KR102411111B1 - Glass Articles Exhibiting Improved Fracture Performance - Google Patents

Abstract

Embodiments of the present disclosure include a first surface defining a thickness t of about 1.1 mm or less and a second surface opposing the first surface; a tempered glass article comprising a compressive stress layer extending from said first surface to a depth of compression (DOC) greater than about 0.11 t; When the glass article breaks, the glass article breaks into a plurality of fragments having an aspect ratio of about 5 or less. In some embodiments, the glass article exhibits a co-biaxial flexural strength of greater than or equal to about 20 kgf after being ground to 90-grit SiC particles at a pressure of 25 psi for 5 seconds. Devices comprising the glass articles described herein and methods of making them are also disclosed.

Description

Glass Articles Exhibiting Improved Fracture Performance

This application claims priority to U.S. Provisional Patent Application No. 62/343,320, filed on May 31, 2016, the entire contents of which are incorporated herein by reference.

The present disclosure relates to glass articles exhibiting improved fracture performance, and more particularly, to glass articles exhibiting improved fracture patterns and dicing behavior.

Consumer electronic devices, including portable devices, such as smartphones, tablets, e-book readers and laptops, often incorporate tempered glass articles chemically for use as cover glass. Because the cover glass is bonded directly to a substrate, such as a touch-panel, display, or other structure, when a tempered glass article breaks, the article breaks into a stored storage product created by a combination of surface compressive stress and tensile stress underneath the surface of the glass. The energy can eject small debris or particles from the free surface. As used herein, the term fracture includes cracks and/or the formation of cracks. These small fragments may crack, particularly if the fracture occurs in a delayed manner in close proximity to the user's face (ie, eyes and ears) and if the user continues to use and touch the fractured surface, particularly It is a potential concern for device users when relatively long distances and fragments with sharp corners and edges are present, and therefore susceptible to minor cuts or abrasions.

Thus, when the glass article breaks, a glass exhibiting deformed fragmentation behavior, such as, for example, exhibiting improved dicing behavior, such as a dicing effect resulting in a shorter crack length and fewer ejected particles. There is a need for a product. In addition, there is also a need for glass articles that, upon breaking, release fewer fragments and fragments with less kinetic energy and momentum.

A first aspect of the present disclosure is a first surface defining a thickness t of less than or equal to about 1.1 mm and a second surface opposing the first surface, the compression of greater than about 0.11 t from the first surface. A tempered glass article comprising a compressive stress layer extending to a depth (DOC). In some embodiments, after the glass article is ruptured, the glass article comprises a plurality of fragments, wherein at least 90% of the plurality of fragments comprises about and an aspect ratio of 5 or less, and the glass article breaks into a plurality of fragments in less than 1 second.

In some embodiments, the tempered glass article exhibits an equibiaxial flexural strength of at least about 20 kgf after being ground to 90-grit SiC particles at a pressure of 25 psi for 5 seconds. In some embodiments, the tempered glass article may include breaks that, after the glass article breaks, at least 50% of the breaks extend only partially through the thickness.

A third aspect of the present disclosure provides, as described herein, a tempered glass substrate, a containment layer; and a support, wherein the device comprises a tablet, a transparent display, a mobile phone, a video player, an information terminal device, an electronic-reader, a laptop computer, or a non-transparent display.

A fourth aspect of the present disclosure is a housing having a front surface; an electrical component provided at least partially within the housing and comprising at least a controller, a memory, and a display; and a cover glass disposed on the front side of the housing and over the display, the cover glass comprising a tempered glass article as described herein.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be apparent to those skilled in the art from the following detailed description, or practice of the embodiments described herein, including the following detailed description, claims, as well as the appended drawings. will be easily recognized.

It is to be understood that both the foregoing background and the following detailed description are merely representative and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain the principles and operation of the various embodiments.

1A is a side view of a glass article in accordance with one or more embodiments;
1B is a side view of the glass article of FIG. 1A after breaking;
2 is a cross-sectional view through the thickness of a known thermally tempered glass-based article;
3 is a cross-sectional view through the thickness of a known chemically strengthened glass-based article;
4 is a cross-sectional view through the thickness of a strengthened glass-based article in accordance with one or more embodiments;
5 is a schematic cross-sectional view of a ring-on-ring apparatus;
6 is a schematic cross-sectional view of an embodiment of an apparatus used to perform an inverse ball (IBoS) test on sandpaper described in this disclosure;
7 is a schematic cross-sectional view of the main mechanisms for failure due to bending as well as introduction of damage typically occurring in glass-based articles used in mobile or portable electronic devices;
8 is a flowchart of a method for performing an IBoS test in the device described herein;
9A is a side view of the glass article of FIG. 1A including a hermetic layer;
9B is a side view of the glass article of FIG. 9A including a second hermetic layer;
10 is a front view of an electronic device incorporating one or more embodiments of glass articles described herein;
11 is a graph showing the AROR test results of Example 1;
12 is a graph showing the drop test results of Example 2;
13 is a plot showing the concentration of K ₂ O as a function of ion exchange depth for Example 4;
14 is a plot showing the stress profile of Example 4G;
15A-15D are broken images of Example 5;
16A-16D are images showing the readability of Example 6 after fracture at different viewing angles;
17 is a plot of stored tensile energy calculated as a function of ion-exchange time, for Example 7;
18 is a plot of calculated central tension as a function of ion-exchange time, for Example 7; and
19 is a plot showing the stress profile of Example 6, with compressive and tensile stresses plotted as a function of depth.

Reference will now be made in great detail to various embodiments, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. It is to be understood that the embodiments disclosed herein are representative only and each incorporates certain advantages of the present invention. With reference generally to the drawings, it will be understood that the examples are for the purpose of illustrating particular embodiments, and are not intended to limit the present disclosure or the claims appended thereto. The drawings are not necessarily to scale, and certain features and certain views of the drawings may be shown schematically or exaggerated to scale for clarity and conciseness.

In the following detailed description, the same reference numerals designate the same or corresponding parts throughout several figures shown in the figures. Also, unless otherwise stated, terms such as "upper", "lower", "outer", "internal", and the like are understood to be words of convenience and not to be construed as limiting terms. Additionally, where a group is described as comprising at least one of a group of elements and combinations thereof, the group includes, consists essentially of, or consists of any number of those elements recited individually or in combination with each other. , or may be made. Similarly, where a group is described as consisting of at least one of a group of elements and combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with one another. Unless otherwise stated, when recited, ranges of values include both the upper and lower limits of the range as well as any ranges therebetween. As used herein, "a" and "plural" are used without distinction, and unless otherwise stated, both "a" and "plural" mean "at least one" or "one or more". It is also understood that the various features disclosed herein and in the drawings may be used in any one and all combinations.

It is noted that the terms "substantially" and "about" may be utilized herein to denote a degree of inherent uncertainty that can be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to denote the extent to which a quantitative expression can vary from a specified criterion without resulting in a change in the basic function of the subject matter in question.

As used herein, the term "glass article" is used in its broadest sense to include any object made wholly or in part of glass. Glass articles include laminates of glass and non-glass materials, laminates of amorphous and crystalline materials, and glass-ceramics (including amorphous and crystalline phases). Unless otherwise noted, all compositions are expressed in mole percent (mol %).

As discussed herein, embodiments of glass articles may include tempered glass or glass ceramic materials that exhibit improved mechanical performance and reliability compared to known glass articles, particularly known cover glass articles. Embodiments of the glass articles described herein may exhibit fragmentation behavior not exhibited by known cover glass articles. In this disclosure, glass-based substrates, generally not strengthened, and glass-based articles generally refer to glass-based substrates that have been strengthened (eg, by ion exchange).

A first aspect of the present disclosure is that it exhibits the ability to fracture in a dense fracture pattern with a dicing effect similar to fully thermally tempered glass used in shower panels or automobile window panels. It relates to tempered glass products. In some embodiments, the fragments are intended to be less harmful to humans. These articles exhibit this behavior despite being chemically strengthened and having a thickness that is significantly less than that achievable by currently known thermal tempering processes. In some embodiments, the fragments are even smaller or finer than the fragments observed in known thermally tempered glass. For example, embodiments of the glass article may exhibit a "dicing" effect when the glass article breaks, such that the shards resemble cubes rather than splinters, as described in greater detail below in connection with FIG. 1A . , "diced" fragments have a small aspect ratio, and the fractured and as-formed surfaces form larger angles (ie, fewer blade-like or knife-like angles). do. In some instances, the diced fragments are limited to a maximum or longest dimension of no more than 2 millimeters (mm) in any direction of the major plane of the glass article. In some instances, when ruptured or after the glass article breaks, the glass article has about 10 or less or about 5 or less (eg, about 4.5 or less, about 4 or less, about 3.5 or less, or 3 or less, about 2.5 or less; and a plurality of fragments having an average aspect ratio of about 2 or less). In some embodiments, the average aspect ratio of the plurality of fragments ranges from about 1 to about 2. In some instances, at least about 90%, or at least about 80% of the plurality of fragments exhibit an average aspect ratio described herein. As used herein, the term “aspect ratio” refers to the ratio of the longest or largest dimension of a fragment to the shortest or smallest dimension of the fragment. The term “dimension” may include length, width, diagonal, or thickness. Glass articles that exhibit such fragments after breaking can be characterized herein as exhibiting “dicing” behavior.

1A and 1B , in one or more embodiments, a glass article 10 described herein will have a sheet shape having opposing major surfaces 12 , 14 and opposing minor surfaces 16 , 18 . can The at least one major surface 12 forms an “as-formed” surface of the glass article. When broken, a new surface created by the breakage of the glass article is formed (ie, a “fracture-generated” surface), as indicated by reference numeral 19 in FIG. 1B . The angle α between the fractured surface and the as-formed surface (after the glass article has broken) ranges from about 85 degrees to about 95 degrees or from about 88 degrees to about 92 degrees. In one or more embodiments, at least about 90% of the plurality of fragments in the glass article exhibits an angle between the as-formed surface and any fracture occurring surfaces after the glass article breaks.

In one or more embodiments, at least 50% (e.g., about 60% or more, about 70% or more, about 80% or more, or about 90% or more) of the plurality of fragments is 5 t or less, 4 t or less, or a maximum dimension of 3 t or less. In some instances, at least 50% (eg, at least about 60%, at least about 70%, at least about 80%, or at least about 90%) of the plurality of fragments comprise a maximum dimension that is less than twice the minimum dimension. In some embodiments, the largest dimension is no more than about 1.8 times the minimum dimension, no more than about 1.6 times the minimum dimension, no more than about 1.5 times the minimum dimension, no more than about 1.4 times the minimum dimension, no more than about 1.2 times the minimum dimension, or It is almost the same as the minimum dimension.

In one or more embodiments, at least 50% (eg, at least about 60%, at least about 70%, at least about 80%, or at least about 90%) of the plurality of fragments comprise a volume of about 10 mm 3 or less. In some embodiments, the volume may be about 8 mm 3 or less, about 5 mm 3 or less, or about 4 mm 3 or less. In some embodiments, the volume may range from about 0.1 mm 3 to about 1.5 mm 3 .

As used herein, the phrase “fortified product” includes products that have been chemically fortified, or chemically strengthened and thermally strengthened, but excludes products that have been only thermally strengthened. As shown in Figure 4, the tempered glass article exhibits a stress profile that can be characterized in terms of surface compressive stress (CS), central tension (CT) and depth of compression (DOC).

The stress profile exhibited by the tempered glass article of one or more embodiments can be distinguished between the stress profiles exhibited by the known thermally tempered glass article and the known chemically strengthened glass article. Traditionally, thermally tempered glass has been used to prevent breakage, where flaws can be introduced into the glass, which prevents the thermally tempered glass from propagating and thus preventing breakage. This is because it often presents a large CS layer (eg, about 21% of the total thickness of the glass) that is preventable. An example of a stress profile generated by thermal tempering is shown in FIG. 2 . In FIG. 2 , the heat treated glass article 100 includes a first surface 101 , a thickness t ₁ , and a surface CS 110 . Glass article 100 exhibits a decreasing CS from first surface 101 to DOC 130 , as defined herein, at which depth the stress changes from compressive to tensile stress, and CT 120 . to reach

Thermal tempering requires that a sufficient thermal gradient be formed between the core and surface of such a product to achieve thermal strengthening and desired residual stresses; glass articles with a thickness (t ₁ )). Products of this thickness are suitable for display (eg, consumer electronics, including cell phones, tablets, computers, navigation systems, and the like), architectural (eg, windows, shower panels, countertops, etc.), transportation (eg, automobiles, trains, aircraft, marine vessels, etc.), consumer electronics, packaging materials, or any application that requires good fracture resistance but thin and light-weight products. It is not desirable or practicable in the application.

Known chemically strengthened glass articles do not exhibit the stress profile of thermally tempered glass articles, although chemical strengthening is not limited by the thickness of the glass article in the same way as thermal tempering. An example of a stress profile generated by chemical strengthening (eg, by an ion exchange process) is shown in FIG. 3 . In FIG. 3 , the chemically strengthened glass article 200 includes a first surface 201 , a thickness t ₂ , and a surface CS 210 . Glass article 200 exhibits a decreasing CS from first surface 201 to DOC 230, as defined herein, at which depth the stress changes from compressive to tensile stress and to CT 220 reach As shown in FIG. 3 , this profile shows a CT region or flat CT region with constant or near constant tensile stress and, often, lower CT values, compared to the CT values shown in FIG. 2 .

The glass article of one or more embodiments of the present disclosure has a thickness (t) of less than about 3 mm (eg, about 2 mm or less, about 1.5 mm or less, or about 1.1 mm or less) and at least about 0.1 t from the first surface The compressive stress layer extending into the DOC is shown. As used herein, DOC refers to the depth at which stress in a glass article changes from compressive to tensile stress. In the DOC, the stress crosses from positive (compressive) stress to negative (tensile) stress (eg, 130 in FIG. 2 ), thus exhibiting a stress value of zero.

According to convention commonly used in the art, compression is expressed as a negative (<0) stress, and tension is expressed as a positive (>0) stress. However, throughout this description, CS is expressed as a positive or absolute value - ie, CS = |CS|, as listed herein.

In particular, the glass articles described herein exhibit a stress profile that is only achievable through tempering of thin and typically thick glass articles (eg, having a thickness of about 2 mm or 3 mm or greater). In some cases, the glass article exhibits a greater surface CS than the tempered glass article. In one or more embodiments, the glass article exhibits a greater depth of compressive layer, wherein CS decreases and increases more gradually than known chemically strengthened glass articles, such that the glass article or device comprising the same is rigid. , even when dropped on a rough surface, the glass article exhibits substantially improved fracture resistance. The glass articles of one or more embodiments exhibit greater CT values than some known chemically strengthened glass substrates.

