Articles including glass-ceramic substrates and methods of making the same

Abstract

Described herein is an article comprising a glass-ceramic substrate comprising a first surface and a second surface. The first surface is opposite the second surface. At least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material. The glass-ceramic substrate further comprises one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass. The one or more glass phase regions have a concentration of Ag2O of at least 5 mol.% at a depth of 200 nm below a surface of the glass phase region. Described herein is a method of forming an article comprising: converting at least a portion of a first surface of a glass-ceramic substrate to a glass phase material; and subjecting the glass phase material to an ion exchange treatment to introduce silver into the glass phase material. At least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material.

Description

[0001] Priority Statement

[0002] This application claims priority to U.S. Provisional Application No. 63 / 531,916, filed August 10, 2023, pursuant to 35 USC § 119. The entire contents of this application are hereby incorporated herein by reference for all purposes. Technical Field

[0003] This specification generally relates to articles of manufacture, and more specifically, to articles comprising glass-ceramic substrates. Background Technology

[0004] Portable electronic devices, such as smartphones, tablets, and wearable devices (e.g., watches and fitness trackers), utilize glass-based materials. For example, the screens on these portable electronic devices can be made from glass-based materials. Optical properties associated with good screen viewing are often sought. Coatings or other surface treatments can be used to enhance glass materials. However, existing glass-based materials have optical limitations.

[0005] Therefore, there is a need for glass-based materials with different optical properties and methods for producing these materials. This disclosure addresses this need, as well as other needs. Summary of the Invention

[0006] The independent claims describe various articles and methods for addressing the aforementioned and other needs in the prior art. The appended claims further describe advantageous embodiments of these various articles and methods.

[0007] According to one or more embodiments, this disclosure provides an article comprising a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; and wherein the one or more glass phase regions have an Ag₂O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase regions. An advantage of the article is that the refractive index of the glass phase regions can be adjusted by modifying the Ag₂O concentration therein, which may be applicable to modifying the optical properties of the article.

[0008] According to one or more embodiments, this disclosure provides an article comprising a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; and wherein the one or more glass phase regions have an Ag₂O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase regions; wherein the one or more glass phase regions on the first surface of the glass-ceramic substrate are textured; wherein a portion of the first surface excluding the one or more glass phase regions comprises one or more glass-ceramic regions containing the glass-ceramic material; and wherein the one or more glass-ceramic regions have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate. An advantage of this article is that it can be used as a transparent diffuser in various applications, such as reducing glare in anti-glare products.

[0009] According to one or more embodiments, this disclosure provides an article comprising a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; wherein a portion of the first surface excluding the one or more glass phase regions comprises one or more glass-ceramic regions containing the glass-ceramic material; wherein, according to an EPA dry test with Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate greater than or equal to 2. The advantage of the article is that it exhibits improved antimicrobial properties compared to conventional articles.

[0010] According to one or more embodiments, this disclosure provides a method for forming an article, the method comprising: converting at least a portion of a first surface of a glass-ceramic substrate into a glass phase material, wherein the glass-ceramic substrate includes the first surface and a second surface opposite to the first surface, and wherein at least 70% of the glass-ceramic substrate remains a glass-ceramic material; and subjecting the glass phase material to ion exchange treatment to introduce silver into the glass phase material. The advantages of this method are that the refractive index of the resulting article can be adjusted so that the article exhibits the optical properties required for its application as a transparent diffuser, and that the resulting article exhibits improved antimicrobial properties superior to conventional articles, or both. Attached Figure Description

[0011] Figure 1 A schematic cross-sectional view of an article of manufacture according to one or more embodiments described herein is depicted.

[0012] Figure 2 This is a conceptual top view of an article having an ordered pattern in the glass phase region according to one or more embodiments described herein;

[0013] Figure 3 This is a conceptual top view of an article having a random pattern in the glass phase region according to one or more embodiments described herein;

[0014] Figure 4 This is a conceptual top view of an article having a first region containing a glass phase region and a second region not containing a glass phase region according to one or more embodiments described herein;

[0015] Figure 5 A schematic cross-sectional view through a portion of the article according to one or more embodiments described herein;

[0016] Figure 6A A portion of an article comprising a glass phase region according to one or more embodiments described herein is schematically depicted;

[0017] Figure 6B A schematic depiction of light passing through a portion of a comparative article that does not contain a glass phase region;

[0018] Figure 6C A schematic depiction of light passing through a portion of an article containing a glass phase region according to one or more embodiments described herein;

[0019] Figure 7A A plan view of an exemplary electronic device incorporating an article of manufacture according to one or more embodiments described herein;

[0020] Figure 7B According to one or more embodiments described herein Figure 7A A perspective view of an exemplary electronic device;

[0021] Figure 8 A flowchart of a method for forming an article of manufacture according to one or more embodiments described herein;

[0022] Figure 9 A method for forming an article of manufacture according to one or more embodiments described herein is schematically depicted;

[0023] Figure 10AA scanning electron microscope image of a cross-sectional view of a laser-processed glass-ceramic substrate according to one or more embodiments described herein;

[0024] Figure 10B The image is a scanning electron microscope image of an enhanced cross-sectional view of a laser-treated glass-ceramic substrate according to one or more embodiments described herein.

[0025] Figure 10C A scanning electron microscope image of a top view of a laser-treated glass-ceramic substrate according to one or more embodiments described herein;

[0026] Figure 11A A scanning electron microscope image of a top view of a laser-treated glass-ceramic substrate according to one or more embodiments described herein;

[0027] Figure 11B A scanning electron microscope image of a top view of a glass-ceramic substrate that has undergone laser processing and chemical etching according to one or more embodiments described herein;

[0028] Figure 11C A scanning electron microscope image of a top view of a laser-treated glass-ceramic substrate according to one or more embodiments described herein;

[0029] Figure 11D A scanning electron microscope image of a top view of a glass-ceramic substrate that has undergone laser processing and chemical etching according to one or more embodiments described herein;

[0030] Figure 12A A scanned electronic image of an article of manufacture according to one or more embodiments described herein;

[0031] Figure 12B This is an elemental analysis map of the glassy phase region determined by scanning electron microscopy energy-dispersive X-ray spectroscopy according to one or more embodiments described herein; and

[0032] Figure 12C This is an elemental analysis diagram of a glass-ceramic region determined by scanning electron microscopy energy-dispersive X-ray spectroscopy according to one or more embodiments described herein. Detailed Implementation

[0033] Reference will now be made in detail to articles comprising a glass-ceramic substrate according to various embodiments, as described herein. Specifically, the articles may include a glass-ceramic substrate comprising a first surface and a second surface, and one or more glass phase regions on the first surface of the glass-ceramic substrate. The glass phase regions may contain an Ag₂O concentration greater than or equal to 5 mol%. In some embodiments, the incorporation of Ag₂O into the glass phase regions may be used to achieve desired optical properties and / or antimicrobial efficacy, as described herein.

[0034] According to some embodiments, the article may have relatively low glitter, relatively low image sharpness, relatively low haze, relatively high Ag2O concentration, or a combination of these properties. This combination of relatively low glitter, relatively low image sharpness, relatively low haze, and relatively high Ag2O concentration may be more desirable than conventional glass-based articles, in which image sharpness and glitter are typically inversely proportional (meaning a relatively low value for one property may be associated with a relatively high value for another), or conventional glass-based articles with a low Ag2O concentration, which may result in poorer antimicrobial properties.

[0035] In the following description, in the several views shown in the figures, the same reference numerals denote the same or corresponding parts. It should also be understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” and “inward” are for convenience and should not be construed as restrictive terms. Whenever a group is described as consisting of at least one or a combination of elements in a group, it should be understood that the group may consist individually or in combination with each other of any number of those listed elements. Unless otherwise specified, when listing a range of values, the range of values ​​includes the upper and lower limits of the range and any range in between. As used herein, unless otherwise specified, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more.” It should also be understood that the various features disclosed in the specification and figures can be used in any and all combinations.

[0036] Unless otherwise specified, all compositions of the glasses described herein are expressed as mole percentages (mol%), and the compositions are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in degrees Celsius (°C). All scopes disclosed in this specification include any and all scopes and subscopes covered by the broadly disclosed scope, whether expressly stated before or after the scope disclosure.

[0037] It should be noted that the terms “substantially” and “about” may be used herein to indicate the degree of uncertainty attributable to any quantitative comparison, value, measurement, or other representation. These terms are also used herein to indicate the extent to which a quantitative representation may differ from a stated reference without causing a fundamental change in the subject matter. As utilized herein, when the term “about” is used to modify a value, an exact value is also disclosed.

[0038] For reference Figure 1 The image schematically depicts article 100. Article 100 may include a glass-ceramic substrate 110. The glass-ceramic substrate 110 may have a first surface 104 and a second surface 102 opposite to the first surface 104, as well as an edge 106. In one or more embodiments, the first surface 104 and the second surface 102 may be generally planar and parallel, such as... Figure 1 As shown in the illustration. In other embodiments, the first surface 104 and the second surface 102 may be curved and / or non-parallel (as shown in the illustration). Figure 1 (Not depicted). In one or more embodiments, at least a portion of the first surface 104 may be a region including a glass phase region. In one or more embodiments, the region of the first surface 104 including a glass phase region may cover the entire first surface 104. In one or more embodiments, at least a portion of both the first surface 104 and the second surface 102 may be a region including a glass phase region. In some embodiments, the edge 106 may include a glass phase region.

