composition including SiO, AlO, P0, KO, and optionally LiO. In some embodiments, hydrogen species do not diffuse to the center of the glass-based article. In other words, the center of the glass-based article is the portion least affected by the water vapor treatment. Therefore, the center of the glass-based article can have a composition that is substantially the same as or identical to the composition of the glass-based substrate before treatment in a water-containing environment. The composition of the center of the glass-based article refers to the composition measured at any point at a distance of at least 0.5t from each surface of the glass-based article, where t is the thickness of the glass-based article. The composition of the center portion of the glass-based article can be measured by any suitable process, such as microprobe analysis, and can be approximated by the composition of the glass-based substrate used to form the glass-based article.

[0083] The glass-based substrate may contain any appropriate amount of SiO2. SiO2 is the most abundant component, and therefore, the main component of the glass network formed from the glass composition is also SiO2. If the concentration of SiO2 in the glass composition is too high, the formability of the glass composition may decrease. This is because the higher the SiO2 concentration, the more difficult it is to melt the glass, which in turn has an adverse effect on the formability of the glass. In some embodiments, the glass-based substrate can include SiO in an amount of 55.0 mol% or more and 65.0 mol% or less, such as SiO in an amount of 55.5 mol% or more and 64.5 mol% or less, 56.0 mol% or more and 64.0 mol% or less, 56.5 mol% or more and 63.5 mol% or less, 57.0 mol% or more and 63.0 mol% or less, 57.5 mol% or more and 62.5 mol% or less, 58.0 mol% or more and 62.0 mol% or less, 58.5 mol% or more and 61.5 mol% or less, 59.0 mol% or more and 61.0 mol% or less, 59.5 mol% or more and 60.5 mol% or less, 60.0 mol% or more and 65.0 mol% or less, or any subrange formed by the endpoints of any of these ranges.

[0084] The glass-based substrate can contain any suitable amount of Al2O3. Like SiO2, Al2O3 can function as a glass network former. Because Al2O3 is tetrahedrally coordinated in a glass melt formed from the glass composition, excessive Al2O3 content can increase the viscosity of the glass composition and potentially reduce the formability of the glass composition. However, when the Al2O3 concentration is balanced with the SiO2 and alkali oxide concentrations in the glass composition, Al2O3 can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as fusion molding. The inclusion of Al2O3 in the glass-based substrate can prevent phase separation and reduce the number of non-bridging oxygens (NBOs) in the glass. Furthermore, Al2O3 can also improve the effectiveness of ion exchange. In some embodiments, the glass-based substrate can include Al2O3 in an amount of from 10.0 mol% to 15.0 mol%, inclusive, such as from 10.5 mol% to 14.5 mol%, from 11.0 mol% to 14.0 mol%, from 11.5 mol% to 13.5 mol%, from 12.0 mol% to 13.0 mol%, from 12.5 mol% to 13.0 mol%, or any subrange formed by the endpoints of any of these ranges.

[0085] The glass-based substrate can contain any amount of P2O5 sufficient to achieve the desired hydrogen diffusivity. The inclusion of phosphorus in the glass-based substrate promotes rapid interdiffusion. Therefore, the use of phosphorus-containing glass-based substrates allows for the efficient formation of glass-based articles with hydrogen-containing layers. Furthermore, the inclusion of P2O5 allows for the production of glass-based articles with deep layer depths (e.g., greater than about 10 μm) in relatively short processing times. However, if the amount of P2O5 exceeds 6.0 mol%, the glass is prone to platinum defect formation upon contact with platinum-containing glass-forming equipment (e.g., melters and fining equipment) commonly used in commercial glass manufacturing. In other words, glasses containing more than 6.0 mol% P2O5 lack platinum compatibility. On the other hand, if the amount of P2O5 is less than 3.5 mol%, the glass will have undesirable diffusivity, liquidus temperature, and zircon compatibility. Zircon compatibility is important when using common glass-forming equipment, such as zircon isopipes in fusion molding facilities. In embodiments, the glass-based substrate can include P2O5 in an amount of 3.5 mol% or greater and 6.0 mol% or less, such as 3.5 mol% or greater and 5.5 mol% or less, 3.6 mol% or greater and 5.9 mol% or less, 3.7 mol% or greater and 5.8 mol% or less, 3.8 mol% or greater and 5.7 mol% or less, 3.9 mol% or greater and 5.6 mol% or less, 4.0 mol% or greater and 5.5 mol% or less, 4.1 mol% or greater and 5.4 mol% or less, 4.2 mol% or greater and 5.3 mol% or less, or any subrange formed by the endpoints of any of these ranges.

[0086] The glass-based substrate may contain any suitable amount of Li2O. In other embodiments of the glass-based substrate, no intentional Li2O is added. The inclusion of Li2O in the glass-based substrate can improve the resistance of the glass-based article to haze caused by vapor strengthening. The Li2O content in the glass-based substrate is directly correlated to a decrease in the 200P temperature of the glass-based substrate, and thus the inclusion of Li2O improves the meltability of the glass. The Li2O content in the glass-based substrate is also directly correlated to the thermal expansion coefficient of the glass-based substrate. In some embodiments, the glass-based substrate can include LiO in an amount of 2.0 mol% or greater and 5.0 mol% or less, such as 2.1 mol% or greater and 4.9 mol% or less, 2.2 mol% or greater and 4.8 mol% or less, 2.3 mol% or greater and 4.7 mol% or less, 2.4 mol% or greater and 4.6 mol% or less, 2.5 mol% or greater and 4.5 mol% or less, 2.6 mol% or greater and 4.4 mol% or less, 2.7 mol% or greater and 4.3 mol% or less, 2.8 mol% or greater and 4.2 mol% or less, 2.9 mol% or greater and 4.1 mol% or less, 3.0 mol% or greater and 4.0 mol% or less, 3.1 mol% or greater and 3.9 mol% or less, 3.2 mol% or greater and 3.8 mol% or less, 3.3 mol% or greater and 3.7 mol% or less, 3.4 mol% or greater and 3.6 mol% or less, 3.0 mol% or greater and 3.5 mol% or less, or any and all subranges formed by the endpoints of these ranges.

[0087] The glass-based substrate can include any suitable amount of K2O. The inclusion of K2O in the glass-based substrate significantly improves the steam strengthening rate of the glass-based article compared to other alkali metal oxides. In some embodiments, the glass-based substrate can include K2O in an amount of 6.0 mol% to 15.0 mol%, for example, 6.5 mol% to 14.5 mol%, 7.0 mol% to 14.0 mol%, 7.5 mol% to 13.5 mol%, 8.0 mol% to 13.0 mol%, 8.5 mol% to 12.5 mol%, 9.0 mol% to 12.0 mol%, 9.5 mol% to 11.5 mol%, 10.0 mol% to 11.0 mol%, 10.5 mol% to 11.0 mol%, or any and all subranges formed by the endpoints of these ranges.

[0088] The glass-based substrate can include any suitable amount of NaO. In some embodiments, the glass-based substrate can include NaO in an amount of 0 mol% to 11.0 mol%, for example, 0.5 mol% to 10.5 mol%, 1.0 mol% to 9.0 mol%, 1.5 mol% to 8.5 mol%, 2.0 mol% to 8.0 mol%, 2.5 mol% to 7.5 mol%, 3.0 mol% to 7.0 mol%, 3.5 mol% to 6.5 mol%, 4.0 mol% to 6.0 mol%, 4.5 mol% to 5.5 mol%, 4.0 mol% to 5.0 mol%, or any and all subranges formed by the endpoints of these ranges. In some embodiments, the glass-based substrate can be substantially free of NaO or can be free of NaO.

[0089] The glass-based substrate can also further comprise B2O3. The inclusion of B2O3 in the glass-based substrate can improve the damage resistance of the glass-based substrate, and thus improve the damage resistance of a glass-based article formed from the glass-based substrate. In some embodiments, the glass-based substrate can include B2O3 in an amount of 0 mol% to 10.0 mol%, for example, 0.5 mol% to 9.5 mol%, 1.0 mol% to 9.0 mol%, 1.5 mol% to 8.5 mol%, 2.0 mol% to 8.0 mol%, 2.5 mol% to 7.5 mol%, 3.0 mol% to 7.0 mol%, 3.5 mol% to 6.5 mol%, 4.0 mol% to 6.0 mol%, 4.5 mol% to 5.5 mol%, 4.0 mol% to 5.0 mol%, 0.0 mol% to 3.0 mol%, or any and all subranges formed by the endpoints of these ranges. In embodiments, the glass-based substrate can be substantially free of B2O3 or free of B2O3.