CS, Orihara Industrial Co. , Ltd. (Japan), is measured by a surface stress meter (FSM) using a commercially available instrument such as FSM-6000. Surface stress measurements rely on accurate measurements of the stress optical modulus (SOC), which is related to the birefringence of the glass. SOC is ultimately measured according to a revised version of Procedure C described in ASTM Standard C770-98 (2013), entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the entire contents of which are hereby incorporated by reference. incorporated into Said amendment comprises the use of a glass disc as a specimen having a thickness of 5 to 10 mm and a diameter of 12.7 mm, wherein the disc is isotropic and homogeneous, and both parallel and polished, The core is drilled. The amendment also includes calculating the maximum applied force, Fmax. The force should be sufficient to create a compressive stress of at least 20 MPa. Fmax is calculated as follows:

Fmax = 7.854*D*h

here:

Fmax = Newton's force

D = diameter of disk

h = thickness of the light path.

For each applied force, the stress is calculated as:

σ _MPa = 8F/(π*D*h)

here:

F　 = Newton's force

D = diameter of disk

h = thickness of the light path.

CT values are measured using a scattering light polarizer (“SCALP” supplied by Glasstress Ltd., located in Tallinn, Estonia, under model number SCALP-04) and techniques known in the art. SCALP can also be used to measure DOC, as will be described in more detail below.

In some embodiments, the glass article may also exhibit a depth of penetration of potassium ions (“potassium DOL”) that differs from the DOC. The extent of the difference between DOC and potassium DOL depends on the ion exchange treatment that creates stress in the glass substrate composition and the resulting glass article. When a stress in a glass article is generated by the exchange of potassium ions into the glass article, FSM (as described above with respect to CS) is used to measure the potassium DOL. When the stress is caused by the exchange of sodium ions into the glass article, SCALP (as described above with respect to CT) is used to measure the DOC, and the resulting glass article is potassium DOL, since there is no penetration of potassium ions. will not have When stress in a glass article is caused by the exchange of both potassium and sodium ions into the glass, the depth of exchange of sodium represents the DOC, and the depth of exchange of potassium ions represents a change in the magnitude of the compressive stress (however, when the stress is compressed does not change from to tensile); In this embodiment, DOC is measured by SCALP, and potassium DOL is measured by FSM. When both potassium DOL and DOC are present in the glass article, the potassium DOL is typically less than the DOC.

The Refracted near-field (RNF) method, or SCALP, may be used to measure the stress profile in the glass article described herein (regardless of whether the stress is generated by sodium ion exchange and/or potassium ion exchange). can If the RNF method is utilized, the CT values provided by SCALP are utilized. In particular, the stress profile measured by the RNF is force balanced and adjusted with the CT value provided by the SCALP measurement. The RNF method is described in US Pat. No. 8,854,623 entitled "Systems and methods for measuring a profile characteristic of a glass sample," the entire contents of which are incorporated herein by reference. In particular, the RNF method comprises the steps of placing a glass-based article adjacent to a reference block, a polarization-switched light beam switched between orthogonal polarizations at a rate of 1 Hz to 50 Hz. ), measuring an amount of power in the polarization-switched light beam, and generating a polarization-switched reference signal, wherein the measured amount of power at each orthogonal polarization is within 50% of each other. to be. The method comprises transmitting a polarization-switched light beam through the glass sample and a reference block for different depths into the glass sample, then having a signal photodetector that generates a polarization-switched detector signal. relaying the transmitted polarization-switched light beam to a signal photodetector using the system). The method also includes dividing the detector signal by a reference signal to form a normalized detector signal and determining a profile characteristic of the glass sample from the normalized detector signal.

In one or more embodiments in which the stress in the glass article is generated only by potassium ion exchange and the potassium DOL is equal to the DOC, the stress profile also provides priority to U.S. Provisional Patent Application Serial No. 61/489,800, filed May 25, 2011 Allegedly, a US patent filed on May 3, 2012 by Rostislav V. Roussev et al., entitled "Systems And Methods for Measuring the Stress Profile of Ion-Exchanged Glass (hereinafter referred to as "Roussev I")," by Rostislav V. Roussev et al. It can be obtained by the method described in application No. 13/463,322. Roussev I discloses a method for extracting detailed and accurate stress profiles (stress as a function of depth) of chemically strengthened glass using FSM. Specifically, spectra of the bound optical mode for TM and TE polarization are collected through a prism coupling technique, and detailed and accurate TM and TE refractive index profiles n _TM (z) and n _TE (z) These are used as a whole to obtain The contents of these applications are hereby incorporated by reference in their entirety. Detailed index profiles were prepared using the inverse Wentzel-Kramers-Brillouin (IWKB) method, and fitting the measured mode spectra to the numerically computed spectra of a pre-defined functional shape describing the shape of the index profile. obtained from the modal spectrum by the step and step of obtaining the parameters of the functional form from the best fit. A detailed stress profile S(z) is calculated from the difference between the recovered TM and TE index profiles using known stress-optical modulus (SOC) values, as follows:

S(z) = [n _TM (z)-n _TE (z)]/SOC.

Due to the small value of SOC, the birefringence n _TM (z)-n _TE (z) at any depth z is a small fraction (typically around 1%) of the indices n _TM (z) and n _TE (z). In order to obtain a stress profile that is not significantly distorted due to noise in the measured mode spectrum, it is required to determine the mode effective index with an accuracy of approximately 0.00001 RIU. The method disclosed in Roussev I is a technique applied to raw data to ensure high accuracy for the measured mode indices, despite noise and/or poor contrast in the images of the collected TE and TM mode spectra or mode spectra. further includes. These techniques include noise-averaging, filtering, and curve fitting to locate extremes corresponding to modes with sub-pixel resolution.

As noted above, the glass articles described herein can be chemically strengthened by ion exchange and can exhibit stress profiles distinct from those exhibited by known tempered glasses. In this process, ions on or near the surface of the glass article are replaced or exchanged with larger ions having the same valence or oxidation state. In embodiments in which the glass article comprises alkali aluminosilicate glass, ions and larger ions in the surface layer of the glass are formed by: Li ⁺ (if present in the glass article), Na ⁺ , K ⁺ , Rb ⁺ , and Cs ⁺ Same, monovalent alkali metal cations. Optionally, monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag ⁺ or the like.

The ion exchange process is typically performed by immersing the glass article in a molten salt bath (or two or more molten salt baths) containing larger ions to be exchanged with smaller ions in the glass article. It should be noted that aqueous salt baths may also be utilized. Additionally, the composition of the bath(s) may include one or more types of larger ions (eg, Na+ and K+) or single larger ions. Additional steps including, but not limited to, bath composition and temperature, immersion time, number of soaks of glass article in the salt bath (or baths), use of multiple salt baths, annealing, washing, and the like , the parameters for the ion exchange process are generally determined by the composition of the glass article (including the structure of the article and any crystalline phases present) and the desired DOC and CS of the glass article resulting from the strengthening operation. will be recognized by those skilled in the art. As an example, ion exchange of a glass article may be accomplished by immersing the glass article in at least one molten bath containing salts such as, but not limited to, nitrates, sulfates, and chlorides of larger alkali metal ions. . Typical nitrates include KNO ₃ , NaNO ₃ , LiNO ₃ , NaSO ₄ and combinations thereof. The temperature of the molten salt bath typically ranges from about 380° C. to about 450° C., while the immersion time ranges from about 15 minutes to about 100 hours, depending on the glass thickness, bath temperature and glass diffusion rate. However, other temperatures and immersion times than those described above may also be used.

In one or more embodiments, the glass article may be immersed in a molten salt bath of 100% NaNO ₃ having a temperature of about 370° C. to about 480° C. In some embodiments, the glass substrate may be immersed in a molten mixed salt bath comprising from about 5% to about 90% KNO ₃ and from about 10% to about 95% NaNO ₃ . In some embodiments, the glass substrate may be immersed in a molten mixed salt bath comprising Na ₂ SO ₄ and NaNO ₃ and may have a wider temperature range (eg, about 500° C. or less). In one or more embodiments, the glass article may be immersed in the second tub after immersion in the first tub. The immersion in the second bath may include immersion in a molten salt bath containing 100% KNO ₃ for 15 minutes to 8 hours.

Ion exchange conditions may be altered based on the glass composition and the thickness of the glass substrate. For example, a glass substrate having a nominal composition as shown in Example 1 below having a thickness of 0.4 mm has a temperature of about 460° C. for about 10 hours to about 20 hours (NaNO ₃ balanced with constituting) 80-100% KNO ₃ It can be immersed in a molten salt bath. The same substrate having a thickness of about 0.55 mm has a temperature of about 460° C. for a period of about 20 hours to about 40 hours. It can be immersed in a molten salt bath of 70-100% KNO ₃ (balanced with NaNO ₃ ). The same substrate having a thickness of about 0.8 mm can be immersed in a molten salt bath of 60-100% KNO ₃ (balanced with NaNO ₃ ) having a temperature of about 460° C. for a period of about 40 hours to about 80 hours. have.

In one or more embodiments, the glass-based substrate is about NaNO ₃ and KNO having a temperature of less than 420° C. (eg, about 400° C. or about 380° C.) for less than about 5 hours, or even up to about 4 hours. ₃ (eg, 49%/51%, 50%/50%, 51%/49%) can be immersed in a molten, mixed salt bath.

The ion exchange conditions can be adjusted to provide a “spike” or to increase the slope of the stress profile at or near the surface of the resulting glass-based article. This spike may be achieved by a single bath or multiple baths, using bath(s) having a single composition or a mixed composition, due to the unique properties of the glass compositions used in the glass-based articles described herein.

As illustrated in FIG. 4 , the glass article 300 of one or more embodiments includes a first surface 302 defining a thickness t and a second surface 304 opposing the first surface. . In one or more embodiments, the thickness (t) can be less than about 3 mm, less than about 2 mm, less than about 1.5 mm, less than about 1.1 mm, or less than 1 mm (e.g., from about 0.01 mm to about 1.5 mm). , about 0.1 mm to about 1.5 mm, about 0.2 mm to about 1.5 mm, about 0.3 mm to about 1.5 mm, about 0.4 mm to about 1.5 mm, about 0.01 mm to about 1.1 mm, about 0.1 mm to about 1.1 mm, about 0.2 mm to about 1.1 mm, about 0.3 mm to about 1.1 mm, about 0.4 mm to about 1.1 mm, about 0.01 mm to about 1.4 mm, about 0.01 mm to about 1.2 mm, about 0.01 mm to about 1.1 mm, about 0.01 mm to about 1 mm, about 0.01 mm to about 0.9 mm, about 0.01 mm to about 0.8 mm, about 0.01 mm to about 0.7 mm, about 0.01 mm to about 0.6 mm, about 0.01 mm to about 0.5 mm, about 0.1 mm to about 0.5 mm, or in the range of about 0.3 mm to about 0.5 mm).

4 is a cross-sectional view of a stress profile along a thickness t ₁ (shown along the x-axis) of a chemically strengthened glass article 300 . The magnitude of the stress is illustrated on the y-axis with line 301 representing zero stress.

The stress profile 312 includes a CS layer 315 (having a surface CS value 310 ) extending from one or both of the first major surface 302 and the second major surface 304 to the DOC 330 , and a CT layer 325 (with CT 320 ) extending from the DOC 330 to a central portion of the article.

As used herein, DOC refers to the depth at which stress within a glass article changes from compression to tension. In DOC, the stress crosses from positive (compressive) stress to negative (tensile) stress (eg, 330 in FIG. 4 ), thus exhibiting a stress value of zero.

The CS layer has an associated depth or length 317 extending from the major surfaces 302 , 304 to the DOC 330 . CT layer 325 also has an associated depth or length 327 (CT region or layer).

Surface CS 310 can be at least about 150 MPa or at least about 200 MPa (e.g., at least about 250 MPa, at least about 300 MPa, at least about 400 MPa, at least about 450 MPa, at least about 500 MPa, or at least about 550 MPa). Surface CS 310 can be about 900 MPa or less, about 1000 MPa or less, about 1100 MPa or less, or about 1200 MPa or less. In one or more embodiments, the surface CS 310 is from about 150 MPa to about 1200 MPa, from about 200 MPa to about 1200 MPa, from about 250 MPa to about 1200 MPa, from about 300 MPa to about 1200 MPa, from about 350 MPa to about 1200 MPa, about 400 MPa to about 1200 MPa, about 450 MPa to about 1200 MPa, about 500 MPa to about 1200 MPa, about 200 MPa to about 1100 MPa, about 200 MPa to about 1000 MPa, about 200 MPa to about 900 MPa , from about 200 MPa to about 800 MPa, from about 200 MPa to about 700 MPa, from about 200 MPa to about 600 MPa, from about 200 MPa to about 500 MPa, from about 300 MPa to about 900 MPa, or from about 400 MPa to about 600 MPa. can be a range.

CT 320 is at least about 25 MPa, at least about 50 MPa, at least about 75 MPa, at least about 85 MPa, or at least about 100 MPa (e.g., at least about 150 MPa, at least about 200 MPa, at least 250 MPa, or at least about 300 MPa or more) can be In some embodiments, CT 320 is in the range of about 50 MPa to about 400 MPa (e.g., about 75 MPa to about 400 MPa, about 100 MPa to about 400 MPa, about 150 MPa to about 400 MPa, about 50 MPa to about 350 MPa, about 50 MPa to about 300 MPa, about 50 MPa to about 250 MPa, about 50 MPa to about 200 MPa, about 100 MPa to about 400 MPa, about 100 MPa to about 300 MPa, about 150 MPa to about 250 MPa). As used herein, CT is the largest magnitude of central tension in a glass article.

It should be noted that any one or more of surfaces CS 310 and CT 320 may depend on the thickness of the glass article. For example, a glass article having a thickness of about 0.8 mm may have a CT of about 100 MPa or greater. In one or more embodiments, a glass article having a thickness of about 0.4 mm may have a CT of about 130 MPa or greater. In some embodiments, CT can be expressed in terms of the thickness (t) of the glass article. For example, in one or more embodiments, the CT may be greater than or equal to about (100 MPa)/√(t/1 mm), where t is the thickness in mm. In some embodiments, the CT is greater than or equal to (105 MPa)/√(t/1 mm), greater than or equal to (110 MPa)/√(t/1 mm), greater than or equal to (115 MPa)/√(t/1 mm), greater than or equal to (120 MPa)/√( t/1mm) or more or (125MPa)/√(t/1mm) or more.