[0039] For reference Figure 2 and Figure 3 In one or more embodiments, the portion of the first surface 104 that includes the region comprising the glass phase region may include a first plurality of glass phase regions 400. Figure 2 and Figure 3 This is a conceptual top view of a portion of the first surface 104 that includes the glass phase region 400. In one or more embodiments, the glass phase region 400 may... Figure 2 The ordered pattern shown is arranged above the first surface 104. In one or more embodiments, the glass phase region 400 can Figure 3 The random pattern shown is arranged above the first surface 104.

[0040] For reference Figure 4 In one or more embodiments, the glass-ceramic substrate 110 may include a first region 405 including a glass phase region 400 and a second region 410 not including a glass phase region 400.

[0041] In one or more embodiments, the total surface area of ​​one or more glass phase regions may be 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, 90% to 100%, 50% to 90%, 60% to 90%, 70% to 90%, 80% to 90%, 50% to 80%, 60% to 80%, 70% to 80%, 50% to 70%, 60% to 70%, or 50% to 60% of the total surface area of ​​the first surface 104 of the glass-ceramic substrate.

[0042] In one or more embodiments, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of the glass-ceramic substrate may comprise glass-ceramic material. Conventional methods known in the art, such as X-ray diffraction (XRD), can be used to measure the weight percentage of glass-ceramic material present in the glass-ceramic substrate.

[0043] Figure 5 This is a schematic cross-sectional view through a portion of the glass phase region of the first surface 104, according to some embodiments, to illustrate the morphology of the region including the glass phase region 400 within the first surface 104. In embodiments, the glass phase region may be concave. Figure 5 As shown in the cross-section, when viewed from the cross-section, the glass phase region 400 may have peaks 520 and valleys 540. Peaks 520 and valleys 540 appear at points along the cross-section where the slope of a curve drawn along the first surface 104 of the glass-ceramic substrate 110, representing the thickness of the glass-ceramic substrate 110 on the y-axis, will be equal to zero.

[0044] In one or more embodiments, peaks 520 and valleys 540 may define a glass phase region 400. The glass phase region 400 may have an average aperture length size, wherein the aperture size is measured as the length of a line drawn from the top of the first peak 520 to the top of an adjacent second peak 520. l The glass phase region 400 may have a depth d, wherein the depth d is measured as the vertical distance from the top of the shortest peak 520 of the glass phase region 400 to the bottom of the deepest valley 540 of the same glass phase region 400. In one or more embodiments, the glass phase region 400 in the first plurality of glass phase regions may have an average pore length size of 5 micrometers (μm) to 100 μm. In an embodiment, the valley 520 of the glass phase material may be located less than 10 μm below the surface of the first surface that has not been converted into the glass phase material.

[0045] In one or more embodiments, the portion of the glass-ceramic substrate 110 including the glass phase region 400 has relatively low haze, providing desired optical properties and a desirable aesthetic appearance. "Haze" (also known as "transmitted haze") is a surface light scattering characteristic and refers to the percentage of light scattered beyond a 4.0° pyramid according to ASTM procedure D1003. For optically smooth surfaces, transmitted haze is generally close to zero. Low haze can be desirable for applications requiring high display contrast, while high haze can be suitable for optical designs with scattering, such as edge lighting, or for aesthetic reasons, such as reducing the "black hole" appearance of the display when it is off. The general preference for low versus high haze (and the acceptance of performance trade-offs) can be determined by customer or end-user preferences and their final application and usage patterns. For example, haze in the portion of the glass-ceramic substrate 110 including the glass phase region 400 can provide anti-glare capabilities, improving performance under high ambient light conditions, such as bright sunlight. In one or more embodiments, the haze of the portion of the glass-ceramic substrate 110 including the glass phase region 400 is 5% to 40%, for example, 5% to 30%, 5% to 20%, 5% to 10%, 10% to 40%, 10% to 30%, 10% to 20%, 20% to 40%, 20% to 30%, or 30% to 40%. In one or more embodiments, the haze of the portion of the first surface 104 including the glass phase region 400 is less than or equal to 40%, for example, less than or equal to 30%, less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, or less than or equal to 10%.

[0046] The portion of the glass-ceramic substrate 110 described herein, including the glass phase region 400, can be further characterized by gloss. “Gloss,” “gloss level,” or similar terms refer to, for example, surface brightness, luminance, or shine, and more specifically, to a measurement of specular reflectance calibrated according to a standard (e.g., a certified black glass standard) in accordance with ASTM procedure D523, the contents of which are incorporated herein by reference in their entirety. Common gloss measurements are typically performed at incident light angles of 20°, 60°, and 85°, with the most commonly used gloss measurement being performed at 60°. “60° gloss” or “gloss 60°” refers to a measurement of gloss when light is incident on the sample at an angle of 60° away from the normal to the glass phase region of the glass-ceramic substrate, as described in ASTM procedure D523. Unless otherwise indicated, the amount of gloss is reported in this disclosure according to ASTM D523 using any of the following interchangeable names: "Standard Gloss Unit (SGU)" (i.e., "gloss of 30 SGU to 100 SGU") or no unit number (i.e., "gloss of 30 to 100"). In one or more embodiments, the portion of the glass-ceramic substrate 110 including the glass phase region 400 includes a gloss of 20 to 80, for example, 20 to 60 or 20 to 40 at 60°.

[0047] The portion of the glass-ceramic substrate 110 described herein, including the glass phase region 400, can be further characterized by flare intensity. "Flicker intensity," "flare contrast," "display flare intensity," "pixel power deviation," "PPD," or similar terms refer to the visual phenomenon produced when a textured transparent surface is combined with a pixelated display. Generally, quantifying flare intensity involves imaging an illuminated display or analog display with a textured surface in the field of view. The flare intensity of region P is calculated as σ(P) / μ(P), where σ(P) is the standard deviation of the cumulative intensity distribution of each display pixel contained within region P, divided by the average intensity μ(P). Following the guidance in the following: (1) J. Gollier et al., “Apparatus and method for determining sparkle”, US9411180B2, United States Patent and Trademark Office, July 20, 2016; (2) A. Stillwell et al., “Perception of Sparkle in Anti-Glare Display Screens”, JSID 22(2), 129-136 (2014); and (3) C. Cecala et al., “Fourier Optics Modeling of Display Sparkle from Anti-Glare Cover Glass: Comparison to Experimental Data”, Optical Society of America Imaging and Applied Optics Congress, JW5B.8 (2020); a person skilled in the art can construct an imaging system to quantify sparkle. Alternatively, commercially available systems can be used (such as the SMS-1000, Display Messtechnik & Systeme GmbH & Co. KG, Germany). As described herein, flare intensity is measured using a 140 PPI display.Imaging was performed using an f=50 mm lens / machine vision camera combination (e.g., C220503 1:2.850 mm Φ30.5, Tamron, Japan) and Stingray F-125 B, Allied Vision Technologies GmbH, Germany) on a 140 PPI display (e.g., Z50, Lenovo Group Limited, Hong Kong, China) at maximum display brightness, with only the green subpixels (R=0, B=0, G=255) illuminated. The lens was set to aperture f=5.6, depth of field=0.3, and working distance=approximately 290 mm; with these settings, the ratio of display pixels to camera pixels was approximately 1:9. The field of view used for analysis contained approximately 7500 display pixels. Gain and gamma correction were disabled on the camera. Before calculating flare intensity, periodic intensity variations from the display, as well as non-periodic intensity variations such as dead pixels, were removed during analysis.

[0048] In one or more embodiments, the portion of the glass-ceramic substrate 110 including the glass phase region 400 may have a glitter intensity of less than or equal to 5% at 140 ppi. For example, in one or more embodiments, the glitter intensity of the region of the glass-ceramic substrate including the glass phase region at 140 ppi may be less than or equal to 4.9%, less than or equal to 4.8%, less than or equal to 4.7%, less than or equal to 4.6%, less than or equal to 4.5%, less than or equal to 4.4%, less than or equal to 4.3%, less than or equal to 4.2%, less than or equal to 4.1%, less than or equal to 4%, less than or equal to 3.9%, less than or equal to 3.8%, less than or equal to 3.7%, less than or equal to 3.6%, less than or equal to 3.5%, less than or equal to 3.4%, less than or equal to 3.3%, less than or equal to 3.2%, less than or equal to 3.1%, less than or equal to 3. %, less than or equal to 2.9%, less than or equal to 2.8%, less than or equal to 2.7%, less than or equal to 2.6%, less than or equal to 2.5%, less than or equal to 2.4%, less than or equal to 2.3%, less than or equal to 2.2%, less than or equal to 2.1%, less than or equal to 2%, less than or equal to 1.9%, less than or equal to 1.8%, less than or equal to 1.7%, less than or equal to 1.6%, less than or equal to 1.5%, less than or equal to 1.4%, less than or equal to 1.3%, less than or equal to 1.2%, less than or equal to 1.1%, or even less than or equal to 1.0%.