[0090] The glass-based substrate can further include a fining agent. In some embodiments, the fining agent can include tin. In embodiments, the glass-based substrate can include SnO in an amount of greater than or equal to 0 mol% and less than or equal to 0.5 mol%, such as greater than 0 mol% and less than or equal to 0.1 mol%, or any and all subranges formed by the endpoints of these ranges. In embodiments, the glass-based substrate can be substantially free of SnO or can be free of SnO.

[0091] Glass-based substrates can be characterized by an R2O / Al2O3 molar ratio, where R2O is the total amount of monovalent metal oxides, such as alkali metal oxides. In some embodiments, the R2O / Al2O3 molar ratio of the glass-based substrate can be 1.4 or less, such as 1.3 or less, 1.2 or less, 1.1 or less, or less than 1.1. In some embodiments, the R2O / Al2O3 molar ratio of the glass-based substrate can be 1.0 or greater and 1.4 or less, such as 1.1 or greater and 1.4 or greater, 1.2 or greater and 1.3 or less, or any and all subranges formed by the endpoints of these ranges. Maintaining a R2O / Al2O3 molar ratio of 1.4 or less in the glass-based substrate can avoid the formation of a second glass phase within the glass-based substrate, an undesirable phenomenon commonly referred to as phase separation.

[0092] The glass-based substrate may also be characterized by a (RO+PO) / AlO molar ratio, where RO is the total amount of monovalent metal oxides, such as alkali metal oxides. In some embodiments, the glass-based substrate may have a (RO+PO) / AlO molar ratio greater than 1.4 and less than 1.9, such as 1.41 to 1.89, 1.425 to 1.875, 1.45 to 1.85, and all values ​​and subranges therebetween. In some embodiments, the (R2O + P2O5) / Al2O3 molar ratio of the glass-based substrate can be 1.41, 1.42, 1.43, 1.44, 1.45, 1.5, 1.55, 1.6, 1.65, 1.70, 1.75, 1.80, 1.85, 1.86, 1.87, 1.88, 1.89, and all values ​​from 1.4 to 1.9. By maintaining the (R2O + P2O5) / Al2O3 molar ratio of the glass-based substrate between 1.4 and 1.9, phase separation can be avoided.

[0093] The glass-based substrate can also be characterized by the average field strength of the alkali modifier. The field strength of the glass-based substrate is calculated by the following formula: Z / (r A +r O ) 2 In the formula, Z is the charge of the alkali modifier (fixed to a constant of 1), r A is the ionic radius of the alkali ion (Å), r Ois the ionic radius of oxygen (Angstroms). The calculated electric field strengths are 0.23 for Li, 0.19 for Na, and 0.13 for K. The average electric field strength of the alkali modifiers in the glass-based substrate is calculated as a weighted average based on the total alkali content. In several embodiments, the average electric field strength of the alkali modifiers in the glass-based substrate is 0.18 or less, e.g., 0.17 or less, 0.16 or less, 0.15 or less, or less than 0.15. When the average electric field strength of the alkali modifiers in the glass-based substrate is 0.18 or less, the glass-based substrate is less likely to undergo phase separation, particularly when the R2O content is greater than the Al2O3 content. In several embodiments, the average electric field strength of the alkali modifiers in the glass-based substrate is 0.14 or more and 0.18 or less, e.g., 0.15 or more and 0.17 or less, 0.16 or more and 0.18 or less, or any and all subranges formed by the endpoints of these ranges.

[0094] In some embodiments, the glass-based substrate contains Li2O and P2O5, or P2O5 but not Li2O, and does not exhibit phase separation. In this specification, terms such as "phase separation" and "phase-separated glass" refer to a glass-based substrate in which a second glass phase is formed. "Phase-separated glass" can be identified by optical measurement using a spectrophotometer or SEM analysis. Regarding the former, any glass or glass-based substrate having a diffuse transmittance and / or scattering ratio (i.e., diffuse transmittance % / transmittance % × 100) of more than 0.2% at a wavelength of 300 nm when a 1 mm-thick glass or glass-based substrate is used as a sample is considered to be "phase-separated glass." Regarding the latter, phase separation can be identified by SEM analysis of a cross section of the glass-based substrate at a magnification of approximately 100 kx. Phase separation in a glass-based substrate is undesirable because it can cause the glass-based substrate to appear milky white or bluish. Thus, the composition of the glass-based substrate can be specifically selected to prevent phase separation, for example, by selecting the composition of the glass-based substrate so that the R2O / Al2O3 molar ratio and the average electric field strength of the alkali modifier are within the ranges described herein.

[0095] In some embodiments, the glass-based substrate is platinum compatible. This compatibility prevents the formation of platinum globular defects in the glass-based substrate when the glass-based substrate is melted, refined, or formed using platinum-containing equipment. As used herein, the term "globular chain platinum defect" refers to platinum globular chains greater than 100 μm in size observed in glass-based substrates as measured by reflected light optical microscopy or scanning electron microscopy / energy-dispersive x-ray (SEM-EDX) analysis. Furthermore, these platinum globular chains are typically observed as inclusions consisting of two or more connected "globular"-like segments. These globular segments may be spaced apart or may be tightly wrapped around the substrate, connected by multiple planes. Furthermore, the number of "platinum ball-chain defects" herein is determined by optical microscopy or SEM-EDX inspection of the glass-based substrate and normalized by the total mass of the glass being inspected, resulting in a value of the number of defects per pound (approximately 0.45 kg). The size of the platinum ball-chain is defined by its largest dimension. According to some embodiments, the platinum ball-chain defects may include platinum and one or more of rhodium, tin, and iron. In some embodiments, the glass-based substrate contains less than one platinum ball-chain defect per pound (approximately 0.45 kg), e.g., the glass-based substrate is substantially free of or free of platinum ball-chain defects.

[0096] In some embodiments, the glass-based substrate can have a Young's modulus of 50 GPa or greater. In embodiments, the glass-based substrate can have a Young's modulus of 51 GPa or greater, such as 52 GPa or greater, 53 GPa or greater, 54 GPa or greater, 55 GPa or greater, 56 GPa or greater, 57 GPa or greater, 58 GPa or greater, 59 GPa or greater, 60 GPa or greater, 61 GPa or greater, 62 GPa or greater, 63 GPa or greater, 64 GPa or greater, 65 GPa or greater, or greater than 65 GPa. In embodiments, the glass-based substrate can have a Young's modulus in the range of 50 GPa to 70 GPa, for example, 51 GPa to 69 GPa, 52 GPa to 68 GPa, 53 GPa to 67 GPa, 54 GPa to 66 GPa, 55 GPa to 65 GPa, 56 GPa to 64 GPa, 57 GPa to 63 GPa, 58 GPa to 62 GPa, 59 GPa to 61 GPa, 59 GPa to 60 GPa, or any and all subranges formed by the endpoints of these ranges.

[0097] In some embodiments, the glass-based substrate can have a 200P temperature of 1725° C. or less, such as 1720° C. or less, 1715° C. or less, 1710° C. or less, 1705° C. or less, 1700° C. or less, 1695° C. or less, 1690° C. or less, 1685° C. or less, 1680° C. or less, 1675° C. or less, 1670° C. or less, 1665° C. or less, 1660° C. or less, 1655° C. or less, 1650° C. or less, 1645° C. or less, 1640° C. or less, 1635° C. or less, 1630° C. or less, 1625° C. or less, 1620° C. or less, 1615° C. or less, 1610° C. or less, 1605° C. or less, 1600° C. or less, or less than 1600° C. A lower 200P temperature improves the meltability and, therefore, manufacturability of the glass-based substrate composition.

[0098] In some embodiments, the glass-based substrate can have a liquidus viscosity of 10 kP or greater, such as 100 kP or greater, 1000 kP or greater, or greater than 1000 kP. Increasing the Li2O content in the glass-based substrate reduces the liquidus viscosity of the glass-based substrate composition. Maintaining the liquidus viscosity of the glass-based substrate above about 10 kP allows for the production of glass-based substrates on a variety of manufacturing platforms, including fusion molding platforms. To ensure compatibility with fusion molding, a liquidus viscosity of 100 kP or greater is particularly preferred. If the liquidus viscosity is too low, the manufacturability of the glass-based substrate is impaired.