CT 320 may be positioned in a range from about 0.3·t to about 0.7·t, from about 0.4·t to about 0.6·t, or from about 0.45·t to about 0.55·t. It should be noted that any one or more of surfaces CS 310 and CT 320 may depend on the thickness of the glass-based article. For example, a glass-based article having a thickness of about 0.8 mm may have a CT of about 75 MPa or less. When the thickness of the glass-based article decreases, the CT may increase. In other words, CT increases as the thickness decreases (or as the glass-based article becomes thinner).

The Young's modulus of the glass article can affect the CT of the tempered glass article described herein. Specifically, as the Young's modulus of the glass article decreases, the glass article can be strengthened to have a lower CT, for a given thickness, and still exhibit the rupture behavior described herein. For example, when comparing a 1 mm glass article having a relatively lower Young's modulus than another 1 mm-thick glass article having a higher Young's modulus, the lower Young's modulus glass article is, to a lesser extent (i.e., relatively more can be strengthened (with a low CT value) and still exhibit the same breaking behavior as a higher Young's modulus glass (which will have a higher CT compared to a CT glass article).

In some embodiments, the ratio of CT 320 to surface CS ranges from about 0.05 to about 1 (eg, about 0.05 to about 0.5, about 0.05 to about 0.3, about 0.05 to about 0.2, about 0.05 to about 0.1, about 0.5 to about 0.8, about 0.0.5 to about 1, about 0.2 to about 0.5, about 0.3 to about 0.5). In known chemically strengthened glass articles, the ratio of CT 320 to surface CS is 0.1 or less. In some embodiments, the surface CS can be at least 1.5 times (or 2 times or 2.5 times) the CT. In some embodiments, the surface CS may be less than or equal to about 20 times the CT.

In one or more embodiments, the stress profile 312 includes a maximum CS, typically the surface CS 310 , and may be identified on one or both of the first surface 302 and the second surface 304 . have. In one or more embodiments, the CS layer or region 315 extends along a portion of the thickness into the DOC 317 and the CT 320 . In one or more embodiments, DOC 317 may be greater than or equal to about 0.1 t. For example, DOC 317 may be at least about 0.12 t, at least about 0.14 t, at least about 0.15 t, at least about 0.16 t, at least 0.17 t, at least 0.18 t, at least 0.19 t, 0.20 t or more, about 0.21 t or more, or about 0.25 t or less. In some embodiments, DOC 317 is less than maximum chemical depth 342 . The maximum chemical depth 342 may be at least about 0.4·t, at least 0.5·t, at least about 55·t, or at least about 0.6·t.

In one or more embodiments, the glass-based article comprises potassium DOL in a range from about 6 micrometers to about 20 micrometers. In some embodiments, the potassium DOL can be expressed as a function of the thickness (t) of the glass-based article. In one or more embodiments, the potassium DOL may range from about 0.005 tons to about 0.05 tons. In one or more embodiments, the potassium DOL is from about 0.005t to about 0.05t, about 0.005t to about 0.045t, about 0.005t to about 0.04t, about 0.005t to about 0.035t, about 0.005t to about 0.03t, about 0.005t to about 0.025t, about 0.005t to about 0.02t, about 0.005t to about 0.015t, about 0.005t to about 0.01t, about 0.006t to about 0.05t, about 0.008t to about 0.05t, about 0.01 t to about 0.05 t, about 0.015 t to about 0.05 t, about 0.02 t to about 0.05 t, about 0.025 t to about 0.05 t, about 0.03 t to about 0.05 t, or about 0.01 t to about 0.02 t have.

In one or more embodiments, the compressive stress value at the potassium DOL depth may range from about 50 MPa to about 300 MPa. In some embodiments, the compressive stress value at the potassium DOL depth is from about 50 MPa to about 280 MPa, from about 50 MPa to about 260 MPa, from about 50 MPa to about 250 MPa, from about 50 MPa to about 240 MPa, from about 50 MPa to about 220 MPa, about 50 MPa to about 200 MPa, about 60 MPa to about 300 MPa, about 70 MPa to about 300 MPa, about 75 MPa to about 300 MPa, about 80 MPa to about 300 MPa, about 90 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, from about 1100 MPa to about 300 MPa, from about 120 MPa to about 300 MPa, from about 130 MPa to about 300 MPa, or from about 150 MPa to about 300 MPa.

In one or more embodiments, the glass article exhibits a combination of a surface CS in the range of about 450 MPa to about 600 MPa, a CT in the range of about 200 to 300 MPa, and a thickness in the range of about 0.4 mm to 0.5 mm. In some embodiments, the DOC of the glass article ranges from about 0.18 t to about 0.21 t.

In one or more embodiments, the glass article exhibits a combination of a surface CS in the range of about 350 MPa to about 450 MPa, a CT in the range of about 150 to 250 MPa, and a thickness in the range of about 0.4 mm to 0.5 mm. In some embodiments, the DOC of the glass article ranges from about 0.18 tons to about 0.21 tons.

In one or more embodiments, the glass article exhibits a maximum chemical depth of at least about 0.4·t, at least 0.5·t, at least about 0.55·t, or at least about 0.6·t. As used herein, the term “chemical depth” refers to the depth at which ions of a metal oxide or alkali metal oxide (eg, metal ions or alkali metal ions) diffuse into a glass article and the concentration of those ions, EPMA ( It is determined by Electron Probe Micro-Analysis) and means the depth that reaches the minimum value. The ions are ions that have diffused into the chemically strengthened glass article as a result of ion exchange. Maximum chemical depth refers to the maximum diffusion depth for any ion exchanged glass article chemically strengthened by an ion exchange process. For example, if it is a molten salt bath (ie, a molten salt bath of NaNO ₃ and KNO ₃ ) having one or more diffusive ionic species, the different ionic species may enter the chemically strengthened glass article at different depths. can spread. The maximum chemical depth is the greatest diffusion depth of all ionic species that are ion exchanged into the chemically strengthened glass article.

In one or more embodiments, the stress profile 312 may be described as a parabolic-like shape. In some embodiments, the stress profile along a region or depth of the glass-based article exhibiting tensile stress exhibits a parabolic-like shape. In one or more specific embodiments, the stress profile 312 has no portions exhibiting flat stress (ie, compressive or tensile) or substantially constant stress (ie, compressive or tensile). In some embodiments, the CT region exhibits a stress profile that is substantially free of flat stress or substantially free of constant stress. In one or more embodiments, all of the stress profile 312 between a thickness range of from about 0 t to about 0.2 t and greater than about 0.8 t (or from about 0 t to about 0.3 t and greater than 0.7 t) A point includes a tangent that is less than about -0.1 MPa/micrometers or greater than about 0.1 MPa/micrometers. In some embodiments, the tangent may be less than about -0.2 MPa/micrometers or greater than about 0.2 MPa/micrometers. In some more particular embodiments, the tangent may be less than about -0.3 MPa/micrometers or greater than about 0.3 MPa/micrometers. In an even more particular embodiment, the tangent may be less than about -0.5 MPa/micrometers or greater than about 0.5 MPa/micrometers. In other words, the stress profile of one or more embodiments along these thickness ranges (i.e., from 0 t to about 2 t and greater than 0.8 t, or from about 0 t to 0.3 t and 0.7 t or greater) is: As described in , points with tangent lines are excluded. While not wishing to be bound by theory, the known error functions or quasi-linear stress profiles (representing a flat or zero slope stress profile depending on the thickness range, as shown in FIG. 3 , 220) about -0.1 MPa/micrometers to about 0.1 MPa/micrometers, about -0.2 MPa/micrometers to about 0.2 MPa/micrometers, about -0.3 MPa/micrometers to about 0.3 MPa/micrometers, or about -0.5 MPa/micrometers to about in these thickness ranges (i.e., from about 0 t to about 0.2 t and greater than 0.8 t, or from about 0 t to about 0.3 t and 0.7 t or greater), with a tangent in the range of 0.5 MPa/micrometers. have the following points. The glass-based article of one or more embodiments of the present disclosure does not exhibit a stress profile having a flat or zero slope stress profile along these thickness ranges, as shown in FIG. 4 .

In one or more embodiments, the glass-based article exhibits a stress profile in a thickness range of about 0.1·t to 0.3·t and about 0.7·t to 0.9·t inclusive of maximum and minimum tangents. In some instances, the difference between the maximum tangent and the minimum tangent is about 3.5 MPa/micrometers or less, about 3 MPa/micrometers or less, about 2.5 MPa/micrometers or less, or about 2 MPa/micrometers or less.

In one or more embodiments, the glass-based article has a stress profile 312 that is substantially free of any linear segments that extend along at least a portion of the thickness t of the glass-based article or in the depth direction. include In other words, the stress profile 312 increases or decreases substantially continuously along the thickness t. In some embodiments, the stress profile is substantially free of any linear segments in the depth direction having a length of at least about 10 micrometers, at least about 50 micrometers, or at least about 100 micrometers, or at least about 200 micrometers. As used herein, the term “linear” refers to a slope having a magnitude along a linear segment of less than about 5 MPa/micrometers, or less than about 2 MPa/micrometers. In some embodiments, one or more portions of the stress profile substantially free of any linear segments in the depth direction are at least about 5 micrometers (e.g., at least 10 micrometers, or 15 micrometers or more) in glass-based products. For example, along a depth of from about 0 micrometers to less than about 5 micrometers from the first surface, the stress profile may include linear segments, but from a depth greater than about 5 micrometers from the first surface, the stress profile is substantially linear. There are no segments.

In some embodiments, the stress profile can include linear segments at depths from about 0 t to about 0.1 t, and can be substantially free of linear segments at depths from about 0.1 t to about 0.4 t. In some embodiments, the stress profile from a thickness in the range of about 0 t to about 0.1 t may have a slope in the range of about 20 MPa/microns to about 200 MPa/microns. As described herein, such embodiments are formed using a single ion-exchange process or multiple (eg, two or more) ion exchange processes wherein the bath comprises two or more alkali salts or is a mixed alkali salt bath. can be

In one or more embodiments, the glass-based article can be described in terms of the shape of the stress profile along the CT region ( 327 in FIG. 4 ). For example, in some embodiments, the stress profile along the CT region (where the stress is tension) may be approximated by the equation: In some embodiments, the stress profile along the CT region can be approximated by Equation 1:

[Equation 1]

Stress(x) = MaxT - (((CT _n ·(n+1))/0.5 ⁿ )·|(x/t)-0.5| ⁿ )

In Equation 1, stress (x) is the stress value at position x. Here, stress is positive (tension). In Equation 1, MaxT is the maximum tension value and CT _n is the tension value at n and is less than or equal to MaxT. Both MaxT and CT _n are positive values in MPa. the value x is the position along the thickness (t) in micrometers, ranging from 0 to t; x=0 is one surface (302 in FIG. 4), x=0.5t is the center of the glass-based article, stress (x)=MaxCT, and x=t is the opposing surface (304 in FIG. 4). MaxT used in Equation 1 is equal to CT, which may be less than about 71.5/√(t). In some embodiments, MaxT used in Equation 1 is about 50 MPa to about 80 MPa (e.g., about 60 MPa to about 80 MPa, about 70 MPa to about 80 MPa, about 50 MPa to about 75 MPa, about 50 MPa to about 70 MPa, or about 50 MPa to about 65 MPa), and n is from 1.5 to 5 (eg, 2 to 4, 2 to 3 or 1.8 to 2.2) or about 1.5 to about 2 is a fitting parameter. In one or more embodiments, n=2 may provide a parabolic stress profile, and an exponent deviating from n=2 provides a stress profile having a near-parabolic stress profile. 4 is a graph illustrating various stress profiles, in accordance with one or more embodiments of the present disclosure, based on changes in the fit parameter n.

In one or more embodiments, CTn can be less than MaxT when there is a compressive stress spike for one or both of the major surfaces of the glass-based article. In one or more embodiments, CTn is equal to MaxT in the absence of compressive stress spikes for one or both of the major surfaces of the glass-based article.

In some embodiments, the stress profile may be altered by heat treatment. In such embodiments, the thermal treatment may occur before any ion-exchange process, between ion-exchange processes, or after all ion-exchange processes. In some embodiments, the heat treatment may result in a decrease in the slope of the stress profile at or near the surface. In some embodiments, if a steep or larger gradient is desired at the surface, an ion-exchange process after heat treatment can be utilized to provide a "spike" or increase the slope of the stress profile at or near the surface.

In one or more embodiments, the stress profile 312 (and/or the estimated stress profile 340 ) is generated due to a non-zero concentration of metal oxide(s) that varies along a portion of the thickness. A change in concentration may be referred to herein as a gradient. In some embodiments, the concentration of metal oxide is non-zero and varies along a thickness range from about 0·t to about 0.3·t. In some embodiments, the concentration of the metal oxide is non-zero, and from about 0·t to about 0.35·t, from about 0·t to about 0.4·t, from about 0·t to about 0.45·t, or from about 0·t to It varies along a thickness range of about 0.48·t. Metal oxides can be described as stress-generating in glass-based articles. The change in concentration may be continuous along the above-mentioned thickness range. A change in concentration may include a change in metal oxide concentration of about 0.2 mol % along a thickness segment of about 100 micrometers. This change can be measured by methods known in the art, including microprobes, as shown in Example 1. Metal oxides that are non-zero in concentration and vary along a portion of the thickness can be described as stress-generating in glass-based articles.

The change in concentration may be continuous along the above-mentioned thickness range. In some embodiments, the change in concentration may be continuous along the thickness segment in a range from about 10 micrometers to about 30 micrometers. In some embodiments, the concentration of the metal oxide decreases from the first surface to a point between the first surface and the second surface and increases from that point to the second surface.

The concentration of metal oxide may include one or more metal oxides (eg, a combination of Na ₂ O and K ₂ O). In some embodiments, when two metal oxides are utilized and the ions have different radii, the concentration of the ion with the larger radius exceeds the concentration of the ion with the smaller radius than at the shallow depth, while At deep depths, the concentration of ions with a smaller radius exceeds the concentration of ions with a larger radius. For example, when a single Na- and K-containing bath is used in an ion exchange process, the concentration of K+ ions in the glass-based article exceeds the concentration of Na+ ions at a shallower depth, whereas the concentration of Na+ is At greater depths, the concentration of K+ ions is exceeded. This is due, in part, to the size of the ions. In such glass-based articles, regions at or near the surface contain a larger CS due to a greater amount of larger ions (ie, K+ ions) at or near the surface. This larger CS can be represented by a stress profile with a steeper slope at or near the surface (ie, a spike within the stress profile at the surface).