[0049] The portion of the glass-ceramic substrate 110 described herein, including the glass phase region 400, can be further characterized by image sharpness. The terms “reflective image sharpness,” “image sharpness,” “DOI,” or similar terms are defined by Method A of ASTM Procedure D5767 (ASTM 5767), entitled “Standard Test Methods for Instrumental Measurements of Distinctness-of-ImageGloss of Coating Surfaces.” According to Method A of ASTM 5767, the glass reflectivity factor of the glass phase region of the glass-ceramic substrate is measured at a specular view and at angles slightly deviating from the specular view. The values ​​obtained from these measurements are combined to provide the DOI value. Specifically, the DOI is calculated according to equation (1):

[0050] (1)

[0051] Where Rs is the relative magnitude of reflectivity in the specular direction and Ros is the relative magnitude of reflectivity in the outward direction. As described herein, unless otherwise specified, Ros is calculated by averaging the reflectivity over an angular range of 0.2° to 0.4° away from the specular direction. Rs can be calculated by averaging the reflectivity over an angular range of ±0.05° centered on the specular direction. Both Rs and Ros are measured using a goniophotometer (Rhopoint Instruments) calibrated to a certified black glass standard as specified in ASTM procedures D523 and D5767. The goniophotometer uses a detector array where the specular angle is centered on the highest value in the detector array. The DOI is evaluated using a 1-sided (black absorber coupled to the back of the glass) method, where the result is referred to as “coupled image sharpness”. A 2-sided (allowing reflections from both glass surfaces, with nothing coupled to the glass) method is also used to evaluate the DOI, where the result is referred to as “uncoupled image sharpness”. DOI measurement can comprehensively determine the gloss, reflectance, and DOI of the glass phase region of a glass-ceramic substrate. This can be achieved according to the description above for R... s and R os Calculate R using the average value obtained os / R sThe term "20° DOI" or "DOI 20°" refers to the measurement of DOI when light is incident on the sample at an angle of 20° away from the normal to the glass surface, as described in ASTM D5767. Measurements of DOI or ordinary gloss using a one-sided or two-sided method are best performed in a dark room or enclosed space, such that the measured values ​​for these properties are zero when no sample is present. The scale values ​​obtained using the measurement procedures in ASTM D5767 range from 0 to 100, where a value of 100 represents perfect DOI (image sharpness).

[0052] In one or more embodiments, the portion of the glass-ceramic substrate 110 including the glass phase region 400 may have a coupled image sharpness of less than 20%. For example, in one or more embodiments, the glass phase region of the glass-ceramic substrate may have a coupled image sharpness of less than 15%, less than 10%, or even less than 5%.

[0053] In one or more embodiments, the portion of the glass-ceramic substrate 110 including the glass phase region 400 may exhibit a root mean square (RMS) roughness height (i.e., in the z-direction) greater than 40 nanometers (nm) "R". q For example, the R q Greater than 60 nm, greater than 80 nm, greater than 100 nm, greater than 150 nm, greater than 200 nm, greater than 300 nm, greater than 400 nm, greater than 500 nm, greater than 600 nm, or even greater than 700 nm. R is measured using methods known in the art. q The methods described herein include, for example, atomic force microscopy (AFM), stylus profilometry, and optical interferometric profilometry. q Preferably, measurements are taken on a sample surface portion with a size of at least about 0.5 mm × 0.5 mm to capture a representative average value, which includes the number of typical surface features in the range of about 10 to about 1000.

[0054] In one or more embodiments, the glass phase region 400 may include Ag₂O at a depth of 200 nm below the surface of the glass phase region at a concentration greater than or equal to 5 mol%, for example, a concentration greater than or equal to 6 mol%, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, or greater than or equal to 10 mol%. The Ag₂O concentration at a depth of 200 nm below the surface of the glass phase region 400 may be 5 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, or any range with any two of these values ​​as endpoints. In some embodiments, the Ag₂O concentration at a depth of 200 nm below the surface of the glass phase region 400 is 5 mol% to 30 mol%, or 10 mol% to 25 mol%.

[0055] In one or more embodiments, at all depths of the glass phase region 400 on the first surface 104, the glass phase region 400 may include Ag₂O at a concentration greater than or equal to 5 mol%, for example, a concentration greater than or equal to 6 mol%, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, or greater than or equal to 10 mol%. The Ag₂O concentration at all depths of the glass phase region 400 on the first surface 104 may be 5 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, or any range with any two of these values ​​as endpoints. In some embodiments, the Ag₂O concentration at all depths of the glass phase region 400 on the first surface 104 is 5 mol% to 30 mol%, or 10 mol% to 25 mol%.

[0056] The concentration of Ag₂O in the glass phase region 400 can be determined using conventional elemental analysis methods known in the art, such as, but not limited to, scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM / EDS), glow discharge photoemission spectroscopy (GDOES), or secondary ion mass spectrometry (SIMS).

[0057] In an embodiment, the glass phase region 400 may include an amorphous glass material with silver ion exchange (IOX).

[0058] In one embodiment, the glass phase region 400 may be textured. In other embodiments, the glass phase region 400 may not be textured. As used herein, the term "textured" refers to an embodiment in which the glass phase region 400 has a depth greater than or equal to 40 nm, wherein the depth (d) is measured as... Figure 5 The vertical distance shown is from the top of the shortest peak 520 of the glass phase region 400 to the bottom of the deepest valley 540 of the same glass phase region 400.

[0059] In an embodiment, a portion of the first surface 104 excluding the glass phase region 400 may include one or more glass-ceramic regions. These glass-ceramic regions may comprise a glass-ceramic material. In an embodiment, one or more glass-ceramic regions may have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate. In an embodiment, one or more glass-ceramic regions may have an Ag₂O concentration of less than 5 mol.% at all depths therein.

[0060] In this embodiment, Ag₂O can be introduced into the article 100 via ion exchange, such that a significant amount of Ag₂O in the article 100 is located in the glass phase region 400, and the concentration of Ag₂O in the glass-ceramic region serving as the host material can be significantly lower or zero (considering the presence of impurities). In other words, preferably, the host composition has a low Ag₂O concentration, for example, equal to or less than 1 mol% or 0.1 mol%. It is not desirable to be bound by any particular theory, considering the antimicrobial efficacy as a surface effect, and it is not expected that silver located more than 1 micrometer (1000 nm) from the article surface will significantly contribute to the antimicrobial efficacy. However, silver also exhibits optical effects, such as potentially undesirable discoloration, regardless of whether Ag₂O is present in the host material or concentrated in the glass phase region 400. Minimizing the amount of Ag₂O in the article 100 to below the amount in the glass phase region 400 may minimize these undesirable optical effects without sacrificing antimicrobial efficacy.

[0061] In some embodiments, ΔE is equal to or less than 10, or equal to or less than 7. As used herein, “ΔE” or “color ΔE” refers to L. a b The difference in coordinates is a method for quantifying color changes. Correlation L was measured on a PE X-RITE Color i7-860 using a D65 illuminator. a b Coordinates. By performing L-type measurements on other similar samples before and after silver ion exchange. a b The color change (ΔE) is measured. ΔE is calculated by comparing silver before and after IOX using the following equation:

[0062]

[0063] The subscript "2" indicates the value after IOX, and the subscript "1" indicates the value before IOX.

[0064] A lower ΔE corresponds to a less noticeable color difference. In some embodiments, when combined with articles described herein, silver’s surprising antimicrobial effectiveness achieves superior antimicrobial efficacy without using too much silver, which would unduly alter the appearance of the article.

[0065] In one or more embodiments, the glass-ceramic substrate 110 may be formed of a glass-ceramic material having both a glass phase and a ceramic phase. Exemplary glass-ceramics include those materials in which the glass phase is formed of silicates, borosilicates, aluminosilicates, or boroaluminosilicates and the ceramic phase is formed of β-spodumene, β-quartz, nepheline, hexagonal potassium nepheline, or triclinic nepheline. "Glass-ceramic" includes materials produced by controlled crystallization of glass. Examples of suitable glass-ceramics may include Li2O-Al2O3-SiO2 system (i.e., LAS system) glass-ceramics, MgO-Al2O3-SiO2 system (i.e., MAS system) glass-ceramics, ZnO × Al2O3 ×nSiO2 (i.e., ZAS system) and / or glass-ceramics comprising a major crystalline phase comprising β-quartz solid solution, β-spodumene, cordierite, and lithium disilicate. In an exemplary embodiment, the glass-ceramic substrate 110 comprises any of the glass-ceramic compositions disclosed in U.S. Patent Application Publication No. 2016 / 0102010 A1, filed October 8, 2015, which is incorporated herein by reference in its entirety. The glass-ceramic substrate 110 may be strengthened using a chemical strengthening process.

[0066] In one or more embodiments, the glass-ceramic substrate 110 may comprise an alkaline aluminosilicate glass, such as lithium aluminosilicate glass. Exemplary lithium aluminosilicate glass materials are those described in U.S. Patent Application Publication No. 2019 / 0300422 A1, entitled “Glasses Having High Fracture Toughness,” published October 3, 2019, the contents of which are incorporated herein by reference in their entirety. In additional embodiments, alkaline earth aluminosilicate glasses may be used.

[0067] Conventional products incorporating anti-glare glass surfaces often exhibit glare, which degrades display performance. Anti-glare surfaces can be coated and locally adjusted (IOX) to modify the surface refractive index; however, these methods are difficult to control and use in manufacturing due to complexity, limited control, and high cost. For example, the rapid diffusion of silver ions in all vertical and horizontal dimensions of glass can make adjusting the local refractive index challenging. Furthermore, these modifications can impair glass properties, such as reducing scratch resistance.

[0068] In embodiments, the article described herein can be used as a transparent diffuser. In embodiments, the glass phase region 400 contains an increased Ag2O concentration relative to the Ag2O concentration in the body glass-ceramic region 420. The glass phase region 400 may have an increased refractive index relative to the glass-ceramic material of the glass-ceramic substrate 110. In embodiments, the local refractive index of the glass phase region 400 may be adjusted so that an article comprising a glass-ceramic substrate 110 having the glass phase region 400 can be used as a transparent diffuser in a variety of applications, such as reducing glare on anti-glare products. The glass-ceramic substrate may be textured to provide anti-glare properties. However, conventional substrates containing surface textures may increase glare and / or increase non-uniformity.