[0099] In some embodiments, the glass-based substrate can have a zircon breakdown viscosity of 35 kP or less, such as 30 kP or less, 25 kP or less, 20 kP or less, 19 kP or less, 18 kP or less, 17 kP or less, 16 kP or less, 15 kP or less, 14 kP or less, 13 kP or less, 12 kP or less, 11 kP or less, 10 kP or less, 9 kP or less, 8 kP or less, 7 kP or less, 6 kP or less, 5 kP or less, 4 kP or less, 3 kP or less, 2 kP or less, 1 kP or less, or less than 1 kP. The zircon breakdown viscosity is the viscosity of the glass at the zircon decomposition temperature. Maintaining the zircon breakdown viscosity in the 35 kP or less range can make the composition compatible with fusion molding processes using zircon-containing elements, such as zircon isopipes.

[0100] The glass-based substrate can have any suitable shape. In some embodiments, the glass-based substrate can have a thickness of 2.0 mm or less, for example, 1.9 mm or less, 1.8 mm or less, 1.7 mm or less, 1.6 mm or less, 1.5 mm or less, 1.4 mm or less, 1.3 mm or less, 1.2 mm or less, 1.1 mm or less, 1 mm or less, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, or less than 300 μm. In some embodiments, the glass-based substrate can have a thickness of 300 μm to 2 mm, for example, 400 μm to 1.9 mm, 500 μm to 1.8 mm, 600 μm to 1.7 mm, 700 μm to 1.6 mm, 800 μm to 1.5 mm, 900 μm to 1.4 mm, 1 mm to 1.3 mm, 1.1 mm to 1.2 mm, or any subrange formed by the endpoints of these ranges. In some embodiments, the glass-based substrate can have a plate-like or sheet-like shape. In some other embodiments, the glass-based substrate can have a 2.5-dimensional or three-dimensional shape. As used herein, "2.5D shape" refers to a sheet-like article in which at least a portion of at least one major surface is non-planar and the second major surface is substantially planar. As used herein, the term "3D shape" refers to an article having opposing first and second major surfaces, at least a portion of which is non-planar. The glass-based article can have substantially similar or identical dimensions and shape to the original glass-based substrate.

[0101] The glass-based substrate can be formed by any suitable method, such as slot forming, float forming, rolling process, fusion forming process, etc. The glass-based substrate of the present invention and the glass-based articles produced from the glass-based substrate can be characterized by their forming method. For example, the glass-based substrate can be characterized as float-formable (i.e., formed by a float process), down-drawable, particularly fusion-formable, or slot-drawable (i.e., formed by a down-draw process such as a fusion draw process or a slot draw process).

[0102] Some embodiments of the glass-based substrates described herein can be formed by a down-draw process. Glass-based substrates produced by a down-draw process have uniform thickness and relatively clean surfaces. Because the average bending strength of a glass-based substrate is determined by the amount and size of surface defects, clean surfaces with minimal contact provide higher initial strength. Additionally, glass-based substrates produced by down-draw have very flat and smooth surfaces, allowing them to be used in their final application without costly grinding or polishing.

[0103] Some embodiments of glass-based substrates may also be described as fusion-formable (i.e., formable by a fusion draw process). The fusion draw process employs a drawing vessel having a channel for receiving molten glass frit material. Open-topped weirs are provided on either side of the channel along the length of the channel. When the channel is filled with molten material, the molten glass overflows the weirs. Gravity then causes the molten glass to flow down the exterior surfaces of the drawing vessel in two glass film streams. These vessel exteriors extend downward and inward, meeting at the lower edge of the vessel. The two glass film streams meet at this edge and fuse together to form a single glass article stream. This fusion of the glass films forms a fusion line in the glass-based substrate, which allows a fusion-formed glass-based substrate to be identified as having been fusion-formed without the need for a separate verification of its manufacturing history. The fusion draw process fuses two glass films flowing through a flow channel, which has the advantage that the outer surface of the resulting glass article does not come into contact with any part of the equipment, and therefore the surface properties of the glass article produced by the fusion draw process are not affected by such contact.

[0104] The compositions of the glass-based substrates described herein are specifically selected to be compatible with the fusion molding process. This compatibility depends on the liquidus viscosity and zircon decomposition viscosity of the glass-based substrate composition. In embodiments, the glass-based substrate has a liquidus viscosity of 100 kP or greater and a zircon decomposition viscosity of 35 kP or less.

[0105] Some embodiments of the glass-based substrates described herein can be formed by a slot-draw process. The slot-draw process is a distinct process from the fusion draw method. In the slot-draw process, molten raw glass is fed into a drawing vessel. The drawing vessel has an opening with a nozzle at the bottom that extends the entire length of the opening. The molten glass flows through the slot (nozzle) and is drawn downward into a continuous glass-based substrate that is then delivered to an annealing area.

[0106] The glass-based article can be produced by exposing the glass-based substrate to water vapor under any suitable conditions. The exposure can be carried out in any suitable device, such as a furnace with controlled relative humidity. The exposure can also be carried out at high pressure, for example, in a furnace or autoclave with controlled relative humidity and pressure.

[0107] In some embodiments, glass-based articles can be produced by exposing a glass-based substrate to a water vapor-containing environment at a pressure greater than ambient pressure. The exposure environment can have a pressure greater than 0.1 MPa and a water partial pressure of 0.05 MPa or greater, e.g., 0.075 MPa or greater. Increasing the pressure of the exposure environment can increase the water vapor concentration in the exposure environment, particularly when the temperature is increased. For a constant volume, such as inside a furnace or autoclave, increasing the temperature reduces the amount of water available to diffuse into the glass-based substrate and form the glass-based article. Thus, while increasing the temperature of the water vapor treatment environment may increase the rate of diffusion of hydrogen species into the glass-based substrate, if the pressure remains constant, the compressive stress decreases due to the decrease in total water vapor concentration and stress relaxation at high temperatures. Thus, when the temperature of the exposure environment is increased, e.g., to a high temperature above atmospheric pressure saturation conditions, increasing the pressure until saturation conditions are reached significantly increases the water vapor concentration in the exposure environment.

[0108] The water vapor saturation condition at atmospheric pressure (0.1 MPa) is 99.61°C. In a fixed volume environment, such as the interior of a furnace or autoclave, increasing the temperature reduces the amount of water that can diffuse into the glass-based substrate and be used to form the glass-based article. Thus, increasing the temperature of the water vapor treatment environment may increase the rate of diffusion of hydrogen species into the glass-based substrate, but may also reduce the effectiveness of the treatment.

[0109] Therefore, when the temperature rises to a high temperature, for example, exceeding the atmospheric pressure saturation condition, increasing the pressure of the exposure environment until the saturation condition is reached significantly increases the water vapor concentration in the exposure environment. Figure 3 shows the water vapor saturation condition as a function of pressure and temperature. As shown in Figure 3, the area above the curve is an undesirable area where water vapor condenses and liquefies. Therefore, the water vapor treatment conditions used herein can be preferably located on or below the curve in Figure 3, and more preferably located on or just below the curve to maximize the water vapor content. For the above reasons, water vapor treatment of glass-based substrates can be performed at elevated pressures.

[0110] Glass-based articles manufactured under high temperature and pressure conditions have been found to have a hazy appearance. The hazy appearance correlates with the concentration of hydrogen species incorporated into the glass-based article, with the concentration of hydrogen species increasing with increasing temperature and pressure. The occurrence of haze during moisture treatment processes can be addressed by employing the lithium-containing compositions described herein or by selecting treatment conditions to control the amount of hydrogen species incorporated into the glass-based article. For example, at high temperatures, treatment pressures below saturation pressure can be used to reduce the concentration of hydrogen species in the glass-based article. The concentration of hydrogen species can be reduced by reducing the total amount of hydrogen species diffused into the glass-based article, and this reduction can be confirmed by a reduced mass gain during steam treatment or an increased depth of layer for the same mass gain. Haze mitigation strategies can be achieved by combining compositions and treatment conditions.