A concentration gradient or change in the one or more metal oxides is produced by chemically strengthening a glass-based substrate, as already described herein, wherein the plurality of first metal ions in the glass-based substrate comprises: is exchanged with The first ion may be an ion of lithium, sodium, potassium, and rubidium. The second metal ion may be one of sodium, potassium, rubidium, and cesium, provided that the second alkali metal ion has an ionic radius greater than that of the first alkali metal ion. The second metal ion is present in the glass-based substrate as its oxide (eg, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, or combinations thereof).

In one or more embodiments, the metal oxide concentration gradient extends through the total thickness (t) or a substantial portion of the thickness (t) of the glass-based article, including the CT layer 327 . In one or more embodiments, the concentration of the metal oxide is at least about 0.5 mol % in the CT layer 327 . In some embodiments, the concentration of metal oxide may be about 0.5 mol % or greater (eg, about 1 mol % or greater) along the entire thickness of the glass-based article, and the first surface 302 and/or It is greatest at the second surface 304 and decreases substantially constant to a point between the first surface 302 and the second surface 304 . At this point, the metal oxide concentration is minimal along the entire thickness (t); But the concentration is also non-zero at that point. In other words, the non-zero concentration of that particular metal oxide extends along a substantial portion or the entire thickness t (as described herein) of the thickness t. In some embodiments, the lowest concentration in a particular metal oxide is in the CT layer 327 . The total concentration of certain metal oxides in the glass-based article may range from about 1 mol % to about 20 mol %.

In one or more embodiments, the glass-based article comprises a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is about 0 along a first thickness range of about 0 t to about 0.5 t. mol% to about 15 mol%, and wherein the second metal oxide concentration is from about 0 mol% to about 10 mol% from a second thickness range of from about 0 micrometers to about 25 micrometers (or from about 0 micrometers to about 12 micrometers) range; However, the concentration of one or both of the first metal oxide and the second metal oxide is non-zero along the entire thickness or a substantial portion of the glass-based article. The glass-based article may include an optional third metal oxide concentration. The first metal oxide may include Na ₂ O, but the second metal oxide may include K ₂ O.

The concentration of metal oxide may be determined from a reference amount of metal oxide in the glass-based article prior to being modified to include this concentration gradient of metal oxide.

In some embodiments, the stress profile can be altered by heat treatment. In such embodiments, the thermal treatment may occur before any ion-exchange process, between ion-exchange processes, or after all ion-exchange processes. In some embodiments, the heat treatment may result in a decrease in the slope of the stress profile at or near the surface. In some embodiments, if a steep or larger gradient is desired at the surface, an ion-exchange process after heat treatment can be utilized to provide a "spike" or to increase the slope of the stress profile at or near the surface. .

In one or more embodiments, the stress profile 312 is generated due to the non-zero concentration of metal oxide(s) varying along a portion of the thickness. A change in concentration may be referred to herein as a gradient. In some embodiments, the concentration of metal oxide is non-zero and varies along a thickness range from about 0·t to about 0.3·t. In some embodiments, the concentration of the metal oxide is non-zero, and from about 0·t to about 0.35·t, from about 0·t to about 0.4·t, from about 0·t to about 0.45·t, or from about 0·t to It varies with the thickness range of about 0.48·t. Metal oxides can be described as stress-generating in glass-based articles. The change in concentration may be continuous along the above-mentioned thickness range. A change in concentration may include a change in metal oxide concentration of about 0.2 mol % along a thickness segment of about 100 micrometers. This change can be measured by methods known in the art including microprobes, as shown in Example 1. Metal oxides that are non-zero in concentration and vary along a portion of the thickness can be described as stress-generating in glass-based articles.

The change in concentration may be continuous along the above-mentioned thickness range. In some embodiments, the change in concentration may be continuous along the thickness segment in the range of about 10 micrometers to about 30 micrometers. In some embodiments, the concentration of metal oxide decreases from the first surface to a point between the first and second surfaces and increases from that point to the second surface.

The concentration of metal oxide may include one or more metal oxides (eg, a combination of Na ₂ O and K ₂ O). In some embodiments, when two metal oxides are utilized and the ions have different radii, the concentration of the ion with the larger radius exceeds the concentration of the ion with the smaller radius at the shallower depth, while at the greater depth. , the concentration of ions with a smaller radius exceeds the concentration of ions with a larger radius. For example, if a single Na- and K-containing bath is used in an ion exchange process, the concentration of K+ ions in the glass-based product exceeds the concentration of Na+ ions at shallower depths, whereas the concentration of Na+ is At greater depths, the concentration of K+ ions is exceeded. This is due, in part, to the size of the ions. In such glass-based articles, regions at or near the surface contain a larger CS due to a greater amount of larger ions (ie, K+ ions) at or near the surface. This larger CS can be represented by a stress profile with a steeper slope at or near the surface (ie, a spike within the stress profile at the surface).

A concentration gradient or change in the one or more metal oxides is produced by chemically strengthening a glass-based substrate, as already described herein, wherein the plurality of first metal ions in the glass-based substrate comprises a plurality of second metal ions and are exchanged The first ion may be an ion of lithium, sodium, potassium, and rubidium. The second metal ion may be one of sodium, potassium, rubidium, and cesium, provided that the second alkali metal ion has an ionic radius greater than that of the first alkali metal ion. The second metal ion is present in the glass-based substrate as an oxide thereof (eg, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, or combinations thereof).

In one or more embodiments, the metal oxide concentration gradient extends through the total thickness (t) or a substantial portion of the thickness (t) of the glass-based article, including the CT layer 327 . In one or more embodiments, the concentration of metal oxide is at least about 0.5 mol % in CT layer 327 . In some embodiments, the concentration of metal oxide may be about 0.5 mol % or greater (eg, about 1 mol % or greater) depending on the overall thickness of the glass-based article, and the first surface 302 and/or It is greatest at the second surface 304 and decreases substantially constant to a point between the first surface 302 and the second surface 304 . At this point, the concentration of metal oxide is minimal, depending on the overall thickness (t); However, the concentration is not zero at that point. In other words, the non-zero concentration of that particular metal oxide extends along the total thickness t or a substantial portion of the thickness t (as described herein). In some embodiments, the lowest concentration of a particular metal oxide is in the CT layer 327 . The total concentration of certain metal oxides in the glass-based article may range from about 1 mol % to about 20 mol %.

In one or more embodiments, the glass-based article comprises a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is about 0 mol depending on the first thickness range of about 0 t to about 0.5 t. % to about 15 mol%, and the second metal oxide concentration ranges from about 0 mol% to about 10 mol% from a second thickness range of from about 0 micrometers to about 25 micrometers (or from about 0 micrometers to about 12 micrometers). as; However, the concentration of one or both of the first metal oxide and the second metal oxide is non-zero depending on the total thickness or substantial portion of the glass-based article. The glass-based article may include an optional third metal oxide concentration. The first metal oxide may include Na ₂ O, while the second metal oxide may include K ₂ O.

The concentration of metal oxide may be determined from a reference amount of metal oxide in the glass article before being changed to include this concentration gradient of metal oxide.

The glass articles described herein can exhibit stored tensile energy in the range of at least 15 J/m 2 (eg, from about 15 J/m 2 to about 50 J/m 2 ). For example, in some embodiments, the stored tensile energy may range from about 20 J/m 2 to about 150 J/m 2 . In some instances, the stored tensile energy is about 25 J/m to about 150 J/m, about 30 J/m to about 150 J/m, about 35 J/m to about 150 J/m, about 40 J/m to about 150 J/m, from about 45 J/m to about 150 J/m, from about 50 J/m to about 150 J/m, from about 55 J/m to about 150 J/m, from about 60 J/m to about 150 J/m, about 65 J/m to about 150 J/m, about 25 J/m to about 140 J/m, about 25 J/m to about 130 J/m, about 25 J/m to about 120 J /m, from about 25 J/m to about 110 J/m, from about 30 J/m to about 140 J/m, from about 35 J/m to about 130 J/m, from about 40 J/m to about 120 J/m , or from about 40 J/m2 to about 100 J/m2. The thermally and chemically strengthened glass-based article of one or more embodiments may contain at least about 40 J/m2, at least about 45 J/m2, at least about 50 J/m2, at least about 60 J/m2, or at least about 70 J/m2 of stored storage. It can represent tensile energy.

The stored tensile energy is calculated using Equation 2:

[Equation 2]

Stored tensile energy (J/m2) = [1-υ]/E∫σ^2dt

where v is the Poisson's ratio, E is the Young's modulus, and the integral is calculated only for the tensile region. Equation 2 is, Suresh T. Gulati, Frangibility of Tempered Soda-Lime Glass Sheet, GLASS PROCESSING DAYS, The Fifth International Conference on Architectural and Automotive Glass, 13-15 Sept. In 1997, it is written as Equation (4).

The glass articles of some embodiments exhibit superior mechanical performance, as evidenced by device drop testing or component level testing, as compared to known tempered glass articles. In one or more embodiments, the glass article exhibits improved surface strength when subjected to an abraded ring-on-ring (AROR) test. The strength of a material is defined as the stress at which fracture occurs. The AROR test is a surface strength measurement for testing flat glass specimens, and ASTM C1499-09 (2013), entitled "Standard Test Method for Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperature," - Serves as the basis for the on-ring worn ROR test methodology. The content of ASTM C1499-09 is incorporated herein by reference in its entirety. In one embodiment, the glass specimen, in Annex A2 of ASTM C158-02 (2012), entitled "Standard Test Methods for Strength of Glass by Flexure (Determination of Modulus of Rupture)", is absent from "abrasion Procedures" Abraded prior to the ring-on-ring test with 90 grit silicon carbide (SiC) particles transferred to a glass sample using the method and apparatus described in The content of ASTM C158-02, and particularly of Annex 2, is incorporated herein by reference in its entirety.

Prior to the ring-on-ring test, the surface of the glass article was abraded as described in ASTM C158-02, Annex 2, to standardize and standardize the surface defect condition of the sample using the apparatus shown in Figure A2.1 of ASTM C158-02 / or adjust. The abrasive is typically sandblasted onto the surface 110 of the glass article with a load or pressure of at least 15 psi using a pneumatic pressure of 304 kPa (44 psi). In some embodiments, the abrasive may be sandblasted onto the surface 110 with a load of 20 psi, 25 psi, or even 45 psi. After the air flow is established, 5 cm 3 of abrasive is stacked in a funnel and the sample is sandblasted for 5 seconds after introduction of the abrasive.

During the ring-on-ring test, a glass article having at least one worn surface 112 as shown in FIG. When applied to a deflection between two concentric rings, it is placed between two concentric rings of different sizes to determine the maximum stress that can be maintained. In the worn ring-on-ring structure 100 , the worn glass article 110 is supported by a support ring 120 having a diameter D2 . A force F is applied by a load cell (not shown) to the surface of the glass article by means of a loading ring 130 having a diameter D1 .

The ratio of the diameters of the loading ring and the support ring (D1/D2) may range from about 0.2 to about 0.5. In some embodiments, D1/D2 is about 0.5. The loading and support rings 130 , 120 should be concentrically aligned within 0.5% of the support ring diameter D2. The load cell used for testing shall be accurate to within ±1% of any load within the selected range. In some embodiments, the test is performed at a temperature of 23±2° C. and a relative humidity of 40±10%.

For the fixture design, the radius r of the protruding surface of the loading ring 130 is h/2 ≤ r ≤ 3h/2, where h is the thickness of the glass article 110 . The loading and support rings 130 , 120 are typically made of hardened steel having a hardness HRc>40. ROR fixtures are commercially available.

The intended failure mechanism for the ROR test is to observe the failure of the glass article 110 originating from the surface 130a within the loading ring 130 . Failures that occur outside of this region - ie between the loading ring 130 and the support ring 120 - are omitted from the data analysis. However, due to the thinness and high strength of the glass article 110 , large deflections exceeding ½ of the sample thickness h are sometimes observed. Accordingly, it is common to observe a high percentage of failure originating from below the loading ring 130 . The stress cannot be accurately calculated without knowledge of the origin of failure in each specimen and the stress development both inside and below the ring (collected via strain gage analysis). Therefore, the AROR test focuses on the peak load at failure as the measured response.

The strength of a glass article depends on the presence of surface flaws. However, as the strength of glass is based in fact statistically, the likelihood of a flaw of a given size present cannot be accurately predicted. Therefore, the probability distribution can be used as a statistical representation of the data obtained in general.

In some embodiments, the tempered glass articles described herein exhibit a coaxial flexural strength or breaking load of at least 20 kgf and up to about 45 kgf, as determined by the AROR test using a load of 25 psi or even 45 psi to abrade the surface. . In another embodiment, the surface strength is at least 25 kgf, and in another embodiment, at least 30 kgf.

In some embodiments, the tempered glass article may exhibit improved drop performance. As used herein, drop performance is evaluated by assembling a glass article into a mobile phone device. In some instances, multiple glass articles can be assembled into the same mobile phone device and tested the same. The mobile phone device assembled with the glass article is then dropped onto abrasive paper (which may contain Al ₂ O ₃ particles or other abrasives) for successive drops starting from a height of 50 cm. As each sample withstands a drop from height, the cell phone device with the sample is again dropped from an increasing height until the glass article breaks, at which point the breakage height of the sample is recorded as the maximum breakage height.

In some embodiments, the glass article, when having a thickness of about 1 mm, exhibits a maximum breakage height of at least about 100 cm. In some embodiments, the glass article has a maximum breakage height of about 120 cm or more, about 140 cm or more, about 150 cm or more, about 160 cm or more, about 180 cm or more, or about 200 cm or more, at a thickness of about 1 mm. indicates. The glass article of one or more embodiments exhibits a diced fracture pattern after failure at the break height. The diced fracture patterns include those exhibiting the aspect ratios described herein.