[0069] Figure 6A A portion of a glass-ceramic substrate 110 comprising a glass phase region 400 and a main glass-ceramic region 420 is schematically depicted, wherein the glass phase region 420 is concave and has an increased Ag2O concentration. Figure 6B A portion of a comparative glass-ceramic substrate used with a display is schematically depicted, comprising a main glass-ceramic region 420, a concave glass-ceramic region 620, and light emitted from pixels 640 and 650 of the display. Light traveling through the comparative glass-ceramic substrate from pixel 640 may be defocused 660, and light traveling through the comparative glass-ceramic substrate from pixel 650 may be focused 670, which may respectively cause non-uniformity and flare. Figure 6C A portion of a glass-ceramic substrate for use with a display is schematically depicted, comprising a main glass-ceramic region 420, a concave glass phase region 400, and light emitted from pixels 640 and 650 of the display. Without being bound by any particular theory, it is understood that by increasing the local refractive index of the glass phase region relative to the main glass-ceramic region 420, the refractive index can be adjusted so that light traveling from pixels 640 and 650 can pass through the glass-ceramic substrate without severe focusing or defocusing 680, thereby minimizing display non-uniformity and glare. The embodiments disclosed herein can be used as transparent diffusers in other applications, such as on windows, to provide anti-glare functionality without diffusing or blurring the transmitted image.

[0070] In the embodiments, the articles described herein have enhanced antimicrobial efficacy as described in U.S. Patent Application US20220169557A1, the contents of which are incorporated herein by reference in their entirety.

[0071] The “EPA dry test” refers to the test published by the EPA as “Test Method for Efficacy of Copper Alloy Surfaces as a Sanitizer,” which can be used to assess antimicrobial efficacy. In the event of any discrepancy between the content described in the EPA protocol and the content described herein, references to “dry test” refer to the content described herein. A Staphylococcus aureus sample is placed on a dry sample surface. The surface is kept at room temperature (25°C) and room humidity (42% relative humidity) for 2 hours. The amount of surviving bacteria is then measured to determine the “logarithmic kill rate” resulting from two hours of exposure to the surface at room temperature and humidity. A logarithmic kill rate of 1% surviving bacteria is 1, 1% surviving bacteria is 2, 0.1% surviving bacteria is 3, and so on.

[0072] The high silver concentration in the glass phase region 400 is thought to result in a surprisingly high kill rate under the EPA dry test described herein. According to the EPA dry test, the article may exhibit a logarithmic kill rate equal to or greater than 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, or 5. According to the EPA dry test, the logarithmic kill rate may be 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, or any range with any two of these values ​​as endpoints. In some embodiments, the logarithmic kill rate is 2 to 5 according to the EPA dry test. It should be noted that achieving high logarithmic kill rates under EPA dry testing is significantly more difficult than under wet testing, which is often used to assess antimicrobial efficacy. This is because EPA dry testing conditions involve limited or no liquid water to facilitate the diffusion of antimicrobial ions from the product. Therefore, kill rate reports for various samples under other tests do not determine whether those samples will pass EPA dry testing, and for many products, the kill rate under EPA dry testing is expected to be much lower than that under wet testing.

[0073] The “JIS Z 2801 test” refers to a test published by the Japanese Standards Association (JSA) that can be used to evaluate the antimicrobial activity and efficacy of plastic materials and other rigid antimicrobial surfaces. The contents of this test are incorporated herein by reference in their entirety. According to the JIS Z 2801 test with Staphylococcus aureus, the article may exhibit a logarithmic kill rate equal to or greater than 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, or 5. According to the JIS Z 2801 test with Staphylococcus aureus, the logarithmic kill rate may be 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, or any range with any two of these values ​​as endpoints. In some embodiments, the logarithmic kill rate according to the JIS Z 2801 test with Staphylococcus aureus is 3 to 5.

[0074] The article 100 disclosed herein can be incorporated into another article, such as an article having a display (or a display article) (e.g., consumer electronic devices, including mobile phones, tablets, computers, navigation systems, etc.), building articles, transport articles (e.g., automobiles, trains, airplanes, ships, etc.), electrical articles, or any article requiring a certain degree of transparency, scratch resistance, abrasion resistance, antimicrobial properties, or a combination thereof. Exemplary articles incorporating any of the articles 100 disclosed herein... Figure 7A and Figure 7B As shown in the image. To be precise, Figure 7A and Figure 7B A consumer electronic device 200 is shown, comprising a housing 202 having a front surface 204, a rear surface 206, and a side surface 208; electrical components (not shown) at least partially or entirely located within the housing, and including at least a controller, memory, and a display 210 located at or adjacent to the front surface of the housing; and a cover plate 212 located at or above the front surface of the housing such that it is positioned above the display. In embodiments, at least a portion of at least one of the cover plate 212 and / or the housing 202 may comprise any of the articles of manufacture 100 disclosed herein.

[0075] In embodiments, the article 100 disclosed herein can be incorporated into structures that may include transparent luminaires, transparent displays, head-up displays, head-mounted displays, transparent backlights, touchscreen displays, liquid crystal displays, aquariums, laser-based reflective head-up displays, wearable displays, windows, vehicle dashboards, automotive windows, waveguides, light guides, or architectural windows. In embodiments, the structure may include a microlens array, which can be used in applications such as optical and sensing systems. In embodiments, the fabrication of the microlens array, including the article 100 disclosed herein, with specific properties can be adjusted not only by the shape of the glass phase region 400 but also by localized adjustment of the refractive index. Furthermore, the article 100 disclosed herein can be used as a superlens, for example, when the wavelength of interest is greater than the lateral feature size.

[0076] The article 100 disclosed herein can be incorporated into a glass screen protector for a smartphone. The glass screen protector may include a cover glass and an adhesive backing disposed on the cover glass. In an embodiment, the adhesive backing is used for attachment to a smartphone. In an embodiment, at least a portion of the cover glass includes any of the glass-ceramic substrate 110 disclosed herein, or any of the article 100 disclosed herein.

[0077] For reference Figure 8 The method 800 described herein may include: at step 810, converting at least a portion of a first surface of a glass-ceramic substrate into a glass phase material; and at step 820, subjecting the glass phase material to ion exchange treatment to introduce silver into the glass phase material. The article formed by method 800 may comprise either the article 100 disclosed herein or the glass-ceramic substrate 110.

[0078] like Figure 8 As shown in method 800, at step 810, the method may include converting at least a portion of a first surface of a glass-ceramic substrate into a glass phase material. In an embodiment, the glass-ceramic substrate may include a first surface and a second surface opposite to the first surface. In an embodiment, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of the glass-ceramic substrate may remain a glass-ceramic material after conversion.

[0079] In one or more embodiments, converting at least a portion of the first surface of a glass-ceramic substrate into a glass phase material may include directing radiation from a laser to the first surface of the glass-ceramic substrate to form a glass phase material.

[0080] In one or more embodiments, converting at least a portion of the first surface of a glass-ceramic substrate into a glass phase material may include laser etching of at least a portion of the first surface of the glass-ceramic substrate. In one or more embodiments, laser etching includes heating to a target temperature. In one or more embodiments, the target temperature is at least 300°C, at least 325°C, at least 350°C, at least 375°C, at least 400°C, at least 450°C, at least 475°C, at least 500°C, or even at least 600°C.

[0081] In one or more embodiments, laser etching may include directing pulsed radiation onto at least a portion of a first surface of a glass-ceramic substrate to form a plurality of glass phase regions. Each glass phase region may have a feature size and feature location controlled by the pulsed radiation. Surface features may each have a surface feature shape and surface feature curvature controlled by the pulsed radiation. In one or more embodiments, the laser may be a CO2 laser. In embodiments, laser etching may cause a portion of the glass-ceramic substrate having a surface crystalline phase to melt, which may form glass phase regions upon cooling.

[0082] In one or more embodiments, pulsed radiation from a laser can cause compositional and / or phase-related changes in the material portion of a glass-ceramic substrate near the first surface.

[0083] In one or more embodiments, configuring a laser to emit pulsed radiation to form a glassy phase region includes setting one or more parameters of the laser. These parameters may include laser type, center wavelength, repetition rate, average power, pulse duration, pulse energy, beam shape, focal length, spot size, scanning method, scanning speed, scan line spacing, scan line spacing, laser flux, and other parameters. In an embodiment, the laser may be an ultrafast laser that produces ultrafast short pulse widths (10⁻⁶ Hz). -12 Up to 10 -15 (seconds) and high peak intensity. When used for high-precision manufacturing, it is associated with long pulses (i.e., nanoseconds (10^6) and high peak intensity). -9Compared to fs, ultrafast lasers offer several advantages, such as negligible cracking, minimal heat-affected zone, low recasting rate, and high precision. In embodiments, ultrafast lasers used to form glass phase regions on glass-ceramic surfaces can have various operating wavelengths (i.e., 532 nm, 800 nm, 1030 nm, etc.) and pulse widths can vary from tens of fs to a few ps (i.e., 10 ps). Both fiber-based lasers and solid-state lasers can be used. In embodiments, the size of the focused spot can be controlled by changing the focal length of the F-θ lens. To increase throughput, special optics or spatial light modulators (SLMs) can be used to shape a single Gaussian beam into a multifocal beam on the glass-ceramic substrate for parallel processing. In embodiments, a polygon scanner or other laser system is used to form the glass phase regions. Detailed information (including settings) of one or more parameters is described in the Examples section of this disclosure.

[0084] In one or more embodiments, the method may further include wet etching of a glass-ceramic substrate by contacting at least a portion of the glass phase material with an etchant. In one or more embodiments, the etchant may comprise hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or a combination of two or more thereof. In one or more embodiments, the etchant may comprise an aqueous hydroxide material, such as NaOH, KOH, or a combination thereof. The wet etching is configured to remove material from a first surface and a second surface of the substrate.