[0111] In some embodiments, the lithium-containing glass-based substrates described herein can be exposed to water vapor treatment in a saturated steam environment at temperatures of 85° C. or greater. The lithium-containing glass-based substrates can be processed at higher temperatures and pressures over a wider process window without developing haze, allowing for shorter processing times and more efficient tempering processes. Glass-based articles produced using the haze mitigation strategies described above have a substantially haze-free or haze-free appearance.

[0112] In some embodiments, the glass-based substrate can be exposed to an environment of pressure of 0.1 MPa or greater, for example, 0.2 MPa or greater, 0.3 MPa or greater, 0.4 MPa or greater, 0.5 MPa or greater, 0.6 MPa or greater, 0.7 MPa or greater, 0.8 MPa or greater, 0.9 MPa or greater, 1.0 MPa or greater, 1.1 MPa or greater, 1.2 MPa or greater, 1.3 MPa or greater, 1.4 MPa or greater, 1.5 MPa or greater, 1.6 MPa or greater, 1.7 MPa or greater, 1.8 MPa or greater, 1.9 MPa or greater, 2.0 MPa or greater, 2.1 MPa or greater, 2.2 MPa or greater, 2.3 MPa or greater, 2.4 MPa or greater, 2.5 MPa or greater, 2.6 MPa or greater, 2.7 MPa or greater, 2.8 MPa or greater, 2.9 MPa or greater, 3. The pressure may be 0 MPa or more, 3.1 MPa or more, 3.2 MPa or more, 3.3 MPa or more, 3.4 MPa or more, 3.5 MPa or more, 3.6 MPa or more, 3.7 MPa or more, 3.8 MPa or more, 3.9 MPa or more, 4.0 MPa or more, 4.1 MPa or more, 4.2 MPa or more, 4.3 MPa or more, 4.4 MPa or more, 4.5 MPa or more, 4.6 MPa or more, 4.7 MPa or more, 4.8 MPa or more, 4.9 MPa or more, 5.0 MPa or more, 5.1 MPa or more, 5.2 MPa or more, 5.3 MPa or more, 5.4 MPa or more, 5.5 MPa or more, 5.6 MPa or more, 5.7 MPa or more, 5.8 MPa or more, 5.9 MPa or more, 6.0 MPa or more, or greater than 6.0 MPa.In some embodiments, the glass-based substrate can be exposed to an environment with a pressure of 0.1 MPa to 25 MPa, for example, 0.2 MPa to 24 MPa, 0.3 MPa to 23 MPa, 0.4 MPa to 22 MPa, 0.5 MPa to 21 MPa, 0.6 MPa to 20 MPa, 0.7 MPa to 19 MPa, 0.8 MPa to 18 MPa, 0.9 MPa to 17 MPa, 1.0 MPa to 16 MPa, 1.1 MPa or less than 15MPa, 1.2MPa or more than 14MPa, 1.3MPa or more than 13MPa, 1.4MPa or more than 12MPa, 1.5MPa or more than 11MPa, 1.6MPa or more than 10MPa, 1.7MPa or more than 9MPa, 1.8MPa or more than 8MPa, 1.9MPa or more than 7MPa, 1.9MPa or more than 6.9MPa, 2.0MPa or more than 6.8MPa, 2.1MPa or more than 6.7MPa, 2.2MPa or more than 6.6MPa, 2.3M Pa or more and 6.5MPa or less, 2.4MPa or more and 6.4MPa or less, 2.5MPa or more and 6.3MPa or less, 2.6MPa or more and 6.2MPa or less, 2.7MPa or more and 6.1MPa or less, 2.8MPa or more and 6.0MPa or less, 2.9MPa a or more and 5.9MPa or less, 3.0MPa or more and 5.8MPa or less, 3.1MPa or more and 5.7MPa or less, 3.2MPa or more and 5.6MPa or less, 3.3MPa or more and 5.5MPa or less, 3.4MPa or more and 5.4MPa or less, 3.5MPa or more In some embodiments, the glass-based substrate may be exposed to an environment of pressure ranging from 0.1 MPa to 5.3 MPa, from 3.6 MPa to 5.2 MPa, from 3.7 MPa to 5.1 MPa, from 3.8 MPa to 5.0 MPa, from 3.9 MPa to 4.9 MPa, from 4.0 MPa to 4.8 MPa, from 4.1 MPa to 4.7 MPa, from 4.2 MPa to 4.6 MPa, from 4.3 MPa to 4.5 MPa, 4.4 MPa, or any and all subranges formed by any endpoint of these ranges. In some embodiments, the glass-based substrate may be exposed to an environment of ambient pressure, such as 0.1 MPa.

[0113] In some embodiments, the glass-based substrate can be exposed to an environment having a water partial pressure of 0.05 MPa or greater, for example, 0.075 MPa or greater, 0.1 MPa or greater, 0.2 MPa or greater, 0.3 MPa or greater, 0.4 MPa or greater, 0.5 MPa or greater, 0.6 MPa or greater, 0.7 MPa or greater, 0.8 MPa or greater, 0.9 MPa or greater, 1.0 MPa or greater, 1.1 MPa or greater, 1.2 MPa or greater, 1.3 MPa or greater, 1.4 MPa or greater, 1.5 MPa or greater Above, 1.6MPa or more, 1.7MPa or more, 1.8MPa or more, 1.9MPa or more, 2.0MPa or more, 2.1MPa or more, 2.2MPa or more, 2.3MPa or more, 2.4MPa or more, 2.5MPa or more, 2.6MPa or more, 2.7MPa or more, 2.8MPa or more, 2.9MPa or more, 3.0MPa or more, 3.1MPa or more, 3.2MPa or more, 3.3MPa or more, 3.4MPa or more, 3.5MPa or more, 3.6MPa or more, 3.7MPa or more , 3.8MPa or more, 3.9MPa or more, 4.0MPa or more, 4.1MPa or more, 4.2MPa or more, 4.3MPa or more, 4.4MPa or more, 4.5MPa or more, 4.6MPa or more, 4.7MPa or more, 4.8MPa or more, 4.9MPa or more, 5.0MPa or more, 5.1MPa or more, 5.2MPa or more, 5.3MPa or more, 5.4MPa or more, 5.5MPa or more, 5.6MPa or more, 5.7MPa or more, 5.8MPa or more, 5.9MPa or more, It can be exposed to an environment having a water partial pressure of 6.0 MPa or greater, 7.0 MPa or greater, 8.0 MPa or greater, 9.0 MPa or greater, 10.0 MPa or greater, 11.0 MPa or greater, 12.0 MPa or greater, 13.0 MPa or greater, 14.0 MPa or greater, 15.0 MPa or greater, 16.0 MPa or greater, 17.0 MPa or greater, 18.0 MPa or greater, 19.0 MPa or greater, 20.0 MPa or greater, 21.0 MPa or greater, 22.0 MPa or greater, or greater than 22.0 MPa.In some embodiments, the glass-based substrate can be exposed to an environment having a water partial pressure of 0.05 MPa or more and 22 MPa or less, for example, 0.075 MPa or more and 22 MPa or less, 0.1 MPa or more and 21 MPa or less, 0.2 MPa or more and 20 MPa or less, 0.3 MPa or more and 19 MPa or less, 0.4 MPa or more and 18 MPa or less, 0.5 MPa or more and 17 MPa or less, 0.6 MPa or more and 16 MPa or less, 0.7 MPa or more and 15 MPa or less, 0.8 MPa or more and 14 MPa or less, 0.9MPa to 13MPa, 1.0MPa to 12MPa, 1.1MPa to 11MPa, 1.2MPa to 10MPa, 1.3MPa to 9MPa, 1.4MPa to 8MPa, 1.5MPa to 7M Pa or less, 1.6 MPa or more and 6.9 MPa or less, 1.7 MPa or more and 6.8 MPa or less, 1.8 MPa or more and 6.7 MPa or less, 1.9 MPa or more and 6.6 MPa or less, 2.0 MPa or more and 6.5 MPa or less, 2.1 MPa or more and 6.4 MPa or less 2.2MPa or more and 6.3MPa or less, 2.3MPa or more and 6.2MPa or less, 2.4MPa or more and 6.1MPa or less, 2.5MPa or more and 6.0MPa or less, 2.6MPa or more and 5.9MPa or less, 2.7MPa or more and 5.8MPa or less, 2.8MPa or more and 5.7MPa or less, 2.9MPa or more and 5.6MPa or less, 3.0MPa or more and 5.5MPa or less, 3.1MPa or more and 5.4MPa or less, 3.2MPa or more and 5.3MPa or less, 3.3MPa or more and 5.2MPa or less, 3.4MPa or more and 5.5 ... The material may be exposed to an environment having a water partial pressure of from 3.5 MPa to 5.0 MPa, from 3.6 MPa to 4.9 MPa, from 3.7 MPa to 4.8 MPa, from 3.8 MPa to 4.7 MPa, from 3.9 MPa to 4.6 MPa, from 4.0 MPa to 4.5 MPa, from 4.1 MPa to 4.4 MPa, from 4.2 MPa to 4.3 MPa, or any and all subranges formed by any endpoint of these ranges.