In one or more embodiments, the glass article herein, when the glass article is directly bonded to a substrate (ie, a display unit), after the glass article ruptures, at least 50% of the cracks are sub-surface cracks (where the cracks are It exhibits fracture behavior, such that it extends only partially through the thickness and is impeded below the surface). For example, in some instances, the crack may extend partially through the thickness t of the glass article, eg, 0.05 t to 0.95 t. The percentage of cracks in the glass article extending only partially through the thickness t may be at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

In some embodiments, the strengthened glass-based articles described herein can be described in terms of performance in an Inverse Ball on Sandpaper (IBoS) test. The IBoS test, as schematically shown in FIG. 6 , is a dynamic component level test that mimics the main mechanisms for failure due to bending plus introduction of damage commonly occurring in glass-based products used in mobile or portable electronic devices. In situ, damage introduction ( FIG. 7 a ) occurs at the top surface of the glass-based article. Fracture begins at the upper surface of the glass-based article and the damage either penetrates the glass-based article ( FIG. 7 b ) or the breakage can result from bending of the upper surface of the glass-based article or from an internal portion of the glass-based article ( It is propagated from c) in FIG. 7 . The IBoS test is designed to simultaneously introduce damage to the glass surface and to apply bending under dynamic loading. In some instances, a glass-based article, when including compressive stress, exhibits improved dropping performance than when the same glass-based article does not include compressive stress.

The IBoS test apparatus is schematically shown in FIG. 6 . The device 500 includes a test bench 510 and a ball 530 . Ball 530 is, for example, a hard or solid ball, such as a stainless steel ball, or the like. In one embodiment, ball 530 is a 4.2 gram stainless steel ball with a diameter of 10 mm. The ball 530 is dropped directly onto the glass-based article sample 518 from a predetermined height h. The test bench 510 includes a solid base 512 comprising a hard, hard material, such as granite or the like. A sheet 514 with an abrasive disposed thereon rests on the upper surface of the solid substrate 512 with the abrasive-bearing surface facing up. In some embodiments, sheet 514 is a sandpaper having a 30 grit surface, and in other embodiments, a 180 grit surface. The glass-based article sample 518 is held in place over the sheet 514 by the sample holder 515 such that there is an air gap 516 between the glass-based article sample 518 and the sheet 514 . An air gap 516 between the sheet 514 and the glass-based product sample 518 causes the glass-based product sample 518 to bend onto the abrasive surface of the sheet 514 upon impact by the ball 530 . make it possible to lose In one embodiment, the glass-based article sample 518 is clamped across all corners to ensure repeatability and to maintain the bend included only at the point of ball impact. In some embodiments, the sample holder 514 and test bench 510 are adapted to receive a sample thickness of about 2 mm or less. The air gap 516 ranges from about 50 μm to about 100 μm. The air gap 516 is tailored for adjustment for differences in the stiffness (Young's modulus, Emod) of the material, but also includes the Young's modulus and thickness of the sample. Adhesive tape 520 may be used to cover the top surface of the glass-based article sample to collect debris in the event of rupture of the glass-based article sample 518 upon impact of the ball 530 .

A variety of materials can be used as the abrasive surface. In one specific embodiment, the abrasive surface is sandpaper, such as silicon carbide or alumina sandpaper, engineered sandpaper, or any abrasive known to those skilled in the art having a similar hardness and/or sharpness. In some embodiments, sandpaper with 30 grit can be used because it has a more consistent surface topography than concrete or asphalt, and a grain size and sharpness that produces the desired level of specimen surface damage.

In one aspect, a method 600 of performing an IBoS test using the apparatus 500 described above is shown in FIG. 8 . In step 610 , a glass-based article sample ( 518 in FIG. 6 ) is placed on a test bench 510 , as previously described, and an air gap 516 is placed on a glass-based sheet 514 with an abrasive surface. It is secured to the sample holder 515 to form between the product samples 518 . The method 600 assumes that the sheet 514 with the abrasive surface has already been placed on the test bench 510 . However, in some embodiments, the method may include placing the sheet 514 on the test bench 510 with the abrasive surface facing up. In some embodiments (step 610a ), adhesive tape 520 is applied to the top surface of the glass-based article sample 518 prior to securing the glass-based article sample 518 to the sample holder 510 .

In step 620, the ball 530 is attached to the upper surface (or to the upper surface) at the approximate center of the upper surface (ie, within 1 mm, or within 3 mm, or within 5 mm, or within 10 mm of the center) of the upper surface. A solid ball 530 of a predetermined mass and size is dropped onto the upper surface of the glass-based article sample 518 at a predetermined height h to impact the adhesive tape 520 ). After impact in step 620, the extent of damage to the glass-based article sample 518 is determined (step 630). As previously described above, the term “rupture” means that when a substrate is dropped on or impacted by an object, the crack propagates across the entire thickness and/or entire surface of the substrate.

In method 600, sheet 514 having an abrasive surface is to be replaced after each drop to avoid the “aging” effect observed with repeated use of other types of drop test surfaces (eg, concrete or asphalt). can

Various predetermined drop heights (h) and increments are commonly used in method 600 . The test may utilize, for example, a minimum drop height for initiation (eg, about 10-20 cm). The height can then be increased for successive falls in set increments or variable increments. The test described in method 600 is interrupted when glass-based article sample 518 breaks or breaks (step 631 ). Optionally, if the drop height h reaches a maximum drop height (eg, about 100 cm) without breaking, the drop test of method 600 is also stopped, or step 620 is performed until breaking occurs. Can be repeated at maximum height.

In some embodiments, the IBoS test of method 600 is performed only once for each glass-based article sample 518 at each predetermined height h. However, in other embodiments, each sample may be subjected to multiple tests at each height.

When rupture of the glass-based article sample 518 occurs (step 631 in FIG. 7 ), the IBoS test according to method 600 ends (step 640 ). If no fracture resulting from falling of the ball is observed at the predetermined drop height (step 632), then the drop height is increased by a predetermined increment (step 634) - such as for example 5, 10 or 20 cm - and step ( 620 and 630 are repeated until sample failure is observed (631) or the maximum test height is reached without sample failure (636). When step 631 or 636 is reached, the test according to method 600 ends.

When subjected to the inverse ball to sandpaper (IBoS) test described above, embodiments of the glass-based article described herein have a survival rate of at least about 60% when the ball is dropped onto a glass surface from a height of 100 cm . For example, a glass-based article may contain five identical (or nearly identical) samples (ie, approximately the same composition, as described herein, and, when strengthened, approximately the same compressive stress and depth of compression or compressive stress layer). three) are described as having a 60% survival rate when dropped from a given height if they survive the IBoS drop test without breakage when dropped from the stated height (here 100 cm). In other embodiments, the viability in the 100 cm IBoS test of the strengthened glass-based article is at least 70%, in other embodiments, at least about 80%, and in other embodiments, at least about 90%. In another embodiment, the viability of a tempered glass-based article dropped from a height of 100 cm in an IBoS test is at least about 60%, in another embodiment at least about 70%, in another embodiment at least about 80% , and in other embodiments, at least about 90%. In one or more embodiments, the viability of a tempered glass-based article dropped from a height of 150 cm in the IBoS test is at least about 60%, in another embodiment, at least about 70%, in another embodiment, at least about 80%, and in other embodiments, at least about 90%.

In order to determine the viability of a glass-based article when dropped from a predetermined height using the IBoS test method and apparatus described above above, a larger number (e.g., 10, 20, 30, etc.) samples At least five identical (or nearly identical) (ie, approximately identical composition, and, if reinforced, approximately identical compressive stress and compression or layer ) the sample is tested. Each sample is dropped once from a predetermined height (eg, 100 cm or 150 cm) or, optionally, from a progressively higher height until a predetermined height is reached without breaking, and Evidence (crack formation and propagation across the entire thickness and/or entire surface of the sample) is examined visually (ie, visually). A sample is considered "surviving" in a drop test if no fracture is observed after being dropped from a predetermined height, and "broken" (or "surviving" if failure is observed when the sample is dropped from a height that is less than or equal to a predetermined height). not") is considered. Survival is determined as the percentage of the sample population that survived the drop test. For example, if 7 out of a group of 10 samples did not break when dropped from a predetermined height, the survival rate of the glass would be 70%.

In one or more embodiments, the glass article exhibits a lower delayed rupture rate (ie, the glass article breaks quickly or even immediately upon break). In some embodiments, this rate of failure may be due to deep DOC and high levels of CT. Specifically, the glass article is less likely to spontaneously break long after damage has occurred to the glass article that induces breakage or breakage. In one or more embodiments, when the glass article ruptures, the glass article is described in Z. Tang, et al. Automated Apparatus for Measuring the Frangibility and Fragmentation of Strengthened Glass. It fractures into a plurality of fragments within 2 seconds or within 1 second after impact as measured by the "Fragility Test", as described in Experimental Mechanics (2014) 54:903-912. Fragility testing was performed with a stylus with a tungsten carbide tip, (available from Fisher Scientific Industries, under the trade name TOSCO® and with manufacturer identification number #13-378, 60 degree conical-spherical tip), weighing 40 g, and a 50 mm Use the drop height of the stylus. In some embodiments, the primary rupture (or the first visible rupture that produces two fragments) occurs immediately or within 0 seconds or 0.1 seconds after the impact causing the fracture to the glass article. In one or more embodiments, the probability of primary failure occurring within the time period described herein, as measured by the fragility test, is at least about 90%. In some embodiments, the secondary fracture(s) occurs in 5 seconds or less (eg, 4 seconds or less, 3 seconds or less, 2 seconds or less, or about 1 second or less). As used herein, "secondary fracture" means a fracture that occurs after a primary fracture. In one or more embodiments, the probability of secondary failure(s) occurring within the time period described herein, as measured by the fragility test, is at least about 90%.

In one or more embodiments, upon breakage, the glass article emits fewer and fewer fragments of potential concern to the user than exhibited by known glass articles currently used in portable electronic devices. As used herein, the terms “released” or “released” refer to fragments that migrate from their original location or placement in a glass article after the glass article has been ruptured. In some embodiments, after the glass article is ruptured and a plurality of fragments are formed, about 10% or less (eg, about 8% or less, about 6% or less, or about 5% or less) of the plurality of fragments is released. In some embodiments, after the glass article is ruptured and a plurality of fragments are formed, at least about 50% of the ejected portions of the plurality of fragments have a maximum dimension of less than 0.5 mm. In some embodiments, the number or amount of debris released may be characterized by weight, relative to the glass article before and after breaking. For example, the difference between the weight of the glass article prior to breaking (including the total weight of the ejected portion of the plurality of fragments and the non-emitted portion of the fragment after breaking) and the weight of the non-emitted portion of the fragment is , about 1% or less of the pre-impact weight. In some instances, the difference between the weight of the glass article prior to breaking and the weight of the non-emitted portion of the fragment is , less than about 0.0005 g (eg, 0.0004 g or less, 0.0003 g or less, 0.0002 g or less, or 0.0001 g or less).

In one or more embodiments, the glass article exhibits dicing of height in a more uniform pattern across the surface and volume thereof. In some embodiments, when the glass article has a non-uniform thickness (ie, is formed to have a three-dimensional or 2.5-dimensional shape), this height of dicing and uniformity is exhibited. Without wishing to be bound by theory, it is to strengthen the thinnest portion of a glass article to a sufficient degree, as defined by current industry standards, that some portions of the glass article exhibit fragility, while others do not. make it possible

In one or more embodiments, the glass article (which is bonded directly to the substrate, ie, the display unit) exhibits haze after breaking, due to the high-density fracture pattern. The readability depends on the viewing angle and thickness of the glass-based article. At a viewing angle of 90 degrees relative to the major surface of the glass article, or at normal incidence, the ruptured glass article exhibits low haze such that the underlying image or text is visible to the naked eye. At viewing angles of 70 degrees or less with respect to the major surface of the glass article (or at angles greater than 30 degrees from normal incidence), the broken glass article exhibits a haze that prevents the underlying image or text from being visible to the naked eye. It is to be understood that such a haze is present when the fragments of the glass article are still clustered together or when less than 10% of the fragments are released from the glass article. While not wishing to be bound by theory, it is believed that, after breaking, the glass article can provide privacy screen functionality due to the low haze at 90 degrees and the high haze at smaller viewing angles.

In some embodiments, at least one major surface of the glass article has a low surface roughness after the glass article is ruptured. This property is desirable when cuts and abrasions to the user are minimized or reduced even if the user uses or touches the glass article even after the glass article is broken.

In one or more embodiments, the glass articles described herein may be combined with a hermetic layer. The hermetic layer is a material that, if broken, may contain fragments of glassware. For example, the sealing layer may include a polymer material. In one or more embodiments, the sealing layer may comprise an adhesive (such as a pressure sensitive adhesive). In one or more embodiments, the hermetic layer may have a Young's modulus in the range of about 0.5 to about 1.2 MPa. In one or more embodiments, the hermetic layer may comprise a filled epoxy, an unfilled epoxy, a filled urethane, or an unfilled urethane.

Examples of filled epoxy include 70.69 wt% Nanopox C620 colloidal silica sol (40% silica nanoparticles in alicyclic epoxy resin), 23.56 wt% Nanopox C680 (50 wt% in 3-ethyl-3-hydroxymethyl-oxetane) % silica nanoparticles), 3 wt% Coatosil MP-200 epoxy functional silane (adhesive promoter), 2.5 wt% Cyracril UVI-6976 (a cationic photoinitiator comprising triarylsulfonium hexafluoroantimonate salt in propylene carbonate) ), 0.25 wt% Tinuvine 292 amine stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate and 1-(methyl)-8-(1,2,2) , 6,6-pentamethyl-4-piperidinyl)-sebacate) UV derived catalytic epoxy.

Examples of unfilled epoxy materials include 48 wt% Synasia S06E cycloaliphatic epoxy, 48 wt% Synasia S-101 (3-ethyl-3-oxetanemethanol), 1 wt% UVI-6976 (cationic photoinitiator) and 3 wt% Silquest A-186 (epoxy functional silane).

In some embodiments, low modulus urethane acrylates may be used in the hermetic layer. In some embodiments, the material may include a silica filling. Examples of low modulus urethane acrylates include 31.5 wt% Doublemer 554 (aliphatic urethane diacrylate resin), 1.5 wt% Genomer 4188/M22 (monofunctional urethane acrylate), 20 wt% NK Ester A-SA (beta-acrylic Royl oxyethyl hydrogen succinate), 10 wt % Sartomer SR339 2 (phenoxyethyl acrylate), 4 wt % Irgacure 2022 (photoinitiator, acyl phosphine oxide/alpha hydroxy ketone), 3 wt % adhesion promoter (eg For example, Silquest A-189, gamma-mercaptopropyltrimethoxysilane). To form the filled urethane, 4 wt % silica powder (such as Hi Sil 233) can be added.