[0085] In one or more embodiments, the contact time between the glass-ceramic substrate and the etchant can be greater than or equal to 5 minutes and less than or equal to 200 minutes, for example, greater than or equal to 5 minutes and less than or equal to 150 minutes, greater than or equal to 5 minutes and less than or equal to 100 minutes, greater than or equal to 5 minutes and less than or equal to 50 minutes, greater than or equal to 5 minutes and less than or equal to 25 minutes, greater than or equal to 25 minutes and less than or equal to 200 minutes, greater than or equal to 25 minutes and less than or equal to 150 minutes, greater than or equal to 25 minutes and less than or equal to 100 minutes, greater than or equal to 50 minutes and less than or equal to 200 minutes, greater than or equal to 100 minutes and less than or equal to 200 minutes, greater than or equal to 100 minutes and less than or equal to 150 minutes, greater than or equal to 150 minutes and less than or equal to 200 minutes, or any combination of these ranges.

[0086] During the etching process, the etchant can be exposed to high temperatures. High temperatures can increase the etching rate. In one or more embodiments, the temperature of the etchant is greater than or equal to 90°C and less than or equal to 140°C, for example, greater than or equal to 90°C and less than or equal to 132°C, greater than or equal to 95°C and less than or equal to 135°C, greater than or equal to 100°C and less than or equal to 130°C, greater than or equal to 105°C and less than or equal to 125°C, greater than or equal to 110°C and less than or equal to 120°C, greater than or equal to 90°C and less than or equal to 115°C, and any and all subranges formed by the aforementioned endpoints. In one or more embodiments, the etchant can be exposed to ambient temperature.

[0087] The etching rate and etching time can be selected to remove the desired amount of material from the surface of the glass-ceramic substrate 110. If too little material is removed during the etching step, the desired surface properties, such as image sharpness and luster, may not be achieved. Removing too much material from the abraded surface may increase costs and reduce manufacturing yield.

[0088] In one embodiment, the method may include wet etching prior to ion exchange treatment. In other embodiments, the method does not include wet etching.

[0089] like Figure 8 As shown in method 800, at step 820, the method may include ion-exchange treatment of the glass phase material to introduce silver into the glass phase material.

[0090] Without being bound by any particular theory, it is believed that by selectively converting a portion of a glass-ceramic substrate into a glass phase material, the surface of the glass-ceramic substrate can possess tunable ion exchange capacity and efficiency, which provides greater flexibility and control in developing articles with desired properties. For example, the glass phase material can have a higher IOX rate and / or IOX capacity than the glass-ceramic material, thereby selectively exchanging more ions with the glass phase material. The increased silver concentration in the glass phase material can be used to adjust the refractive index in applications such as the transparent diffusers discussed herein, or to increase the antimicrobial activity of articles including the glass phase material. Conventional articles (glass or glass-ceramics) can comprise a homogeneous material with similar ion exchange rates and efficiency across the entire surface of the article, thereby limiting the tunability of the ion exchange rate of conventional articles. Furthermore, conventional antimicrobial glass-based articles may only store a limited amount of silver ions in the glass, limited by the available exchangeable ions, thereby limiting their antimicrobial efficacy.

[0091] In embodiments, the ion exchange treatment may involve contacting the glass phase material with a molten salt solution comprising silver. In embodiments, the molten salt solution may include KNO3, NaNO3, and AgNO3.

[0092] In one embodiment, the ion exchange treatment may include contacting the glass phase material with the molten salt solution for a period of time less than or equal to 12 hours, such as less than or equal to 10 hours, less than or equal to 8 hours, less than or equal to 6 hours, or less than or equal to 4 hours. In another embodiment, the ion exchange treatment may include contacting the glass phase material with the molten salt solution for a period of time greater than or equal to 5 minutes, greater than or equal to 30 minutes, greater than or equal to 1 hour, or greater than or equal to 2 hours.

[0093] During the ion exchange process, the molten salt solution can be at a high temperature. High temperature can increase the ion exchange rate. In one or more embodiments, the temperature of the molten salt solution is greater than or equal to 250°C and less than or equal to 500°C, for example, greater than or equal to 250°C and less than or equal to 450°C, greater than or equal to 250°C and less than or equal to 450°C, greater than or equal to 300°C and less than or equal to 400°C, greater than or equal to 250°C and less than or equal to 350°C, and any and all subranges formed by the aforementioned endpoints.

[0094] Figure 9 The diagram depicts a method for forming an article of articles according to embodiments described herein. Figure 9 In this process, the glass-ceramic substrate 910 undergoes condition 920 to form an intermediate substrate 930, such that at least a portion of the first surface of the glass-ceramic substrate 910 is converted into a glass phase material 940, and at least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material 950. The intermediate substrate 930 is then subjected to ion exchange treatment under condition 960 to form an article 970, such that silver is introduced into the glass phase material 940 to form a silver-containing glass phase material 980.

[0095] Example

[0096] The embodiments will be further illustrated by the following examples. It should be understood that these examples are not limited to the embodiments described above.

[0097] Example 1 — Forming a laser-treated glass-ceramic substrate

[0098] In Example 1, the laser-treated glass-ceramic substrate is formed from an initial glass-ceramic substrate. An initial glass-ceramic substrate according to Table 1 is provided. The initial glass-ceramic substrate of Example 1 comprises a lithium feldspar crystalline phase (Li2O-Al2O3-8SiO2), a lithium disilicate crystalline phase (Li2O-2SiO2, "LS2"), a lithium phosphate crystalline phase (Li3O4P, "L3P"), and a glass phase.

[0099] Table 1

[0100]

[0101] The initial glass-ceramic substrate was then treated with an ultrafast laser system (Pharos, Light Conversion) to convert at least a portion of the substrate's surface into a glassy phase region, thereby forming a laser-treated glass-ceramic substrate. Specifically, the center wavelength, pulse width, and repetition rate of the diode-pumped solid-state laser were set to 1030 nm, 300 fs, and 200 kHz, respectively. The laser's output power (maximum) was 4 W, and the actual power used for fabrication was approximately 10 μJ / pulse. The laser beam was manipulated using a galvanometer scanner and focused onto the initial glass-ceramic substrate through a conventional F-θ lens with a focal length of 80 mm. At the focal point, the spot size in air was approximately 17 μm. The initial glass-ceramic substrate sample was rapidly scanned at a pitch of 25 μm using a crosshair method. The scanner speed was set to 500 mm / s, which caused a portion of the glass-ceramic substrate's surface to be converted into a glassy phase region, thus forming the laser-treated glass-ceramic substrate. Because the laser treatment is focused on the surface of the glass-ceramic substrate, only the glass-ceramic surface at the focal point is transformed into a glass phase region, while the remaining bulk material remains glass-ceramic. The laser-treated glass-ceramic substrate is then further characterized.

[0102] The laser-treated glass-ceramic substrate was characterized using scanning electron microscopy (SEM) imaging, as shown in Figure 10. Figure 10A A cross-sectional view of a laser-treated glass-ceramic substrate is shown (scale bar: 10 μm). Figure 10B An enhanced cross-sectional view (scale bar 1 μm) of a laser-treated glass-ceramic substrate 710 is shown, and Figure 10C A top view (scale bar 10 μm) of a laser-treated glass-ceramic substrate is shown. As shown in Figure 10, the laser treatment of the initial glass-ceramic substrate produces a concave surface feature comprising a glass phase region 400 with a crescent-shaped cross-section positioned on the glass-ceramic body 420. The thickness of the glass phase layer is approximately 3 μm.

[0103] The optical parameters and surface morphology of the laser-treated glass-ceramic substrates were characterized by measuring haze, transmittance (“Trans”), gloss (at 20°, 60°, and 85°), Ra, Rq, and Rsk. These measurement results are summarized in Table 2.

[0104] Table 2.

[0105]

[0106] Example 2 — Modified laser conditions for forming laser-treated glass-ceramic substrates

[0107] In Example 2, two different laser-treated glass-ceramic substrates were formed from the initial glass-ceramic substrate of Example 1. The laser-treated glass-ceramic substrate of Example 2-1 was formed according to the laser treatment parameters of Example 1. The laser-treated glass-ceramic substrate of Example 2-2 was formed according to the laser treatment parameters of Example 1, except that in Example 2-2, the actual power used for manufacturing was reduced to approximately 6 μJ / pulse.

[0108] Example 3 — Chemical etching of laser-treated glass-ceramic substrates

[0109] In Example 3, the laser-treated glass-ceramic substrates of Examples 2-1 and 2-2 were treated with a chemical etchant to produce the laser-treated and chemically etched glass-ceramic substrates of Examples 3-1 and 3-2, respectively. Specifically, Examples 2-1 and 2-2 were treated with an etchant solution (50 wt.% NaOH) at 112°C for 3 hours.

[0110] Example 4 — Silver ion exchange treatment of glass-ceramic substrates after laser treatment and laser treatment and chemical etching

[0111] In Example 4, the laser-treated glass-ceramic substrates of Examples 2-1 and 2-2, and the laser-treated and chemically etched glass-ceramic substrates of Examples 3-1 and 3-2, were subjected to ion exchange at 390°C for 1 hour with a molten salt solution containing silver to produce silver-ion-exchanged glass-ceramic substrates. Specifically, Examples 2-1, 2-2, 3-1, and 3-2 were treated in a molten salt solution containing 42.5 wt.% KNO3, 42.5 wt.% NaNO3, 5 wt.% AgNO3, and 0.5 wt.% silica. The silver concentration in the glass phase region of the glass-ceramic substrates was determined by glow discharge photoemission spectroscopy (GDOES). The silver concentration in the glass phase region of the glass-ceramic substrates was quantified at a depth of 200 nm within the glass phase region and is summarized in Table 3.