[0114] In some embodiments, the glass-based substrate can be exposed to an environment having a relative humidity of 10% or greater, such as 25% or greater, 50% or greater, 75% or greater, 80% or greater, 85% or greater, 90% or greater, 95% or greater, 99% or greater, or greater than 99%. In some embodiments, the glass-based substrate can be exposed to an environment having a relative humidity of 100%. In some embodiments, the exposure environment can be a saturated steam environment.

[0115] In some embodiments, the glass-based substrate can be exposed to an environment having a temperature of 85°C or greater, for example, 90°C or greater, 100°C or greater, 110°C or greater, 120°C or greater, 130°C or greater, 140°C or greater, 150°C or greater, 160°C or greater, 170°C or greater, 180°C or greater, 190°C or greater, 200°C or greater, 210°C or greater, 220°C or greater, 230°C or greater, 240°C or greater, 250°C or greater, 260°C or greater, 270°C or greater, 280°C or greater, 290°C or greater, 300°C or greater, 310°C or greater, 320°C or greater, 330°C or greater, 340°C or greater, 350°C or greater, 360°C or greater, 370°C or greater, 380°C or greater, 390°C or greater, 400°C or greater, or greater than 400°C. In some embodiments, the glass-based substrate can be exposed to an environment having a temperature of 85°C or higher and 400°C or lower, for example, 100°C or higher and 390°C or lower, 110°C or higher and 380°C or lower, 115°C or higher and 370°C or lower, 120°C or higher and 360°C or lower, 125°C or higher and 350°C or lower, 130°C or higher and 340°C or lower, 135°C or higher and 330°C or lower, 140°C or higher and 320°C or lower, 145°C or higher and 310°C or lower, 150°C or higher and 300°C or lower, 155°C or higher and 295°C or lower, 160°C or higher and 290°C or lower, 165 ... The material may be exposed to an environment having a temperature of 85°C or less, 170°C or more and 280°C or less, 175°C or more and 275°C or less, 180°C or more and 270°C or less, 185°C or more and 265°C or less, 190°C or more and 260°C or less, 195°C or more and 255°C or less, 200°C or more and 250°C or less, 205°C or more and 245°C or less, 210°C or more and 240°C or less, 215°C or more and 235°C or less, 220°C or more and 230°C or less, 220°C or more and 225°C or less, or any and all subranges formed by any endpoint of these ranges.

[0116] In some embodiments, the glass-based substrate can be exposed to a water vapor-containing environment for a time sufficient to cause the glass-based substrate to undergo a desired degree of diffusion of hydrogen-containing species to produce a desired compressive stress layer. In some embodiments, the glass-based substrate can be exposed to the water vapor-containing environment for 2 hours or more, for example, 4 hours or more, 6 hours or more, 8 hours or more, 10 hours or more, 12 hours or more, 14 hours or more, 16 hours or more, 18 hours or more, 20 hours or more, 22 hours or more, 24 hours or more, 30 hours or more, 36 hours or more, 42 hours or more, 48 hours or more, 54 hours or more, 60 hours or more, 66 hours or more, 72 hours or more, 78 hours or more, 84 hours or more, 90 hours or more, 96 hours or more, 102 hours or more, 108 hours or more, 114 hours or more, 120 hours or more, 126 hours or more, 132 hours or more, 138 hours or more, 144 hours or more, 150 hours or more, 156 hours or more, 162 hours or more, 168 hours or more, or more than 168 hours. In some embodiments, the glass-based substrate can be exposed to the water vapor-containing environment for a period of from 2 hours to 10 days, for example, from 4 hours to 9 days, from 6 hours to 8 days, from 8 hours to 168 hours, from 10 hours to 162 hours, from 12 hours to 156 hours, from 14 hours to 150 hours, from 16 hours to 144 hours, from 18 hours to 138 hours, from 20 hours to 132 hours, from 22 hours to 126 hours, from 24 hours to 120 hours, from 30 hours to 114 hours, from 36 hours to 108 hours, from 42 hours to 102 hours, from 48 hours to 96 hours, from 54 hours to 90 hours, from 60 hours to 84 hours, from 66 hours to 78 hours, 72 hours, or any and all subranges formed from any endpoint of these ranges.

[0117] In some embodiments, a glass-based substrate can be exposed to multiple water vapor-containing environments. In some embodiments, the glass-based substrate can be exposed to a first environment to form a first glass-based article. The first glass-based article has a first compressive stress layer extending from a surface of the first glass-based article to a first compressed depth. The first glass-based article can then be exposed to a second environment to form a second glass-based article. The second glass-based article has a second compressive stress layer extending from a surface of the second glass-based article to a second compressed depth. The first environment has a first water partial pressure and a first temperature, and the glass-based substrate is exposed to the first environment for a first period of time. The second environment has a second water partial pressure and a second temperature, and the first glass-based article is exposed to the second environment for a second period of time.

[0118] The first and second water partial pressures can be any suitable partial pressure, such as 0.05 MPa or greater or 0.075 MPa or greater. The first and second water partial pressures can be any of the values ​​disclosed herein for water partial pressures employed in the processing methods. In some embodiments, the first and second environments can independently have a relative humidity of 10% or greater, such as 25% or greater, 50% or greater, 75% or greater, 80% or greater, 90% or greater, 95% or greater, or a relative humidity equal to 100%. In some embodiments, at least one of the first and second environments has a relative humidity of 100%. In some embodiments, the first and second environments can independently be saturated steam environments.

[0119] The first compressive stress layer has a first maximum compressive stress, and the second compressive stress layer has a second maximum compressive stress. In embodiments, the first maximum compressive stress is less than the second maximum compressive stress. The second maximum compressive stress may be comparable to a compressive stress "spike" of the type formed by multi-stage ion exchange or mixed bath ion exchange techniques. The first maximum compressive stress and the second maximum compressive stress may have any of the values ​​disclosed herein for compressive stress of glass-based articles. In embodiments, the second maximum compressive stress may be 50 MPa or greater.

[0120] The first compression depth can be equal to or less than the second compression depth. In some embodiments, the first compression depth is less than the second compression depth. The first compression depth and the second compression depth can have any of the values ​​disclosed herein for compression depth. In some embodiments, the second compression depth is greater than 5 μm.

[0121] The first temperature can be equal to or greater than the second temperature. In some embodiments, the first temperature is greater than the second temperature. The first and second temperatures can be any of the temperatures disclosed in connection with the processing methods.

[0122] The first period of time can be less than or equal to the second period of time. In some embodiments, the first period of time is less than the second period of time. The first period of time and the second period of time can be any of the periods of time disclosed in connection with the high-pressure processing method.

[0123] In some embodiments, any or all of the multiple exposures to water vapor-containing environments can be performed at elevated pressures. For example, at least one of the first and second environments can have a pressure greater than 0.1 MPa. The first and second environments can have any of the pressures disclosed in connection with the processing methods.

[0124] In some embodiments, three or more exposure environments can be used in the multiple water vapor environment exposure method. In several embodiments, a second glass-based article can be exposed to a third environment to form a third glass-based article. The third environment has a third water partial pressure and a third temperature, and the second glass-based article is exposed to the third environment for a third period of time. The third glass-based article has a third compressive stress layer extending from the surface of the third glass-based article to a third compression depth and having a third maximum compressive stress. The third water partial pressure can be 0.05 MPa or greater or 0.075 MPa or greater. Values ​​of any properties of the third environment and the third glass-based article can be selected from the corresponding property values ​​disclosed in connection with the high-pressure processing method.

[0125] In some embodiments, the first glass-based article can be cooled to ambient temperature or otherwise removed from the first environment after the first period of time and before exposure to the second environment. In some embodiments, the first environmental condition can be changed to the second environmental condition after the first period of time has expired, without the first glass-based article being cooled to ambient temperature or removed from the water vapor-containing environment, while the first glass-based article remains in the first environment.