In one or more embodiments, the glass article may be combined with a hermetic layer that may or may not be adhered thereto. In some embodiments, the glass article may be adhered to and disposed of in the hermetic layer. The glass article may be temporarily or permanently adhered to the hermetic layer. As shown in FIG. 9A , the hermetic layer 20 is disposed on at least one major surface of the glass article (eg, 12 , 14 in FIG. 1A ). 9A , the hermetic layer 20 is not disposed on any of the minor surfaces 16 , 18 ; However, the hermetic layer 20 may extend from a major surface at least partially along one or both of the minor surfaces 16 , 18 or along the entire length of one or both of the minor surfaces 16 , 18 . . In such embodiments, the hermetic layer may be formed from the same material. In one or more alternative embodiments, the hermetic layer formed on the major surface can be different from the hermetic layer formed on any portion of the minor surface. 9B illustrates an embodiment in which the hermeticity layer 20 is disposed on the major surface 14 and the second hermetic layer 22 is disposed on both the minor surfaces 16 , 18 . In one or more embodiments, the hermetic layer 20 is compositionally different from the second hermetic layer 22 .

In one or more embodiments, the glass article may comprise a stress profile comprising spikes, as described herein, such that the surface CS ranges from about 400 MPa to about 1200 MPa, and (as shown in FIG. 9B ) together) a sealing material 20 on one major surface 14 , and a second hermetic material 22 on two minor surfaces 16 , 18 . In one or more embodiments, the glass article may comprise a stress profile without spikes, such that the surface CS ranges from about 150 MPa to about 500 MPa, and (as shown in FIG. 9A ) on the major surface 14 . contains only the sealing material (20). The glass articles described herein can be incorporated into a variety of products and products, such as consumer electronic products or devices (eg, cover glasses for portable electronic devices and touch-enabled displays). The glass article may also be a display (or display article) (eg, billboards, point-of-sale systems, computers, navigation systems, and the like), architectural articles (walls, fixtures, panels, windows, etc.) , transport products (eg, automotive applications, trains, aircraft, marine vessels, etc.), consumer electronics (eg washing machines, dryers, dishwashers, refrigerators and the like), packaging (eg For example, pharmaceutical packaging or containers) or any product that requires some rupture resistance.

As shown in FIG. 10 , an electronic device 1000 can include a glass-based article 100 according to one or more embodiments described herein. The device 100 includes a housing 1020 having a front surface 1040 , a rear surface 1060 , and sides 1080 ; and electrical components (not shown) residing at least partially or wholly within the housing and including at least a controller, a memory, and a display 1120 in front or adjacent to the front of the housing. The glass-based article 100 is shown as a cover disposed on or on the front of the housing such that it is over the display 1120 . In some embodiments, a glass-based article may be used as a back cover.

In some embodiments, the electronic device may include a tablet, a transparent display, a mobile phone, a video player, an information terminal device, an electronic-reader, a laptop computer, or a non-transparent display.

In one or more embodiments, the glass articles described herein may be used in packaging. For example, the packaging may include a glass article in the form of a bottle, vials or container containing a liquid, solid or gaseous substance. In one or more embodiments, the glass article is a vial containing a chemical, such as a pharmaceutical substance. In one or more embodiments, the packaging comprises a housing comprising an opening, an outer surface, and an inner surface defining an enclosure. The housing may be formed from the glass articles described herein. Glass articles include a hermetic layer. In some embodiments, the enclosure is filled with a chemical or pharmaceutical substance. In one or more embodiments, the opening of the housing may be closed or sealed by a cap. In other words, the cap may be disposed on the opening to close or seal the enclosure.

The glass article may include an amorphous substrate, a crystalline substrate, or a combination thereof (eg, a glass-ceramic substrate). The glass article may comprise alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminophosphosilicate glass or alkali aluminoborosilicate glass. In one or more embodiments, the glass article substrate (prior to being chemically strengthened as described herein) has SiO ₂ in the range of about 40 to about 80, Al ₂ O ₃ in the range of about 10 to about 30, about 0 a glass having a composition comprising B ₂ O ₃ in the range of from about 0 to about 10, R ₂ O in the range of about 0 to about 20, and RO, in mole %, in the range of about 0 to about 15; may include In some instances, the composition may include one or both of ZrO ₂ in the range of about 0 mol% to about 5 mol% and P ₂ O ₅ in the range of about 0 to about 15 mol%. TiO ₂ may be present in about 0 mol % to about 2 mol %.

In some embodiments, the glass composition contains SiO ₂ in mol % from about 45 to about 80, from about 45 to about 75, from about 45 to about 70, from about 45 to about 65, from about 45 to about 60, from about 45 to from about 65, from about 45 to about 65, from about 50 to about 70, from about 55 to about 70, from about 60 to about 70, from about 70 to about 75, or from about 50 to about 65.

In some embodiments, the glass composition contains Al ₂ O ₃ in mol % from about 5 to about 28, from about 5 to about 26, from about 5 to about 25, from about 5 to about 24, from about 5 to about 22, about 5 to about 20, about 6 to about 30, about 8 to about 30, about 10 to about 30, about 12 to about 30, about 14 to about 30, about 16 to about 30, about 18 to about 30, or about 18 to about 28 may be included.

In one or more embodiments, the glass composition comprises, in mol %, B ₂ O ₃ , from about 0 to about 8, from about 0 to about 6, from about 0 to about 4, from about 0.1 to about 8, from about 0.1 to about 6, from about 0.1 to about 4, from about 1 to about 10, from about 2 to about 10, from about 4 to about 10, from about 2 to about 8, from about 0.1 to about 5, or from about 1 to about 3. In some instances, the glass composition may be substantially free of B ₂ O ₃ . As used herein, the phrase "substantially free" of a component of a composition is that the component is not actively or intentionally added to the composition during initial batching, but may be present as an impurity in an amount less than about 0.001 mol %. means

In some embodiments, the glass composition may include one or more alkaline earth metal oxides, such as MgO, CaO and ZnO. In some embodiments, the total amount of one or more alkaline earth metal oxides may be a non-zero amount of up to about 15 mol %. In one or more specific embodiments, the total amount of any one of the alkaline earth metal oxides is up to about 14 mol%, up to about 12 mol%, up to about 10 mol%, up to about 8 mol%, up to about 6 mol%, about 4 up to about 2 mol %, or up to about 1.5 mol %, or up to about 1.5 mol %. In some embodiments, the total amount of the one or more alkaline earth metal oxides, in mole %, is about 0.1 to 10, about 0.1 to 8, about 0.1 to 6, about 0.1 to 5, about 1 to 10, about 2 to 10, or It may range from about 2.5 to 8. The amount of MgO can range from about 0 mol% to about 5 mol% (eg, from about 2 mol% to about 4 mol%). The amount of ZnO may range from about 0 to about 2 mol %. The amount of CaO may be from about 0 mol% to about 2 mol%. In one or more embodiments, the glass composition can include MgO and can be substantially free of CaO and ZnO. In one variation, the glass composition can include either CaO or ZnO, and can be substantially free of the other of MgO, CaO and ZnO. In one or more specific embodiments, the glass composition can include only two of the alkaline earth metal oxides of MgO, CaO and ZnO, and can be substantially free of a third earth metal oxide.

The total amount of alkali metal oxide R ₂ O in the glass composition, in mole %, is about 5 to about 20, about 5 to about 18, about 5 to about 16, about 5 to about 15, about 5 to about 14, about 5 to about 12, about 5 to about 10, about 5 to about 8, about 5 to about 20, about 6 to about 20, about 7 to about 20, about 8 to about 20, about 9 to about 20, about 10 to about 20 , from about 6 to about 13, or from about 8 to about 12.

In one or more embodiments, the glass composition comprises from about 0 mol% to about 18 mol%, from about 0 mol% to about 16 mol%, from about 0 mol% to about 14 mol%, from about 0 mol% to about Na ₂ O about 10 mol%, about 0 mol% to about 5 mol%, about 0 mol% to about 2 mol%, about 0.1 mol% to about 6 mol%, about 0.1 mol% to about 5 mol%, about 1 mol% to from about 5 mol%, from about 2 mol% to about 5 mol%, or from about 10 mol% to about 20 mol%.

In some embodiments, the amounts of Li ₂ O and Na ₂ O are adjusted to specific amounts or ratios to balance formability and ion exchangeability. For example, as the amount of Li ₂ O increases, the liquidus viscosity may decrease, thus preventing the use of some molding methods; However, these glass compositions, as described herein, are ion exchanged to deeper DOC levels. The amount of Na ₂ O can alter liquidus viscosity, but inhibit ion exchange to deeper DOC levels.

In one or more embodiments, the glass composition may include K ₂ O in an amount of less than about 5 mol %, less than about 4 mol %, less than about 3 mol %, less than about 2 mol %, or less than about 1 mol %. In one or more optional embodiments, the glass composition can be substantially free of K ₂ O, as defined herein.

In one or more embodiments, the glass composition comprises Li ₂ O from about 0 mol% to about 18 mol%, from about 0 mol% to about 15 mol% or from about 0 mol% to about 10 mol%, from about 0 mol% to from about 8 mol%, from about 0 mol% to about 6 mol%, from about 0 mol% to about 4 mol%, or from about 0 mol% to about 2 mol%. In some embodiments, the glass composition contains Li ₂ O from about 2 mol% to about 10 mol%, from about 4 mol% to about 10 mol%, from about 6 mol% to about 10 mol, or from about 5 mol% to about It may be included in an amount of 8 mol%. In one or more optional embodiments, the glass composition can be substantially free of Li ₂ O, as defined herein.

In one or more embodiments, the glass composition may include Fe ₂ O ₃ . In such embodiments, Fe ₂ O ₃ is less than about 1 mol%, less than about 0.9 mol%, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol%, less than about 0.5 mol%, about 0.4 mol% less than about 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol%, and all ranges and sub-ranges therebetween. In one or more optional embodiments, the glass composition can be substantially free of Fe ₂ O ₃ , as defined herein.

In one or more embodiments, the glass composition may include ZrO ₂ . In such embodiments, ZrO ₂ is less than about 1 mol%, less than about 0.9 mol%, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol%, less than about 0.5 mol%, less than about 0.4 mol%, less than about 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol% and all ranges and sub-ranges therebetween. In one or more optional embodiments, the glass composition can be substantially free of ZrO ₂ , as defined herein.

In one or more embodiments, the glass composition contains P ₂ O ₅ from about 0 mol% to about 10 mol%, from about 0 mol% to about 8 mol%, from about 0 mol% to about 6mol%, from about 0 mol% to about 4 mol%, about 0.1 mol% to about 10 mol%, about 0.1 mol% to about 8 mol%, about 4 mol% to about 8 mol%, or about 5 mol% to about 8 mol% can In some instances, the glass composition may be substantially free of P ₂ O ₅ .

In one or more embodiments, the glass composition may include TiO ₂ . In such embodiments, TiO ₂ may be present in an amount less than about 6 mol %, less than about 4 mol %, less than about 2 mol %, or less than about 1 mol %. In one or more optional embodiments, the glass composition can be substantially free of TiO ₂ , as defined herein. In some embodiments, TiO ₂ is present in an amount ranging from about 0.1 mol % to about 6 mol %, or from about 0.1 mol % to about 4 mol %. In some embodiments, the glass may be substantially free of TiO ₂ .

In some embodiments, the glass composition may include various compositional relationships. For example, the glass composition may include a ratio of the amount of Li ₂ O (mol %) to the total amount of R ₂ O (mol %) in the range of about 0.5 to about 1. In some embodiments, the glass composition can include a difference between the amount of Al ₂ O ₃ (mol %) and the total amount of R ₂ O (mol %) in the range of about -5 to about 0. In some instances, the glass composition may include a difference between the total amount of R _x O (mol %) and the amount of Al ₂ O ₃ in the range of about 0 to about 3. The glass composition of one or more embodiments may exhibit a ratio of the amount of MgO (mol%) to the total amount of RO (mol%) in the range of about 0 to about 2.

In some embodiments, the composition used for the glass substrate comprises 0-2 mol % selected from the group comprising Na ₂ SO ₄ , NaCl, NaF, NaBr, K ₂ SO ₄ , KCl, KF, KBr, and SnO ₂ . It may be batched with at least one fining agent. A glass composition according to one or more embodiments further comprises SnO ₂ in the range of from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 2, from about 0.1 to about 1, or from about 1 to about 2. can The glass compositions disclosed herein may be substantially free of As ₂ O ₃ and/or Sb ₂ O ₃ .

In one or more embodiments, the composition specifically comprises from 62 mol% to 75 mol% SiO ₂ ; 10.5 mol % to about 17 mol % Al ₂ O ₃ ; 5 mol % to about 13 mol % Li ₂ O; 0 mol% to about 4 mol% ZnO; 0 mol% to about 8 mol% MgO; 2 mol % to about 5 mol % TiO ₂ ; 0 mol % to about 4 mol % B ₂ O ₃ ; 0 mol % to about 5 mol % Na ₂ O; 0 mol % to about 4 mol % K ₂ O; 0 mol % to about 2 mol % ZrO ₂ ; 0 mol % to about 7 mol % P ₂ O ₅ ; 0 mol % to about 0.3 mol % Fe ₂ O ₃ ; 0 mol % to about 2 mol % MnOx; and 0.05 mol% to about 0.2 mol% SnO ₂ .

In one or more embodiments, the composition comprises from 67 mol % to about 74 mol % SiO ₂ ; 11 mol % to about 15 mol % Al ₂ O ₃ ; 5.5 mol % to about 9 mol % Li ₂ O; 0.5 mol % to about 2 mol % ZnO; 2 mol% to about 4.5 mol% MgO; 3 mol % to about 4.5 mol % TiO ₂ ; 0 mol % to about 2.2 mol % B ₂ O ₃ ; 0 mol % to about 1 mol % Na ₂ O; 0 mol % to about 1 mol % K ₂ O; 0 mol % to about 1 mol % ZrO ₂ ; 0 mol % to about 4 mol % P ₂ O ₅ ; 0 mol % to about 0.1 mol % Fe ₂ O ₃ ; 0 mol% to about 1.5 mol% MnOx; and 0.08 mol% to about 0.16 mol%SnO ₂ .

In one or more embodiments, the composition comprises: 70 mol% to 75 mol% SiO ₂ ; 10 mol % to about 15 mol % Al ₂ O ₃ ; 5 mol % to about 13 mol % Li ₂ O; 0 mol% to about 4 mol% ZnO; 0.1 mol% to about 8 mol% MgO; 0 mol % to about 5 mol % TiO ₂ ; 0.1 mol % to about 4 mol % B ₂ O ₃ ; 0.1 mol % to about 5 mol % Na ₂ O; 0 mol % to about 4 mol % K ₂ O; 0 mol % to about 2 mol % ZrO ₂ ; 0 mol % to about 7 mol % P ₂ O ₅ ; 0 mol % to about 0.3 mol % Fe ₂ O ₃ ; 0 mol % to about 2 mol % MnOx; and 0.05 mol% to about 0.2 mol% SnO ₂ .