[0112] Table 3

[0113]

[0114] Example 5 — Characterization of glass-ceramic substrates

[0115] In Example 5, Examples 2-1, 2-2, 3-1, and 3-2, as well as Example 4, are further characterized. The laser-treated glass-ceramic substrates of Examples 2-1 and 2-2, before and after the silver ion exchange treatment in Example 4, and the laser-treated and chemically etched glass-ceramic substrates of Examples 3-1 and 3-2, are characterized and summarized in Table 4.

[0116] Table 4

[0117]

[0118] As shown in Table 4, forming a glass phase region in the glass-ceramic substrate and subsequently performing ion exchange treatment on the silver in the glass phase region provides low glitter in the glass phase region of the glass-ceramic substrate. Furthermore, compared to glass-ceramic substrates without chemical etching (Examples 2-1 and 2-2), chemical etching prior to silver ion exchange treatment results in reduced gloss and glitter (Examples 3-1 and 3-2). In other words, the glass-ceramic substrates disclosed herein can be further processed to optimize the desired haze, gloss, and glitter.

[0119] The laser-treated glass-ceramic substrates of Examples 2-1 and 2-2, and the laser-treated and chemically etched glass-ceramic substrates of Examples 3-1 and 3-2 were imaged using SEM imaging, as shown in Figure 11. Figure 11A A top view (scale bar 50 μm) of the laser-treated glass-ceramic substrate of Example 2-1 is shown. Figure 11B A top view (scale bar 50 μm) of a glass-ceramic substrate of Example 3-1 that has undergone laser treatment and chemical etching is shown. Figure 11C A top view (scale bar 50 μm) of a laser-treated glass-ceramic substrate of Example 2-2 is shown. Figure 11D A top view (scale bar 50 μm) of a glass-ceramic substrate of Example 3-2 that has undergone laser treatment and chemical etching is shown.

[0120] Elemental analysis was used to further characterize the laser-treated glass-ceramic substrate of Example 2-1 after ion exchange treatment according to Example 4, to quantify silver deposition in the glass phase region and the glass-ceramic region of the glass-ceramic substrate, as shown in Figure 12. Specifically, scanning electron microscopy energy-dispersive X-ray spectroscopy was performed at a first point 1210 in the glass phase region and a second point 1220 within the glass-ceramic portion of the glass-ceramic substrate, as shown in Figure 12. Figure 12A As shown in the image. Figure 12B The figure shows an elemental analysis of the first point 1210 in the glass phase region using EDS. Figure 12B The peak value of 1230 is caused by silver. Figure 12C The figure shows an elemental analysis of the second point 1220 within the glass-ceramic region of the glass-ceramic substrate. The EDS plot was analyzed using a standard-free quantitative procedure, with the mol% of SiO2, Al2O3, ZrO2, P2O5, and Ag2O normalized to 100% by oxide, and reported in Table 5. Figure 12B , Figure 12C As shown in Table 5, the glass phase region of the glass-ceramic substrate has significantly more silver than the glass-ceramic region of the glass-ceramic substrate.

[0121] The compositional difference between the glass-ceramic region and the glass phase region is considered to play a significant role in the observed ion exchange rate and the resulting increase in Ag₂O concentration in the glass phase region. Although the initial glass-ceramic substrate contains approximately 22 mol.% Li₂O, the amount of ion-exchangeable Li₂O is much smaller because approximately 18 mol% of Li₂O is in an inactive (non-ion-exchangeable) crystalline phase. After the glass phase region is formed on the surface of the glass-ceramic substrate, all Li₂O in the glass phase region becomes active (ion-exchangeable) and can exchange with silver. Therefore, a significantly larger amount of Ag₂O can be stored in the glass phase region during the ion exchange process. Thus, the method described herein for selectively forming glass phase regions on the glass-ceramic substrate and subsequently ion-exchanging the entire substrate results in selective ion exchange of silver in the glass phase region.

[0122] Table 5

[0123]

[0124] Example 6 — Antimicrobial efficacy of glass-ceramic substrates

[0125] In Example 6, the antimicrobial efficacy of Examples 2-1 and 3-1 after ion exchange treatment according to Example 4 was evaluated using a test method published by the EPA as "Test Method for Efficacy of Copper Alloy Surfaces as a Bactericide". Detailed information is also provided herein, with the steps numbered according to the EPA protocol:

[0126] 1. Stock Culture: Initiate a new stock culture from ATCC lyophilized culture at least every 18 months. Open the lyophilized ampoule of the organism according to the manufacturer's instructions.

[0127] 2. Using a test tube containing 5 to 6 mL of trypsin soybean broth (TSB), aseptically extract 0.5 to 1.0 mL of the culture and rehydrate the lyophilized culture. Aseptically transfer the entire rehydrated precipitate back into the original culture tube. Mix thoroughly. Incubate the liquid culture at 36±1℃ for 24±2 hours.

[0128] 3. After incubation, streak a loopful of the suspension onto trypsin-soybean agar (TSA) to obtain isolated colonies. Incubate the plates at 36±1℃ for 18 to 24 hours.

[0129] 4. Select 3 to 5 isolated colonies from the test organism and resuspend them in 1 mL TSB. For Staphylococcus aureus, select only golden-yellow colonies. Spread 0.1 mL of the suspension onto each of 6 to 10 TSA culture plates using the plate spreading method. Incubate the plates at 36 ± 1 °C for 18 to 24 h.

[0130] 5. After incubation on agar plates, place approximately 5 mL of sterile cryoprotectant solution on the surface of each plate. Using a sterile applicator, resuspend the growth in the cryoprotectant solution without damaging the agar surface. Pipette the suspension from the plate into a sterile container large enough to hold approximately 30 mL. Repeat the growth collection process with the remaining plates, continuing to add suspension to the containers (using more than one tube of suspension if necessary). Thoroughly mix the contents of one or more containers; if using more than one container, collect the containers before aliquoting the culture. Immediately after mixing, aliquot 0.5 to 1 mL of the collected suspension into cryovials; these are the frozen stock cultures.

[0131] 6. Store the frozen vials at -70±5℃ for up to 18 months, then restart the stock culture with new lyophilized culture.

[0132] 7. While freezing, perform quality control checks on the collected cultures. For example, streak one loopful of bacteria onto blood agar plates and selective media such as mannitol agar (MSA) and cetrimide. Incubate all plates at 36±1°C for 24±2 hours. Record the colony morphology (including no growth) observed on the blood agar and selective media plates. Gram stain the growths obtained from the blood agar plates and observe the Gram reaction using a bright-field microscope (oil immersion) at 1000x magnification.

[0133] Test culture

[0134] 8. For Staphylococcus aureus, thaw a single frozen stock culture vial at room temperature and briefly vortex to mix. Each vial should be used only. Add 20 μL of the thawed stock to a test tube containing 10 mL TSB and then vortex to mix. Incubate at 36 ± 1 °C for 18 to 24 hours. After incubation, use the liquid culture to prepare the final test suspension. Briefly vortex the culture before use.

[0135] 9. Dilute the culture with phosphate-buffered saline (PBS) or concentrate it appropriately to achieve the target vector count (4 to 5 logs / vector). Centrifuge the liquid culture for 18 to 24 h to achieve the desired viable cell level on the dried vector. Centrifuge at approximately 5000 gN for 20 ± 5 min and resuspend the precipitate in 6 mL of 1X PBS. Note: Remove the supernatant without disturbing the precipitate. For Staphylococcus aureus, use vortexing or repeated tapping / bumping on a hard surface to disperse the precipitate completely, then resuspend it in 6 mL. If necessary, add 1 mL of PBS to the precipitate to aid dispersion.

[0136] 10. The purity of the final test culture (containing contaminant load) should be determined by streaking on TSA containing 5% sheep blood or other suitable agar plates, incubating (36±℃, 48±4 hr), and checking purity.

[0137] 11. Determine the titer of the final test culture (including contaminant load) for reference. Spread the dilution on a TSA plate or other suitable medium and incubate (36±1°C, 24 to 48 hr) and count. Calculate the colony count to determine the number of organisms per mL of inoculum at the start of the test (i.e., CFU / mL).

[0138] Contaminated load

[0139] 12. Add 0.25 ml of fetal bovine serum (FBS) and 0.05 ml of Triton X-100 to 4.70 ml of bacterial suspension to obtain a 5% FBS and 0.01% Triton X-100 contamination load. After adding the contamination load, vortex the final test suspension for 10 seconds just before use.

[0140] Efficacy testing procedure

[0141] 13. Evaluate the treated test vector and the untreated control vector in the test organism.

[0142] 14. The coated control carrier should be evaluated simultaneously with the coated test carrier.

[0143] 15. Exposure of the inoculum to the carrier surface (contact time) begins immediately after inoculation; therefore, the contact time is calculated from the moment the final test suspension (containing the contaminated load) is placed on the carrier.

[0144] 16. Record the start of the contact time and, using calibrated pipettes (positive displacement pipettes are acceptable), inoculate each vector with 20 μL of the final test culture at staggered intervals.

[0145] 17. Spread the inoculum back and forth on the carrier surface, ensuring complete coverage. Use a curved pipette tip to spread it as far as possible to the edges of the carrier. Use appropriate time intervals (e.g., 30 seconds) to allow sufficient time for careful spreading of the inoculum.

[0146] 18. Exposure should begin immediately after vector inoculation. Record laboratory temperature and relative humidity during the two-hour exposure period.