[0126] The methods for manufacturing glass-based articles disclosed herein do not require an ion exchange treatment using an alkali ion source. In several embodiments, the glass-based articles are manufactured by a method that does not include ion exchange with an alkali ion source. In other words, in some embodiments, the glass-based substrate and glass-based article are not subjected to an ion exchange treatment using an alkali ion source.

[0127] The exposure conditions can also be modified to decrease the time required to diffuse a desired amount of hydrogen-containing species into the glass-based substrate, for example, by increasing the temperature or relative humidity to decrease the time required for the desired degree and depth of diffusion of the hydrogen-containing species into the glass-based substrate.

[0128] The methods and glass-based substrate compositions disclosed herein allow for the production of glass-based articles that have a substantially haze-free or haze-free appearance.

[0129] Illustrative Embodiments Glass-based substrates were formed from glass compositions particularly suited for forming the glass-based articles described herein. The glass compositions are shown in Table 1 below (Examples A-V). The density of the glass compositions was measured using the buoyancy method of ASTM Standard C693-93 (2013). The strain point and annealing point were measured using the beam bending viscosity method of ASTM Standard C598-93 (2013). The Young's modulus values ​​were measured using the general-purpose resonant ultrasonic spectroscopy method described in ASTM Standard E2001-13, "Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts." The stress-optical coefficient (SOC) was measured according to Procedure C (glass disk method) described in ASTM Standard C770-16, "Standard Test Method for Measurement of Glass Stress-Optical Coefficient." The refractive index was measured at a wavelength of 589.3 nm. The liquidus temperature was measured in accordance with ASTM standard C829-81 (2015) "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method." The liquidus viscosity was calculated from the measured liquidus temperature (T) using the following formula: log 10 η=A+B / (T-T0) where η is the viscosity, and A, B, and T0 were determined by fitting from high-temperature viscosity (HTV) measurements. High-temperature viscosity was measured using a rotational viscometer according to ASTM standard C965-96 (2012), "Standard Practice for Measuring Viscosity of Glass Above the Softening Point." The zircon decomposition temperature was measured similarly to the liquidus temperature by placing refractory zircon chips in a Pt / Rh boat surrounded by glass debris. After 72 hours of testing, the test slabs were observed under polarized light, reflected light, and scanning electron microscopes to detect secondary zirconia and determine the temperature at which zirconia formed. The zircon decomposition viscosity was determined from the measured zircon decomposition temperature, as with the liquidus viscosity described above.

[0130] [Table 1-1]

[0131] [Table 1-2]

[0132] [Table 1-3]

[0133] Samples (Examples A to T) having the compositions shown in Table 1 were exposed to a water vapor-containing environment to form glass articles with compressive stress layers. The samples were exposed to steam treatment at a pressure of 1.6 MPa and a temperature of 200°C for 16 hours. The exposure environment was saturated. The maximum compressive stress and compression depth obtained were measured using a surface stress meter (FSM). The results are shown in Table 2. When the stress optical coefficient (SOC) and refractive index (RI) could not be obtained, the measurements were performed using their default values ​​of 3.0 nm / mm / MPa and 1.5, respectively. The depth of the hydrogen-containing layer of the treated article was equal to or greater than the measured compression depth (DOC).

[0134] [Table 2]

[0135] Samples (Examples G to T) having the compositions shown in Table 1 were exposed to a water vapor-containing environment to form glass articles with compressive stress layers. The samples were exposed to the steam treatment at a pressure of 2.6 MPa and a temperature of 225°C for 16 hours. The exposure environment was saturated. The maximum compressive stress and compression depth obtained were measured using a surface stress meter (FSM). The results are shown in Table 3. When the stress optical coefficient (SOC) and refractive index (RI) could not be obtained, the measurements were performed using their default values ​​of 3.0 nm / mm / MPa and 1.5, respectively. The depth of the hydrogen-containing layer of the treated article was equal to or greater than the measured compression depth (DOC).

[0136] [Table 3]

[0137] Samples (Examples D to T) having the compositions shown in Table 1 were exposed to a water vapor-containing environment to form glass articles with compressive stress layers. The samples were exposed to steam treatment at a pressure of 0.76 MPa and a temperature of 175°C for 96 hours. The maximum compressive stress and compression depth obtained were measured using a surface stress meter (FSM). The results are shown in Table 4. When the stress optical coefficient (SOC) and refractive index (RI) could not be obtained, the measurements were performed using their default values ​​of 3.0 nm / mm / MPa and 1.5, respectively. The depth of the hydrogen-containing layer of the treated article was equal to or greater than the measured compression depth (DOC).

[0138] [Table 4]

[0139] Samples (Examples A to T) having the compositions shown in Table 1 were exposed to a water vapor-containing environment to form glass articles with compressive stress layers. The samples were exposed to steam treatment at a pressure of 0.1 MPa and a temperature of 300°C for 16 hours. The maximum compressive stress and compression depth obtained were measured using a surface stress meter (FSM), and the results are shown in Table 5. When the stress optical coefficient (SOC) and refractive index (RI) could not be obtained, the measurements were performed using their default values ​​of 3.0 nm / mm / MPa and 1.5, respectively. The depth of the hydrogen-containing layer of the treated article was equal to or greater than the measured compression depth (DOC).

[0140] [Table 5]

[0141] Comparative examples were prepared with the compositions shown in Table 6 (Comparative Examples 1 to 5). The comparative examples were produced in a glass melter, and the composition of the glass melt was gradually changed to achieve the desired composition. Significant amounts of bead-chain platinum defects were observed in all comparative compositions except for Comparative Example 4. Comparative Example 4 did not contain enough phosphorus to achieve the desired hydrogen species diffusivity, and due to the insufficient phosphorus content, it was found to lack compatibility with the zircon device in terms of fusion molding viscosity. Furthermore, all of these comparative glass compositions had an R2O / Al2O3 ratio greater than 1.4, and all except Comparative Example 4 had a (R2O + P2O5) / Al2O3 ratio greater than 1.9.

[0142] [Table 6]

[0143] Figure 4 shows the number of platinum bead-chain defects measured (per pound) as a function of phosphorus (P2O5) content. As shown in Figure 4, glass with a P2O5 content greater than approximately 6 mole percent contains the platinum bead-chain defects of interest. Measurements of platinum bead-chain defects were performed on glass pieces measuring 12 cm wide, 50 cm long, and 0.4 cm thick, weighing approximately 1.25 pounds (0.57 kg). The observed number of defects was then normalized by the mass of the glass being inspected to determine the number of platinum bead-chain defects per pound (approximately 0.45 kg), as shown in the table. Figure 5 shows the platinum bead-chain defects detected at 10x magnification.

[0144] Further, additional comparative examples were prepared with the compositions shown in Table 7 (Comparative Examples 6A to 6F). The comparative examples were produced in a glass melter, and the composition of the glass melt was gradually changed to achieve the desired composition. All of these comparative compositions exhibited a significant amount of phase separation. It was also confirmed that all of these comparative glass compositions had an R2O / Al2O3 ratio greater than 1.4 and a (R2O + P2O5) / Al2O3 ratio greater than 1.9.

[0145] [Table 7]

[0146] FIG. 6A is a plot of diffuse scattering transmittance (%) versus wavelength (i.e., 300 nm to 850 nm) for a glass composition of the present invention (Example V) and comparative glass compositions (Comparative Examples 6A to 6F) in Table 1. FIG. 6B is a plot of scattering ratio (%) versus wavelength for the same glass compositions. Measurements shown in FIGS. 6A and 6B were performed using 1 mm thick samples with an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer equipped with an integrating sphere or standard axial detector. While FIGS. 6A and 6B show data using light wavelengths from 300 nm to 850 nm, data was also analyzed in more common visible wavelength ranges, such as 380 to 780 nm and 400 to 700 nm. Furthermore, the diffuse scattering transmittance (%) data shown in FIG. 6A was generated by a spectrophotometer. For the scattering ratio (%) shown in FIG. 6B, the diffuse transmittance shown in FIG. 6A was calculated using Tdiffuse , the total transmittance of the sample is T total In this case, (T diffuse (%) / T total The value given by (%) × 100. Regarding the data shown in Figures 6A and 6B, it can be seen that the comparative glass compositions (Comparative Examples 6A-6F) that exhibit phase separation have scattering ratios and diffuse transmittances at 300 nm that are significantly greater than 0.2%, while the glass composition of the present invention (Example V) has scattering ratios and diffuse transmittances at 300 nm that are below 0.2%. Thus, the scattering ratio and diffuse transmittance measurements can be used to quantify the extent of phase separation in glass compositions of the present disclosure. Without being bound by theory, it is believed that the phase separation threshold also varies from 0.2% for samples having thicknesses different from 1 mm.