In one or more embodiments, the composition comprises from 52 mol % to about 63 mol % SiO ₂ ; 11 mol % to about 15 mol % Al ₂ O ₃ ; 5.5 mol % to about 9 mol % Li ₂ O; 0.5 mol % to about 2 mol % ZnO; 2 mol% to about 4.5 mol% MgO; 3 mol % to about 4.5 mol % TiO ₂ ; 0 mol % to about 2.2 mol % B ₂ O ₃ ; 0 mol % to about 1 mol % Na ₂ O; 0 mol % to about 1 mol % K ₂ O; 0 mol % to about 1 mol % ZrO ₂ ; 0 mol % to about 4 mol % P ₂ O ₅ ; 0 mol % to about 0.1 mol % Fe ₂ O ₃ ; 0 mol% to about 1.5 mol% MnOx; and 0.08 mol % to about 0.16 mol % SnO ₂ .

In some embodiments, the composition can be substantially free of any one or more of B ₂ O ₃ , TiO ₂ , K ₂ O and ZrO ₂ .

In one or more embodiments, the composition may comprise at least 0.5 mol % of P ₂ O ₅ , Na ₂ O and optionally Li ₂ O, wherein Li ₂ O (mol %)/Na ₂ O (mol %) < 1 Additionally, these compositions may be substantially free of B ₂ O ₃ and K ₂ O. In some embodiments, the composition may include ZnO, MgO and SnO ₂ .

In some embodiments, the composition comprises: from about 58 mol % to about 65 mol % SiO ₂ ; from about 11 mol % to about 19 mol % Al ₂ O ₃ ; about 0.5 mol % to about 3 mol % P ₂ O ₅ ; about 6 mol % to about 18 mol % Na ₂ O; 0 mol% to about 6 mol% MgO; and 0 mol % to about 6 mol % ZnO. In some embodiments, the composition comprises from about 63 mol% to about 65 mol% SiO ₂ ; 11 mol % to about 17 mol % Al ₂ O ₃ ; about 1 mol % to about 3 mol % P ₂ O ₅ ; about 9 mol % to about 20 mol % Na ₂ O; 0 mol% to about 6 mol% MgO; and 0 mol % to about 6 mol % ZnO.

In some embodiments, the composition can include the compositional relationship R ₂ O(mol%)/Al ₂ O ₃ (mol%) < 2, where R ₂ O = Li ₂ O+Na ₂ O. In some embodiments, 65 mol % < SiO ₂ (mol %)+P ₂ O ₅ (mol %) < 67 mol %. In certain embodiments, R ₂ O(mol%)+R'O(mol%)-Al ₂ O ₃ (mol%)+P ₂ O ₅ (mol%) > -3 mol%, where R ₂ O = Li ₂ O+Na ₂ O, and R′O is the total amount of divalent metal oxide present in the composition.

Other representative compositions of glass articles prior to chemical strengthening, as described herein, are shown in Table 1.

Representative composition before chemical strengthening. mol% line. A line. B line. C line. D line. E line. F SiO ₂ 71.8 69.8 69.8 69.8 69.8 69.8 Al ₂ O ₃ 13.1 13 13 13 13 13 B ₂ O ₃ 2 2.5 4 2.5 2.5 4 Li ₂ O 8 8.5 8 8.5 8.5 8 MgO 3 3.5 3 3.5 1.5 1.5 ZnO 1.8 2.3 1.8 2.3 2.3 1.8 Na ₂ O 0.4 0.4 0.4 0.4 0.4 0.4 TiO ₂ 0 0 0 One One One Fe ₂ O ₃ 0 0 0 0.8 0.8 0.8 SnO ₂ 0.1 0.1 0.1 0.1 0.1 0.1

Other representative compositions of glass-based articles prior to chemical strengthening, as described herein, are shown in Table 1A. Table IB lists selected physical properties determined for the embodiments listed in Table IA. The physical properties listed in Table 1B are: density; low and high temperature CTE; strain point, annealing point and softening point; 10 ¹¹ Poise, 35 kP, 200 kP, liquidus, and zircon decomposition temperatures; zircon decomposition and liquidus viscosity; Poisson's ratio; Young's modulus; refractive index, and stress optical coefficient. In some embodiments, the glass-based articles and glass substrates described herein have a high temperature CTE of 30 ppm/° C. or less and/or a Young's modulus of at least 70 GPa, and in some embodiments, a Young's modulus of up to 80 GPa.

[Table 1A]

Representative composition before chemical strengthening.

[Table 1B]

Selected physical properties of the glasses listed in Table 1A.

When the glass article comprises a glass-ceramic, the crystalline phase may comprise β-spodumene, rutile, gahnite or other known crystalline phases and combinations thereof.

The glass article may be substantially planar, although other embodiments may utilize curved or other shaped or engraved substrates. In some instances, the glass article may have a 3D or 2.5D shape. The glass article may be substantially optically clear, transparent, and free from light scattering. The glass article may have a refractive index in the range of about 1.45 to about 1.55. As used herein, refractive index values are for a wavelength of 550 nm.

Additionally or alternatively, the thickness of the glass article may be constant along one or more dimensions or may vary one or more of its dimensions for aesthetic and/or functional reasons. For example, the edge of the glass article may be thicker as compared to a more central region of the glass article. The length, width, and thickness dimensions of the glass article may also vary depending on the article application or use.

The glass article may be characterized by the manner in which it was formed. For example, the glass article may be float-formable (ie formed by a float process), down-drawable, and in particular, fusion-formable or slot-drawable (ie a fusion draw process or a slot draw process and molded by the same down-drawing process).

Float-formable glass articles can be characterized by a smooth surface, and a uniform thickness is created by flowing the molten glass over a layer of molten metal, typically tin. In an exemplary process, molten glass poured onto the surface of a layer of molten tin forms a floating glass ribbon. As the glass ribbon flows through the tin bath, the temperature gradually decreases until the glass ribbon solidifies into a solid glass article that can be lifted from the tin onto a roller. Upon removal from the bath, the glass article may be further cooled and annealed to reduce internal stresses. When the glass article is a glass ceramic, the glass article formed from the float process may be subjected to a ceramization process in which one or more crystalline phases are generated.

The down-draw process produces a glass article of uniform thickness that retains a relatively pristine surface. Since the average flexural strength of a glass article is controlled by the amount and size of surface flaws, the pristine surface with the least contact has a higher initial strength. When this high strength glass article is then further strengthened (eg, chemically), the resulting strength can be higher than that of a glass article having a lapped and polished surface. The down-drawn glass article may be drawn to a thickness of less than about 2 mm. Additionally, the down drawn glass article has a very flat, smooth surface that can be used in its final application without costly grinding and polishing. When the glass article is a glass ceramic, the glass article formed from the down draw process may be subjected to a ceramization process in which one or more crystalline phases are generated.

The fusion drawing process uses, for example, a drawing tank having channels for receiving molten glass stock. The channel has weirs with openings at the top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the weir. Due to gravity, the molten glass flows down the outer surface of the drawing tank into two flowing glass films. These outer surfaces of the drawing tank extend down and inwardly such that they engage at the edge below the drawing tank. Two flowing glass films join at this edge to fuse and form a single flowing glass article. The fusion draw method offers the advantage that since the two glass films overflowing the channel fuse together, none of the external surfaces of the resulting glass article are in contact with any part of the device. Thus, the surface properties of the fusion drawn glass article are not affected by such contact. When the glass article is a glass ceramic, the glass article formed from the fusion process may be subjected to a ceramization process in which one or more crystalline phases are generated.

The slot draw process is distinct from the fusion draw process. In the slot drawing process, molten raw glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle extending the length of the slot. Molten glass flows through the slot/nozzle and is drawn downward into a continuous glass article and into the annealing zone. When the glass article is a glass ceramic, the glass article formed from the slot draw process may be subjected to a ceramization process in which one or more crystalline phases are generated.

In some embodiments, the glass article is disclosed in U.S. Patent No. 8,713,972 entitled "Precision Glass Roll Forming Process and Apparatus," U.S. Patent No. 9,003,835 entitled "Precision Roll Forming of Textured Sheet Glass," As described in U.S. Patent Publication No. 20150027169 entitled "Methods And Apparatus For Forming A Glass Ribbon," and U.S. Patent Publication No. 20050099618, entitled "Apparatus and Method for Forming Thin Glass Articles." may be formed using a rolling process, the entire contents of which are incorporated herein by reference. More specifically, the glass article may be formed by supplying a vertical stream of molten glass, a supplied feed of molten glass or glass-ceramic having a pair of forming rolls maintained at a surface temperature of at least about 500°C or at least about 600°C. forming a stream to form a formed glass ribbon having a formed thickness; producing a sized glass ribbon having a desired thickness and a desired thickness uniformity. The apparatus used to form the glass ribbon comprises: a glass injection apparatus for supplying a fed stream of molten glass; A pair of forming rolls maintained at a surface temperature of at least about 500° C., receiving a fed stream of molten glass to form a formed glass ribbon of a formed thickness and thinning the fed stream of molten glass between the forming rolls. a forming roll proximately spaced apart from each other defining a glass forming gap between the forming rolls having a glass forming gap positioned vertically below the glass injection apparatus for and a pair of sizing rolls maintained at a surface temperature of 400° C. or less, wherein the sizing rolls are configured to heat the formed glass ribbon to produce a sized glass ribbon having a desired thickness and a desired thickness uniformity. A glass sizing gap is defined between the sizing rolls having a glass sizing gap positioned vertically below the forming roll for receiving and thinning the formed glass ribbon so as to be closely spaced from each other.

In some instances, the thin rolling process may be utilized where the viscosity of the glass does not allow the use of fusion or slot draw methods. For example, thin rolling can be utilized to form glass articles when the glass exhibits a liquidus viscosity of less than 100 kP.

The glass article may be acid polished or otherwise treated to eliminate or reduce the effects of surface flaws.

Another aspect of the present disclosure relates to a method of forming a break-resistant glass article. The method includes providing a glass substrate having a first surface and a second surface defining a thickness of about 1 millimeter or less and a stress profile in the glass substrate, as described herein, to provide a break-resistant glass article. It includes the step of generating In one or more embodiments, generating the stress profile comprises ion exchanging a plurality of alkali ions into the glass substrate to form an alkali metal oxide concentration gradient comprising a non-zero concentration of alkali metal oxide extending along a thickness; ion exchange step. In one embodiment, generating the stress profile comprises a nitrate of Na+, K+, Rb+, Cs+, or a combination thereof, having a temperature of at least about 350°C (eg, from about 350°C to about 500°C). and immersing the glass substrate in a molten salt bath. In one embodiment, the molten bath may include NaNO ₃ and may have a temperature of about 485° C. In another embodiment, the bath may include NaNO ₃ , and may have a temperature of about 430°C. The glass substrate may be cured for at least about 2 hours, to about 48 hours (eg, from about 12 hours to about 48 hours, from about 12 hours to about 32 hours, from about 16 hours to about 32 hours, from about 16 hours to about 24 hours. , or from about 24 hours to about 32 hours).

In some embodiments, the method may include chemically strengthening or ion exchanging the glass substrate in one or more steps using successive immersion steps in one or more baths. For example, two or more bathtubs may be used in series. The composition of more than one bath may include a single metal (eg, Ag+, Na+, K+, Rb+, or Cs+) or a combination of metals in the same bath. Where more than one bath is utilized, the baths may have the same or different compositions and/or temperatures. The immersion time in each of these baths can be varied to provide the same or a desired stress profile.

In one or more embodiments, a second or subsequent bath may be utilized to generate a larger surface CS. In some instances, the method includes immersing the glass material in a second or subsequent bath to generate a greater surface CS without significantly affecting the DOC and/or chemical depth of the layer. In such embodiments, the second or subsequent bath may include a single metal (eg, KNO ₃ or NaNO ₃ ) or a mixture of metals (KNO ₃ and NaNO ₃ ). The temperature of the second or subsequent bath may be adjusted to generate a larger surface CS. In some embodiments, the immersion time of the glass material in the second or subsequent bath can also be adjusted to generate a greater surface CS without affecting the DOC and/or chemical depth of the layer. For example, the immersion time in the second or subsequent bath may be less than 10 hours (e.g., about 8 hours or less, about 5 hours or less, about 4 hours or less, about 2 hours or less, about 1 hour or less, about 30 minutes) or less, about 15 minutes or less, or about 10 minutes or less).

In one or more optional embodiments, the method may include one or more thermal treatment steps that may be used in combination with the ion-exchange processes described herein. The heat treatment includes heat treating the glass article to obtain a desired stress profile. In some embodiments, heat treating comprises annealing, tempering, or heating the glass material to a temperature in the range of about 300°C to about 600°C. The heat treatment may last from 1 minute to up to 18 hours. In some embodiments, the heat treatment may be used after one or more ion-exchange processes, or between ion-exchange processes.

Example

Various embodiments will be made clear by the following examples.

Example 1

The glass articles according to Examples 1A-1B and Comparative Examples 1C-1G have 58 mol% SiO ₂ , 16.5 mol% Al ₂ O ₃ , 17 mol% Na ₂ O, 3 mol% MgO, and 6.5 mol% P ₂ O It is made by providing a glass substrate having a nominal glass composition of ₅ . The glass substrate has a thickness of 0.4 mm and dimensions of a length and a width of 50 mm. The glass substrate is chemically strengthened by an ion exchange process comprising immersion in a molten salt bath of 80% KNO ₃ and 20% NaNO ₃ having a temperature of about 420° C. for the period shown in Table 2. The resulting glass article was then polished to the major surface of each sample using 90 grit SiC particles at a pressure of 5 psi, 15 psi or 25 psi and AROR as described above, as also shown in Table 2 applied to the test. Table 2 shows the breaking load or average coaxial flexural strength of glassware.