[0147] 19. Allow the culture medium to remain in a horizontal position on a Petri plate for 120 ± 5 minutes under ambient conditions.

[0148] 20. After the exposure period, aseptically transfer the vector sequentially to 20 mL of Letheen broth (neutralizing solution) – this represents 10 0 Dilution

[0149] a. For samples larger than 1"×1", apply a plastic sticker (prepared using a Silhouette cutter system) with a 1"×1" opening to the surface to obtain the correct test area. Add these to a Whirl Pak sampling bag containing 20 mL of neutralizing agent for sonication (next step).

[0150] 21. After all carriers have been transferred to the neutralizing agent, sonicate for 5 minutes ± 30 seconds to suspend and vortex mix any surviving material from the carriers.

[0151] 22. Within 30 minutes after ultrasonic treatment, prepare a series of dilutions (10...) of the neutralization solution. 0 (Dilution), for treated carriers, dilute to 10. -3 Transfer the coated control vector to neutralization subculture medium and spread the appropriate dilution twice to obtain a countable number (maximum 300 colonies per plate). Incubate and count the treated vector plates.

[0152] 23. Take 10 0 1.0 mL aliquots of the diluted sample and 10 0 Up to 10 -3 0.10 mL aliquots of the diluted sample were spread twice on a TSA culture plate using standard plate coating technique.

[0153] 24. Incubate the culture plate at 36±1℃ for 48±4 hours.

[0154] 25. After incubation, count the colonies and record the results.

[0155] 26. Some organisms may require alternative culture conditions. If necessary, culture conditions can be modified to suit the test organism. If required, subculture plates can be stored at 2 to 8°C for up to 3 days prior to counting.

[0156] The various features described in the specification can be combined in any and all combinations, such as those listed in the following examples.

[0157] Example 1. An article is provided, the article comprising: a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; and wherein the one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase region.

[0158] Example 2. An article of Example 1 is provided, wherein one or more glass phase regions on a first surface have an Ag2O concentration of at least 5 mol.% at all depths therein.

[0159] Example 3. An article of Example 1 or Example 2 is provided, wherein one or more glass phase regions on a first surface comprise an amorphous glass material of silver ion exchange (IOX).

[0160] Example 4. An article of any one of Examples 1 to 3 is provided, wherein one or more glass phase regions on the first surface of the glass-ceramic substrate are textured.

[0161] Example 5. An article of any one of Examples 1 to 3 is provided, wherein a portion of the first surface excluding one or more glass phase regions comprises one or more glass ceramic regions containing glass ceramic material.

[0162] Example 6. An article of Example 5 is provided, wherein one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of a glass-ceramic substrate.

[0163] Example 7. An article of Example 5 or Example 6 is provided, wherein one or more glass-ceramic regions therein have an Ag2O concentration of less than 5 mol.% at all depths.

[0164] Example 8. An article of any one of Examples 1 to 7 is provided, wherein at least a portion of one or more glass phase regions is concave.

[0165] Example 9. An article of any one of Examples 1 to 8 is provided, wherein the article has a color ΔE equal to or less than 10 when compared with other equivalent articles that do not contain Ag2O.

[0166] Example 10. An article of any one of Examples 1 to 9 is provided, wherein the total surface area of ​​one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface.

[0167] Example 11. An article of any one of Examples 1 to 10 is provided, wherein the article has a scintillation of less than or equal to 3% at 140 ppi in a region including the glass phase region.

[0168] Example 12. An article of any one of Examples 1 to 11 is provided, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a haze of greater than or equal to 5% and less than or equal to 40%.

[0169] Example 13. An article of any one of Examples 1 to 12 is provided, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a coupled image sharpness (DOI) of less than or equal to 20%.

[0170] Example 14. An article of any one of Examples 1 to 13 is provided, wherein a portion of the glass phase region of the glass-ceramic substrate has a gloss of 60° greater than or equal to 20 and less than or equal to 80.

[0171] Example 15. An article of any one of Examples 1 to 14 is provided, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a surface roughness R greater than or equal to 40 nanometers. q .

[0172] Example 16. An article of any one of Examples 1 to 15 is provided, wherein a portion of the article comprising a glass phase region of a glass-ceramic substrate has a luminosity of less than or equal to 5% at 140 ppi in the region comprising the glass phase region.

[0173] Example 17. An article of any one of Examples 1 to 16 is provided, wherein, according to the EPA dry test with Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate of greater than or equal to 2.

[0174] Example 18. An article is provided, the article comprising: a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; and wherein the one or more glass phase regions have an Ag₂O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase regions; wherein the one or more glass phase regions on the first surface of the glass-ceramic substrate are textured; wherein a portion of the first surface excluding the one or more glass phase regions comprises one or more glass-ceramic regions containing glass-ceramic material; and wherein the one or more glass-ceramic regions have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate.

[0175] Example 19. An article of Example 18 is provided, wherein: a portion of the article comprising the glass phase region of the glass-ceramic substrate has a gloss level of less than or equal to 3% at 140 ppi; a portion of the article comprising the glass phase region of the glass-ceramic substrate has a haze level of greater than or equal to 5% to less than or equal to 40%; a portion of the article comprising the glass phase region of the glass-ceramic substrate has a coupled image sharpness (DOI) of less than or equal to 20%; a portion of the article comprising the glass phase region of the glass-ceramic substrate has a gloss level of greater than or equal to 20 and less than or equal to 80 at 60°; and a portion of the article comprising the glass phase region of the glass-ceramic substrate has a surface roughness R of greater than or equal to 40 nanometers. q Furthermore, according to the EPA dry test using Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate greater than or equal to 2.

[0176] Example 20. An article of Example 18 or Example 19 is provided, wherein: one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at all depths therein; the total surface area of ​​one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface; the article has a color ΔE equal to or less than 10 when compared with other equivalent articles without Ag2O; and at least a portion of one or more glass phase regions is concave.

[0177] Example 21. An article is provided, the article comprising: a glass-ceramic substrate, the glass-ceramic substrate including a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and the glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions comprise amorphous glass; wherein a portion of the first surface excluding the one or more glass phase regions comprises one or more glass-ceramic regions containing glass-ceramic material; wherein, according to an EPA dry test with Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate greater than or equal to 2.

[0178] Example 22. An article of Example 21 is provided, wherein: a portion of the article comprising the glass phase region of the glass-ceramic substrate has a scintillation of less than or equal to 5% at 140 ppi; a portion of the article comprising the glass phase region of the glass-ceramic substrate has a haze of greater than or equal to 5% to less than or equal to 40%; a portion of the article comprising the glass phase region of the glass-ceramic substrate has a coupled image sharpness (DOI) of less than or equal to 20%; and a portion of the article comprising the glass phase region of the glass-ceramic substrate has a gloss of 60° greater than or equal to 20 and less than or equal to 80.

[0179] Example 23. An article of Example 21 or Example 22 is provided, wherein: one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at all depths therein; the total surface area of ​​the one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface; the article has a color ΔE equal to or less than 10 when compared with other equivalent articles without Ag2O; one or more glass-ceramic regions have an Ag2O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate; and at least a portion of the one or more glass phase regions is concave.

[0180] Example 24. A consumer electronics product is provided, the consumer electronics product comprising: a housing including a front surface, a rear surface, and a side surface; electronic components at least partially located within the housing, the electronic components including at least one of a display and a sensor, the display being located at or adjacent to the front surface of the housing, and the sensor being located at or adjacent to the front or rear surface of the housing; and at least one cover disposed over at least one of the display and the sensor, wherein at least one of at least a portion of the cover and at least one of the rear surface comprises an article of manufacture according to any one of Examples 1 to 23.

[0181] Example 25. A structure is provided comprising an article of any one of Examples 1 to 23, wherein the structure is a transparent lamp, a transparent display, a head-up display, a head-mounted display, a transparent backlight, a touch screen display, a liquid crystal display, an aquarium, a laser-based reflective head-up display, a wearable display, a window, a vehicle dashboard, a car window, a waveguide, a light guide, or a building window.

[0182] Example 26. A structure is provided, the structure comprising an article of any one of Examples 1 to 23, wherein the structure is a microlens array.

[0183] Example 27. A glass screen protector for a smartphone is provided, the glass screen protector comprising: a cover glass; and an adhesive backing disposed on the cover glass, wherein the adhesive backing is for attachment to the smartphone, and further wherein at least one portion of the cover glass comprises an article of any one of Examples 1 to 23.

[0184] Example 28. A method for forming an article, the method comprising: converting at least a portion of a first surface of a glass-ceramic substrate into a glass phase material, wherein the glass-ceramic substrate includes a first surface and a second surface opposite to the first surface, and wherein at least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material; and subjecting the glass phase material to ion exchange treatment to introduce silver into the glass phase material.

[0185] Example 29. The method of Example 28 is provided, wherein the article comprises a glass phase region containing a glass phase material, and wherein the glass phase region has an Ag2O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase region.

[0186] Example 30. A method of Example 28 or Example 29 is provided, wherein the article comprises a glass phase region containing a glass phase material, and wherein the entire glass phase region has an Ag2O concentration of at least 5 mol.%

[0187] Example 31. A method of any one of Examples 28 to 30 is provided, wherein converting at least a portion of a first surface of a glass-ceramic substrate into a glass phase material comprises directing radiation from a laser to the first surface of the glass-ceramic substrate to form a glass phase material.

[0188] Example 32. A method of any one of Examples 28 to 31 is provided, wherein the ion exchange treatment includes contacting a glass phase material with a molten salt solution comprising silver.

[0189] Example 33. The method of Example 32 is provided, wherein the molten salt solution comprises KNO3, NaNO3 and AgNO3.