[0147] 7A and 7B, which show scanning electron microscope (SEM) images of two comparative glass compositions exhibiting phase separation: FIG. 7A shows an image of Comparative Example 6B, and FIG. 7B shows an image of Comparative Example 6C (see also Table 7 above). These images were taken using a Zeiss Gemini SEM 450 at 2 kV and a maximum magnification of 100 kx after cross-sectioning the comparative samples and depositing a conductive carbon coating on the cross-section. As evident from these SEM images, the comparative glass compositions exhibit secondary phases ranging from approximately 10 to 40 nm.

[0148] While exemplary embodiments have been described for purposes of illustration, the above description should not be deemed to limit the scope of this disclosure or the appended claims. Accordingly, it is anticipated that those skilled in the art will make various changes, modifications, and alternatives without departing from the spirit and scope of this disclosure or the appended claims.

[0149] Preferred embodiments of the present invention will be described below in detail.

[0150] Embodiment 1 A glass-based article, a compressive stress layer extending from the surface of the glass-based article to a compression depth; a hydrogen-containing layer extending from the surface to a layer depth of the glass-based article; a composition of the center portion of the glass-based article, The composition comprises: SiO2 and Al2O3 and K2O and When the total amount of monovalent metal oxides is R2O, R2O / Al2O3 is 1.4 or less, and 3.5 mol% or more and 6.0 mol% or less of P2O5, 2.0 mol% or more and 5.0 mol% or less of LiO, the compressive stress layer has a compressive stress of 25 MPa or more, the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth; The glass-based article, wherein the depth of layer is greater than 5 μm.

[0151] Embodiment 2 10. The glass-based article of embodiment 1, further comprising a fusion line.

[0152] Embodiment 3 3. The glass-based article of claim 1 or 2, wherein the glass-based article contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0153] Embodiment 4 3. The glass-based article of claim 1 or 2, wherein the glass-based article does not exhibit substantially phase separation.

[0154] Embodiment 5 5. The glass-based article of any one of embodiments 1 to 4, wherein the composition of the center portion of the glass-based article further comprises B2O3.

[0155] Embodiment 6 6. The glass-based article of any one of claims 1 to 5, wherein the composition of the center portion of the glass-based article further comprises Na2O.

[0156] Embodiment 7 7. The glass-based article of any one of claims 1 to 6, wherein the composition of the center portion of the glass-based article further comprises SnO2.

[0157] Embodiment 8 8. The glass-based article of any one of embodiments 1 to 7, wherein the composition at the center of the glass-based article has an average alkali modifier field strength of 0.18 or less.

[0158] Embodiment 9 The composition of the center portion of the glass-based article is 55.0 mol% or more and 65.0 mol% or less of SiO2; 10.0 mol% or more and 15.0 mol% or less of Al2O3, 0 mol% or more and 10.0 mol% or less of B2O3, 6.0 mol% or more and 15.0 mol% or less of K2O; 9. The glass-based article according to any one of embodiments 1 to 8, comprising:

[0159] Embodiment 10 10. The glass-based article according to any one of embodiments 1 to 9, wherein the composition of the center portion of the glass-based article comprises 4.5 mol % or more and 5.5 mol % or less of P2O5.

[0160] Embodiment 11 11. The glass-based article of any one of claims 1 to 10, wherein the composition of the center portion of the glass-based article comprises greater than 0 mol% and less than or equal to 3.0 mol% B2O3.

[0161] Embodiment 12 12. The glass-based article according to any one of embodiments 1 to 11, wherein a glass having the same composition as the composition of the central portion of the glass-based article has a zircon decomposition viscosity of 35 kP or less.

[0162] Embodiment 13 13. The glass-based article according to any one of embodiments 1 to 12, wherein a liquidus viscosity of glass having the same composition as the composition of the central portion of the glass-based article is 100 kP or more.

[0163] Embodiment 14 14. The glass-based article of any one of embodiments 1 to 13, wherein the glass-based article has a substantially haze-free appearance.

[0164] Embodiment 15 15. The glass-based article of any one of embodiments 1-14, wherein the compression depth is greater than 5 μm.

[0165] Embodiment 16 16. The glass-based article according to any one of embodiments 1 to 15, wherein the compressive stress layer has a compressive stress of 200 MPa or more.

[0166] Embodiment 17 17. The glass-based article of any one of claims 1 to 16, wherein the composition has (R2O+P2O5) / Al2O3, where R2O is the total amount of monovalent metal oxides, such that 1.4<(R2O+P2O5) / Al2O3<1.9.

[0167] Embodiment 18 a housing having a front face, a back face, and a side face; an electrical component at least partially housed within the housing, the electrical component including at least a controller, a memory, and a display provided on the front surface of the housing or adjacent thereto; a cover substrate disposed to cover the display; A consumer electronics product comprising: A consumer electronics product, wherein at least one of the housing and the cover substrate comprises, at least in part, the glass-based article according to any one of embodiments 1 to 17.

[0168] Embodiment 19 A glass-based article, a compressive stress layer extending from the surface of the glass-based article to a compression depth; a hydrogen-containing layer extending from the surface to a layer depth of the glass-based article; a composition of the center portion of the glass-based article, The composition comprises: SiO2 and Al2O3 and K2O and If the total amount of monovalent metal oxides is R2O, then (R2O+P2O5) / Al2O3 is 1.4<(R2O+P2O5) / Al2O3<1.9, and 3.5 mol% or more and 6.0 mol% or less of P2O5, 2.0 mol% or more and 5.0 mol% or less of LiO, the compressive stress layer has a compressive stress of 25 MPa or more, the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth; The glass-based article, wherein the depth of layer is greater than 5 μm.

[0169] Embodiment 20 20. The glass-based article of claim 19, wherein the glass-based article contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0170] Embodiment 21 21. The glass-based article of claim 19 or 20, wherein the glass-based article does not exhibit substantially phase separation.

[0171] Embodiment 22 A glass-based article, a compressive stress layer extending from the surface of the glass-based article to a compression depth; a hydrogen-containing layer extending from the surface to a layer depth of the glass-based article; a composition of the center portion of the glass-based article, The composition comprises: SiO2 and Al2O3 and K2O and If the total amount of monovalent metal oxides is R2O, then (R2O+P2O5) / Al2O3 is 1.4<(R2O+P2O5) / Al2O3<1.9, and 3.5 mol% or more and 6.0 mol% or less of P2O5, the compressive stress layer has a compressive stress of 25 MPa or more, the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth; The glass-based article, wherein the depth of layer is greater than 5 μm.

[0172] Embodiment 23 23. The glass-based article of claim 22, wherein the glass-based article contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0173] Embodiment 24 24. The glass-based article of claim 22 or 23, wherein the glass-based article does not exhibit substantially phase separation.

[0174] Embodiment 25 1. A method comprising forming a glass-based article by exposing a glass-based substrate to a processing environment having a pressure of 0.1 MPa or greater, a water partial pressure of 0.05 MPa or greater, and a temperature greater than 85°C, The glass substrate is SiO2 and Al2O3 and K2O and When the total amount of monovalent metal oxides is R2O, R2O / Al2O3 is 1.4 or less, and 3.5 mol% or more and 6.0 mol% or less of P2O5, 2.0 mol% or more and 5.0 mol% or less of LiO, The glass-based article is a compressive stress layer extending from the surface of the glass-based article to a compression depth, the compressive stress layer having a compressive stress of 25 MPa or more; a hydrogen-containing layer extending from the surface to a depth of the glass-based article, wherein the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the depth of the layer; The method wherein the depth of layer is greater than 5 μm.

[0175] Embodiment 26 26. The method of embodiment 25, wherein the processing environment is a saturated steam environment.

[0176] Embodiment 27 27. The method of claim 25 or 26, wherein the processing environment has a pressure of 1 MPa or more.