[0190] Example 34. The method of claim 32 or claim 33 is provided, wherein the molten salt solution has a temperature of at least 250°C.

[0191] Example 35. A method of any one of Examples 32 to 34 is provided, wherein the ion exchange treatment lasts for a duration of less than 12 hours.

[0192] Example 36. A method of any one of Examples 28 to 35 is provided, the method further comprising wet etching of a glass phase material prior to ion exchange treatment, wherein wet etching comprises contacting at least a portion of the glass phase material with an etchant.

[0193] Example 37. The method of Example 36 is provided, wherein the etchant comprises hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or a combination of two or more thereof.

[0194] Example 38. A method of any one of Examples 28 to 37 is provided, wherein the valley of the surface of the glass phase material is located less than 10 micrometers below the surface of the first surface that has not been converted into the glass phase material.

Claims

1. An article comprising: A glass-ceramic substrate, the glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and The glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions include amorphous glass; and The one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase region.

2. The article of claim 1, wherein the one or more glass phase regions on the first surface have an Ag₂O concentration of at least 5 mol.% at all depths therein.

3. The article of claim 1 or claim 2, wherein the one or more glass phase regions on the first surface comprise amorphous glass material with silver ion exchange (IOX).

4. The article of claim 1 to 3, wherein the one or more glass phase regions on the first surface of the glass-ceramic substrate are textured.

5. The article of any one of claims 1 to 4, wherein a portion of the first surface excluding the one or more glass phase regions comprises one or more glass-ceramic regions containing the glass-ceramic material.

6. The article of claim 5, wherein the one or more glass-ceramic regions have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate.

7. The article of claim 5 or claim 6, wherein the one or more glass-ceramic regions therein have an Ag₂O concentration of less than 5 mol.% at all depths.

8. The article of any one of claims 1 to 7, wherein at least a portion of the one or more glass phase regions is concave.

9. The article of any one of claims 1 to 8, wherein the article has a color ΔE equal to or less than 10 when compared with other equivalent articles that do not contain Ag2O.

10. The article of any one of claims 1 to 9, wherein the total surface area of ​​the one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface.

11. The article of any one of claims 1 to 10, wherein the article has a scintillation of less than or equal to 3% at 140 ppi in the region including the glass phase region.

12. The article of any one of claims 1 to 11, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a haze of greater than or equal to 5% and less than or equal to 40%.

13. The article of any one of claims 1 to 12, wherein a portion of the article of the glass-ceramic substrate including the glass phase region has a coupled image sharpness (DOI) of less than or equal to 20%.

14. The article of any one of claims 1 to 13, wherein a portion of the glass phase region of the glass-ceramic substrate has a gloss of 60° greater than or equal to 20 and less than or equal to 80.

15. The article of any one of claims 1 to 14, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a surface roughness R greater than or equal to 40 nanometers. q .

16. The article of any one of claims 1 to 15, wherein a portion of the article comprising the glass phase region of the glass-ceramic substrate has a luminosity of less than or equal to 5% at 140 ppi in the region comprising the glass phase region.

17. The article of any one of claims 1 to 16, wherein, according to the EPA dry test with Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate greater than or equal to 2.

18. An article of manufacture comprising: A glass-ceramic substrate, the glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and The glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions include amorphous glass; and The one or more glass phase regions have an Ag₂O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase region; The one or more glass phase regions on the first surface of the glass-ceramic substrate are textured; The portion of the first surface that does not include the one or more glass phase regions includes one or more glass-ceramic regions containing the glass-ceramic material; and The one or more glass-ceramic regions therein have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate.

19. The article of manufacture according to claim 18, wherein: A portion of the article comprising the glass phase region of the glass-ceramic substrate has a luminance of less than or equal to 3% at 140 ppi. The glass-ceramic substrate, including a portion of the glass phase region, has a haze of greater than or equal to 5% and less than or equal to 40%. A portion of the article comprising the glass phase region of the glass-ceramic substrate has a coupled image sharpness (DOI) of less than or equal to 20%. A portion of the article comprising the glass phase region of the glass-ceramic substrate has a gloss of 60° that is greater than or equal to 20 and less than or equal to 80. The glass-ceramic substrate, including a portion of the glass phase region article, has a surface roughness R greater than or equal to 40 nanometers. q ;and According to the EPA dry test conducted with Staphylococcus aureus, the first surface of the article exhibited a logarithmic kill rate of greater than or equal to 2.

20. The article of manufacture according to claim 18 or claim 19, wherein: The one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at all depths therein; The total surface area of ​​the one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface; When compared with other equivalent articles that do not contain Ag2O, the article has a color ΔE equal to or less than 10; and At least a portion of the one or more glass phase regions is concave.

21. An article comprising: A glass-ceramic substrate, the glass-ceramic substrate comprising a first surface and a second surface, wherein the first surface is opposite to the second surface, and wherein at least 70 wt.% of the glass-ceramic substrate comprises a glass-ceramic material; and The glass-ceramic substrate further includes one or more glass phase regions on the first surface, wherein the one or more glass phase regions include amorphous glass; The portion of the first surface that does not include the one or more glass phase regions includes one or more glass ceramic regions containing the glass ceramic material; According to the EPA dry test conducted with Staphylococcus aureus, the first surface of the article exhibits a logarithmic kill rate of greater than or equal to 2.

22. The article of manufacture according to claim 21, wherein: A portion of the article comprising the glass phase region of the glass-ceramic substrate has a luminosity of less than or equal to 5% at 140 ppi. A portion of the article comprising the glass phase region of the glass-ceramic substrate has a haze of greater than or equal to 5% and less than or equal to 40%. A portion of the article comprising the glass phase region of the glass-ceramic substrate has a coupled image sharpness (DOI) of less than or equal to 20%; and A portion of the article comprising the glass phase region of the glass-ceramic substrate has a gloss of 60°, which is greater than or equal to 20 and less than or equal to 80.

23. The article of manufacture according to claim 21 or claim 22, wherein: The one or more glass phase regions have an Ag2O concentration of at least 5 mol.% at all depths therein; The total surface area of ​​the one or more glass phase regions is 50% to 100% of the total surface area of ​​the first surface; When compared with other equivalent articles that do not contain Ag2O, the article has a color ΔE equal to or less than 10; The one or more glass-ceramic regions have an Ag₂O concentration of less than 5 mol.% at a depth of 200 nm below the first surface of the glass-ceramic substrate; and At least a portion of the one or more glass phase regions is concave.

24. A consumer electronics product, the consumer electronics product comprising: The housing includes a front surface, a rear surface, and side surfaces; An electronic component, at least partially located within the housing, the electronic component including at least one of a display and a sensor, the display being located at or adjacent to the front surface of the housing, and the sensor being located at or adjacent to the front or rear surface of the housing; and At least one cover, said at least one cover being disposed above at least one of the display and the sensor. At least one of the cover and at least a portion of the rear surface comprises an article of any one of claims 1 to 23.

25. A structure comprising an article of any one of claims 1 to 23, wherein the structure is a transparent luminaire, a transparent display, a head-up display, a head-mounted display, a transparent backlight, a touchscreen display, a liquid crystal display, an aquarium, a laser-based reflective head-up display, a wearable display, a window, a vehicle dashboard, an automotive window, a waveguide, a light guide, or a building window.

26. A structure comprising an article of any one of claims 1 to 23, wherein the structure is a microlens array.

27. A glass screen protector for a smartphone, the glass screen protector comprising: Cover with glass; and An adhesive backing, which is disposed on the cover glass, The adhesive backing is used to attach to the smartphone, and In addition, at least one portion of the cover glass comprises an article of any one of claims 1 to 23.

28. A method of forming an article, the method comprising: At least a portion of the first surface of a glass-ceramic substrate is converted into a glass phase material, wherein the glass-ceramic substrate includes the first surface and a second surface opposite to the first surface, and wherein at least 70 wt.% of the glass-ceramic substrate remains a glass-ceramic material; as well as The glass phase material is subjected to ion exchange treatment to introduce silver into the glass phase material.

29. The method of claim 28, wherein the article comprises a glass phase region containing the glass phase material, and wherein the glass phase region has an Ag2O concentration of at least 5 mol.% at a depth of 200 nm below the surface of the glass phase region.

30. The method of claim 28 or claim 29, wherein the article comprises a glass phase region containing the glass phase material, and wherein the entire glass phase region has an Ag2O concentration of at least 5 mol.%.

31. The method according to any one of claims 28 to 30, wherein converting at least a portion of the first surface of the glass-ceramic substrate into the glass phase material comprises directing radiation from a laser to the first surface of the glass-ceramic substrate to form the glass phase material.

32. The method according to any one of claims 28 to 31, wherein the ion exchange treatment comprises contacting the glass phase material with a molten salt solution comprising silver.

33. The method of claim 32, wherein the molten salt solution comprises KNO3, NaNO3, and AgNO3.

34. The method according to claim 32 or claim 33, wherein the molten salt solution has a temperature of at least 250°C.

35. The method according to any one of claims 32 to 34, wherein the ion exchange treatment lasts for a duration of less than 12 hours.

36. The method according to any one of claims 28 to 35, the method further comprising wet etching the glass phase material prior to the ion exchange treatment, wherein the wet etching comprises contacting at least a portion of the glass phase material with an etchant.

37. The method of claim 36, wherein the etchant comprises hydrofluoric acid, ammonium bifluoride, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide, or a combination of two or more thereof.

38. The method according to any one of claims 28 to 37, wherein the valley of the surface of the glass phase material is located less than 10 micrometers below the surface of the first surface that has not been converted into the glass phase material.

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