[0177] Embodiment 28 28. The method of any one of embodiments 25 to 27, wherein the processing environment has a temperature of 150°C or greater.

[0178] Embodiment 29 29. The method of any one of embodiments 25-28, further comprising manufacturing the glass-based substrate by a fusion molding process.

[0179] Embodiment 30 30. The method according to any one of embodiments 25 to 29, wherein the glass-based substrate is not subjected to an ion exchange treatment using an alkali ion source.

[0180] Embodiment 31 31. The method of any one of embodiments 25 to 30, wherein the glass-based substrate further comprises B2O3.

[0181] Embodiment 32 32. The method of any one of embodiments 25 to 31, wherein the glass-based substrate further comprises Na2O.

[0182] Embodiment 33 33. The method of any one of embodiments 25-32, wherein the glass-based substrate further comprises SnO2.

[0183] Embodiment 34 34. The method of any one of embodiments 25 to 33, wherein the glass-based substrate has an average alkali modifier field strength of 0.18 or less.

[0184] Embodiment 35 The glass substrate is 55.0 mol% or more and 65.0 mol% or less of SiO2; 10.0 mol% or more and 15.0 mol% or less of Al2O3, 0 mol% or more and 10.0 mol% or less of B2O3, 6.0 mol% or more and 15.0 mol% or less of K2O; 35. The method of any one of embodiments 25 to 34, comprising:

[0185] Embodiment 36 36. The method of any one of embodiments 25 to 35, wherein the glass-based substrate comprises 4.5 mol % to 5.5 mol % P2O5.

[0186] Embodiment 37 37. The method of any one of embodiments 25 to 36, wherein the glass-based substrate comprises more than 0 mol % to 3.0 mol % B2O3.

[0187] Embodiment 38 38. The method of any one of embodiments 25 to 37, wherein the glass-based substrate has a fusion line.

[0188] Embodiment 39 39. The method of any one of embodiments 25 to 38, wherein the glass-based substrate contains less than 1 platinum bead-and-chain defect per pound (about 0.45 kg).

[0189] Embodiment 40 40. The method of any one of embodiments 25 to 39, wherein the glass-based substrate has a zircon decomposition viscosity of 35 kP or less.

[0190] Embodiment 41 41. The method of any one of embodiments 25 to 40, wherein the glass-based substrate has a liquidus viscosity of 100 kP or greater.

[0191] Embodiment 42 42. The method of any one of claims 25 to 41, wherein the glass-based article has a substantially haze-free appearance.

[0192] Embodiment 43 43. The method of any one of embodiments 25 to 42, wherein the compression depth is greater than 5 μm.

[0193] EMBODIMENT 44 44. The method of any one of embodiments 25 to 43, wherein the compressive stress layer has a compressive stress of 200 MPa or more.

[0194] Embodiment 45 55.0 mol% or more and 65.0 mol% or less of SiO2; 10.0 mol% or more and 15.0 mol% or less of Al2O3, 0 mol% or more and 10.0 mol% or less of B2O3, 6.0 mol% or more and 15.0 mol% or less of K2O; 3.5 mol% or more and 6.0 mol% or less of P2O5, 2.0 mol% or more and 5.0 mol% or less of Li2O; If the total amount of monovalent metal oxides is R2O, then (R2O+P2O5) / Al2O3 is 1.4<(R2O+P2O5) / Al2O3<1.9, and Glass containing.

[0195] Embodiment 46 46. ​​The glass of embodiment 45, having an average alkali modifier field strength of 0.18 or less.

[0196] Embodiment 47 47. The glass of embodiment 45 or 46 comprising from 4.5 mol % to 5.5 mol % P2O5.

[0197] Embodiment 48 48. The glass of any one of embodiments 45 to 47, further comprising B2O3.

[0198] Embodiment 49 49. The glass of any one of embodiments 45-48, further comprising greater than 0 mol % to 3 mol % B2O3.

[0199] Embodiment 50 50. The glass of any one of embodiments 45 to 49, further comprising Na2O.

[0200] Embodiment 51 51. The glass of any one of embodiments 45 to 50, further comprising from 0 to 11 mol % Na2O.

[0201] Embodiment 52 52. The glass of any one of embodiments 45 to 51, further comprising SnO2.

[0202] Embodiment 53 53. The glass of any one of embodiments 45 to 52, having a zircon decomposition viscosity of 35 kP or less.

[0203] EMBODIMENT 54 54. The glass of any one of embodiments 45 to 53, having a liquidus viscosity of at least 100 kP. [Explanation of symbols]

[0204] 100 Glass products 110 First Surface 112 Second Surface 120 First compressive stress layer 122 Second compressive stress layer 130 Tensile Stress Region 200 Consumer Electronic Devices 202 Case 204 Front 206 Back 208 Side 210 Display 212 Cover Plate

Claims

1. A glass-based article, a compressive stress layer extending from the surface of the glass-based article to a compression depth; a hydrogen-containing layer extending from the surface to a layer depth of the glass-based article; a composition of the center portion of the glass-based article, The composition comprises: SiO ２ and, Al ２ O ３ と、 K ２ O and The total amount of monovalent metal oxides is R ２ When O is used, R is 1.4 or less ２ O / Al ２ O ３ and, 3.5 mol % or more and 6.0 mol % or less of P ２ O ５ and, and 2.0 mol% or more and 5.0 mol% or less of Li 2 O, the compressive stress layer has a compressive stress of 25 MPa or more, the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the layer depth; The glass-based article, wherein the layer depth is greater than 5 μm.

2. The composition contains a total amount of monovalent metal oxides of R ２ When R ２ O+P ２ O ５ ) / Al ２ O ３ <1.9 (R ２ O+P ２ O ５ ) / Al ２ O ３ 2. The glass-based article of claim 1, having

3. 3. The glass-based article of claim 1 or 2, wherein the glass-based article contains less than one platinum bead-and-chain defect per pound (about 0.45 kg).

4. the glass-based article does not exhibit phase separation; 3. The glass-based article of claim 1 or 2, wherein the glass-based article has a haze-free appearance.

5. 3. The glass-based article of claim 1 or 2, wherein the composition of the center portion of the glass-based article has an average alkali modifier field strength of 0.18 or less.

6. The composition of the center portion of the glass-based article is 55.0 mol% or more and 65.0 mol% or less of SiO ２ and, 10.0 mol% or more and 15.0 mol% or less of Al ２ O ３ and, 0 mol % or more and 10.0 mol % or less of B ２ O ３ and, 6.0 mol% or more and 15.0 mol% or less of K ２ O and The glass-based article of claim 1 or 2, comprising:

7. The composition of the center portion of the glass-based article is 4.5 mol % or more and 5.5 mol % or less of P ２ O ５ 7. The glass-based article of claim 6, comprising:

8. a housing having a front face, a back face, and a side face; an electrical component at least partially housed within the housing, the electrical component including at least a controller, a memory, and a display provided on the front surface of the housing or adjacent thereto; a cover substrate disposed to cover the display; A consumer electronics product comprising: A consumer electronics product, wherein at least one of the housing and the cover substrate comprises, at least in part, the glass-based article according to any one of claims 1 to 7.

9. 1. A method comprising forming a glass-based article by exposing a glass-based substrate to a processing environment having a pressure of 0.1 MPa or greater, a water partial pressure of 0.05 MPa or greater, and a temperature greater than 85°C, The glass substrate is SiO ２ and, Al ２ O ３ と、 K ２ O and The total amount of monovalent metal oxides is R ２ When O is used, R is 1.4 or less ２ O / Al ２ O ３ and, 3.5 mol % or more and 6.0 mol % or less of P ２ O ５ and, 2.0 mol% or more and 5.0 mol% or less of Li ２ O, The glass-based article is a compressive stress layer extending from the surface of the glass-based article to a compression depth, the compressive stress layer having a compressive stress of 25 MPa or more; a hydrogen-containing layer extending from the surface to a depth of the glass-based article, wherein the hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration toward the depth of the layer; The method wherein the depth of layer is greater than 5 μm.

10. the processing environment is a saturated steam environment; The processing environment has a pressure of 1 MPa or more, 10. The method of claim 9, wherein the processing environment has a temperature of 150°C or greater.

11. 11. The method of claim 9 or 10, further comprising manufacturing the glass-based substrate by a fusion molding process.

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