Chemical strengthening conditions and AROR results for Example 1 line. Ion exchange conditions Average kgf at 5 psi
(Standard Deviation) Average kgf at 15 psi
(Standard Deviation) Average kgf at 25 psi
(Standard Deviation) 1C 420℃ / 4 hours 49.4 (7.1) 17.4 (7.2) 0.3 (0.9) 1D 420℃/8 hours 49.9 (7.1) 36.5 (6.7) 19.3 (6.4) 1A 420℃/16 hours 47.5 (6.0) 38.3 (2.8) 30.0 (5.4) 1B 420℃/32 hours 36.9 (4.3) 30.9 (3.1) 26.2 (2.8) 1E 420℃/64 hours 18.7 (1.5) 15.3 (0.9) 13.5 (1.2) 1F 420℃/128 hours 5.9 (0.5) 5.4 (0.3) 4.5 (0.3)

The failure load or average coaxial flexural strength of the examples after abrasion at 15 psi and 25 psi is plotted in FIG. 11 . 11 , Examples 1A and 1B exhibit the greatest average coaxial flexural strength after abrasion at 25 psi. Thus, the AROR performance of Examples 1A and 1B shows that these glassware exhibit a highly diced fracture pattern, exhibiting improved retention strength, particularly for deeper wear depths resulting from higher wear pressures.

Example 2

Glass articles according to Examples 2A-2C and Comparative Examples 2D-2F were made by providing a glass substrate and chemically strengthening the glass substrate. The glass substrates used in Examples 2A-2C and Comparative Examples 2E-2F were: 69.2 mol% SiO ₂ , 12.6 mol% Al ₂ O ₃ , 1.8 mol% B ₂ O ₃ , 7.7 mol% Li ₂ O, 0.4 mol% It has a nominal glass composition of Na ₂ O, 2.9 mol% MgO, 1.7 mol% ZnO, 3.5 mol% TiO ₂ and 0.1 mol% SnO ₂ . The substrate used in Comparative Example 2D had the same composition as in Example 1.

The glass substrate has a thickness of 1 mm and dimensions of length and width to allow assembly with known mobile device housings. The glass substrates were chemically strengthened by the ion exchange process shown in Table 3. The CT and DOC values for Examples 2A-2C were determined by SCALP and are also shown in Table 3.

Ion exchange conditions and drop test results for Example 2 Example melt bath composition Melting bath temperature (℃) Immersion time (hours) CT (MPa) DOC (μm) Example 2A 100% NaNO ₃ 430 24 128 160 Example 2B 100% NaNO ₃ 430 29 153 200 Example 2C 100% NaNO ₃ 430 33 139 200 Comparative Example 2D Comparative Example 2E 100% NaNO ₃ 390 3.5 Comparative Example 2F 100% NaNO ₃ 430 48

Comparative Example 2D was ion exchanged to exhibit an error function stress profile with a DOC greater than 75 micrometers (as measured by Roussev I with IWKB analysis). The resulting glass article is then remounted in the same carrier housing and subjected to a drop test as described above onto 30 grit sandpaper. 12 shows the maximum failure height for an embodiment. 12 , Examples 2A-2C exhibit significantly greater maximum break heights (ie, 212 cm, 220 cm and 220 cm, respectively) and dicing behavior. Comparative Example 2F, having the same composition, does not exhibit the same dicing behavior and exhibits a lower maximum failure height compared to Examples 2A-2C.

Example 3

Glass articles according to Examples 3A-3K and Comparative Examples 3L-3X were made by providing a glass substrate and strengthening the glass substrate. The substrates used in Examples 3A-3D had the same composition as Example 1, and the substrates used in Comparative Examples 3L-3X had 69 mol% SiO ₂ , 10.3 mol% Al ₂ O ₃ , 15.2 mol% Na ₂ O, 5.4 mol % MgO, and 0.2 mol % SnO ₂ nominal glass composition.

The glass substrate has a thickness of 0.4 mm and dimensions of a length and a width of 50 mm x 50 mm. The glass substrate is chemically strengthened by ion exchange. Examples 3A-3K were ion exchanged in a molten salt bath of 80% KNO ₃ and 20% NaNO ₃ at a temperature of 460° C. for 12 hours. Comparative Examples 3L-3X were ion exchanged and each resulting glass article exhibited a surface CS of 912 MPa and a DOC of 37 μm, as measured by FSM.

The resulting glass article is then impacted against one major surface of each article with a tungsten carbide conical spherical scribe for a single blow from the drop distance (as shown in Tables 4 and 5) and the glass article This is applied to fracture by evaluating the fracture or fracture pattern in terms of how many fragments result, and the fragility of the glass article, whether it fractures immediately or does not fracture at all.

Fracture characteristics and fracture mechanics of Examples 3A-3K. line. number of hits Number of fragments (#) Break (Y/N) Fall distance (inches) time to break 3A One 100+ Yes 0.611 Immediately 3B One DNB DNB 0.561 DNB 3C One DNB DNB 0.511 DNB 3D One DNB DNB 0.461 DNB 3E One DNB DNB 0.411 DNB 3F One DNB DNB 0.361 DNB 3G One DNB DNB 0.311 DNB 3H One 100+ Yes 0.261 Immediately 3I One DNB DNB 0.211 DNB 3J One DNB DNB 0.161 DNB 3K One DNB DNB 0.111 DNB

*DNB = unbreakable

Fracture characteristics and rupture mechanics of Comparative Example 3L-3X. line. number of hits Number of fragments (#) Break (Y/N) Fall distance (inches) time to break 3L One 9 No 0.226 Immediately 3M One 7 No 0.221 Immediately 3N One 5 Yes 0.216 30 seconds 3O One 6 Yes 0.211 30 seconds 3P One 2 No 0.206 30 seconds 3Q One 7 Yes 0.201 1 minute 3R One DNB DNB 0.196 DNB 3S One 5 Yes 0.191 30 seconds 3T One 6 Yes 0.186 10 seconds 3U One 9 Yes 0.181 10 seconds 3V One 6 Yes 0.176 15 seconds 3W One 10+ Yes 0.171 10 seconds 3X One 8 Yes 0.111 30 seconds

*DNB = non-breaking As shown in Tables 4-5, the frangibility limit (Frangibility It is clear that glass articles chemically strengthened to conditions near the limit (ie, Comparative Examples 3L-3X) are much more likely to experience delayed failure. Specifically, more than 80% of Comparative Examples 3L-3X failed in a delayed manner, whereas the samples in Table 4 failed or did not break immediately. In addition, Comparative Examples 3L-3X exhibited fewer, larger, and more debris fragments than Examples 3A-4K, which failed with high dicing and exhibited fragments with low aspect ratios.

Example 4

Glass articles according to Examples 4A-4B and Comparative Examples 4C-4F were made by providing a glass substrate having the same nominal composition as Example 1 and strengthening the glass substrate. The glass substrate had a thickness of 0.4 mm and was chemically strengthened by an ion exchange process in which the glass substrate was immersed in a molten salt bath of 80% KNO ₃ and 20% NaNO ₃ having a temperature of 430° C. for the period shown in Table 6. do.

Ion exchange period for Example 5. Example Immersion time (hours) Example 4A 16 Example 4B 32 Comparative Example 4C 4 Comparative Example 4D 8 Comparative Example 4E 64 Comparative Example 4F 128

The concentration of K ₂ O in the glass article is measured using Glow-Discharge Optical Emission Spectroscopy (GDOES). In FIG. 13 , the mol % (expressed as K ₂ O) of larger K+ ions displacing smaller Na+ in the glass substrate is plotted on the vertical axis and plotted as a function of ion-exchange depth. Examples 4A and 4B exhibit higher stored tensile energy (and central tension) than the other profiles, and maximize the DOC as well as the magnitude of surface compression.

14 is an example of Example 4G formed by providing the same substrates as Examples 4A and 4B and immersing in a molten salt bath of 70% KNO ₃ and 30% KNO ₃ having a temperature of 460° C. for 12 hours. , as measured by Roussev I with IWKB analysis applied, represent the stress profile.

Example 5

Glass articles according to Examples 5A-5D (Examples B and C are comparative examples) were made by providing a glass substrate having the same nominal composition as Examples 2A-2C and strengthening the glass substrate. The glass substrate is chemically strengthened by the ion exchange process shown in Table 7.

Ion exchange conditions for Example 5. Example melt bath composition Melting bath temperature (℃) Immersion period (hours) 5A 80% KNO _3/ 20% NaNO ₃ 460 12 Comparative Example 5B 65% KNO _3/ 35% NaNO ₃ 460 12 Comparative Example 5C 100% NaNO ₃ 430 4 5D 100% NaNO ₃ 430 16

Examples 5A and 5B are adhered to the transparent substrate using a pressure sensitive adhesive supplied by 3M under the trade designation 468 MP, applied in the same manner and in the same thickness. Examples 5A and 5B were broken, and the resulting broken glass article was evaluated. 15A and 15B show fracture images of Example 5A and Comparative Example 5B, respectively. As shown in FIG. 15A , Example 5A exhibits higher dicing behavior, and results in fragments having an aspect ratio of less than about 2. As shown in FIG. 15B , Comparative Example 5B results in fragments with higher aspect ratios.

Comparative Examples 5C and 5D were not constrained by the adhesive and were broken. The resulting broken glass article is evaluated. 15c and 15d show the fracture images of Comparative Example 5C and Example 5D, respectively. As shown in FIG. 15C , Comparative Example 5C exhibits larger fragments. As shown in Figure 15D, Example 5D resulted in fragments exhibiting dicing. It is believed that the sub-fragments (not shown) did not extend through the thickness of the glass article.

Example 6

A glass article according to Example 6 was made having the same nominal composition as Examples 3A-3K and providing a glass substrate strengthened in the same manner. Example 6 was evaluated for haze or readability after fracture, at different viewing angles. After breaking, Example 6 shows a high degree of dicing, but still shows good readability at 90° viewing angle, for the surface plane or major surface of the glass article. The readability deteriorates as the viewing angle decreases, as illustrated in the images of FIGS. 16A-16D . 16A shows that the text placed behind Example 6 is still visible and legible at a viewing angle of 90 degrees to the surface plane or major surface of the glass article. Figure 16b shows that it is somewhat visible and legible at a viewing angle of about 67.5 degrees. According to FIGS. 16C-16D , the text is not clear or readable at viewing angles of 45 degrees and 22.5 degrees with respect to the surface plane or major surface of the glass article. Thus, Embodiment 6 can function as a privacy screen when used in a display such that only a viewer can clearly read or see the display, but other viewers next to the viewer cannot clearly read the display .

Example 7

Glass articles according to Examples 7A-7C were made by providing glass substrates having a 2.5-dimensional shape but each having a different thickness (ie, Example 7A had a thickness of 1 mm, Example 7B had a thickness of 0.8 mm). thickness, and Example 7C has a thickness of 0.5 mm). A 2.5-dimensional shape includes a flat major surface and an opposing curved major surface. The composition of the glass substrate is the same as in Examples 2A-2C. The storage tensile energy of each substrate is calculated as a function of ion exchange time using a molten bath with a temperature of 430°C. The stored tensile energy is calculated using the total positive stress across the CT region (327 in FIG. 4) measured by SCALP. The calculated stored tensile energy is plotted as a function of ion exchange time in FIG. 17 . For illustrative purposes, a dashed line at a stored tensile energy value of 10 J/m 2 is drawn to indicate an approximate threshold for fragility. The highlighted area represents the ion-exchange conditions for a single part with a thickness range of 0.5-1.0 mm exhibiting the behavior described herein. Specifically, this range allows for optimal mechanical performance and a similar degree of dicing across the region of the part when the part breaks.

When the known fragility limit is used to determine the ion exchange parameters for various thicknesses, at time A, the ion exchange time at which the stored tensile energy reaches less than 10 J/m2, a glass substrate with a thickness of 1 mm becomes brittle It is not easy, and a glass substrate with a thickness of 0.5 mm will have a low CS. At time C, a glass substrate having a thickness of 0.5 mm is not brittle, and a glass substrate having a thickness of 1 mm to 0.8 mm is considered fragile. Thus, using the current definition of vulnerability, Figure 17 shows a relatively thick portion in a given bath at a given temperature, or This indicates that we choose a fairly long ion-exchange time for the region of non-uniform thick part. To provide a fully-finished 2.5D part having substantially improved drop performance and reliability, and a relatively uniform degree of fragmentation or dicing, the part is ion-exchanged for a shorter period of time to avoid fragmentation or dicing. It would be desirable to install a higher stored tensile energy that would be chosen to limit the extent.

18 shows that the installed tensile energy shown in 11 is expressed as central tension (CT), which is used as a more common descriptor of tensile energy in the central region of an ion-exchanged specimen. The sample shown in FIG. 17 is shown.

Example 8

Example 8 includes a glass article made by providing a glass substrate having the same nominal composition as Example 1 and strengthening the glass substrate. The glass substrate had a thickness of 0.4 mm, and was chemically strengthened by a two-step ion exchange process, wherein the glass substrate was first formed of 80% KNO ₃ and 20% NaNO ₃ having a temperature of 460° C. for 12 hours. It is immersed in a molten salt bath, removed from the first molten salt bath, and immersed in a second molten salt bath of 100% KNO ₃ having a temperature of 390° C. for 12 minutes. The resulting glass article has a surface compressive stress of 624.5 MPa, a DOC of about 83.3 micrometers (equivalent to 0.208t), and a maximum CT of about 152.6 MPa, measured by Roussev I subjected to IWKB analysis. 19 shows compressive stress (represented as negative values) and tensile stress (represented as positive values) as a function of depth in micrometers.

Aspect (1) of the present disclosure includes a first surface defining a thickness t of about 1.1 mm or less and a second surface opposing the first surface; a tempered glass article comprising a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; wherein, after the glass article is ruptured according to a fragility test, the glass article comprises a plurality of fragments, wherein at least 90% of the plurality of fragments have an aspect ratio of about 5 or less.

Aspect (2) of the present disclosure is the tempered glass article of aspect (1), wherein the glass article breaks into a plurality of fragments in 1 second or less, as measured by a fragility test.

Aspect (3) of the present disclosure, in the tempered glass article of aspect (1) or (2), wherein at least 80% of the plurality of fragments have a maximum dimension of 3·t or less.

Aspect (4) of the present disclosure, in the tempered glass article of any one of aspects (1) to (3), wherein at least 50% of the plurality of fragments comprise an aspect ratio of 2 or less.

Aspect (5) of the present disclosure, in the tempered glass article of any one of aspects (1) to (4), wherein at least 50% of the plurality of fragments comprise a volume of about 10 mm 3 or less.

Aspect (6) of the present disclosure provides, in the tempered glass article of any one of aspects (1) to (5), wherein the plurality of fragments comprises an ejected portion of the fragment, wherein the ejected portion of the fragment comprises: , including 10% or less of the plurality of fragments.

Aspect (7) of the present disclosure provides that the tempered glass article of any one of aspects (1) to (6), wherein the glass article comprises a first weight prior to breaking, and wherein the plurality of fragments comprises: and a non-released portion of the debris, wherein the non-released portion of the debris has a second weight, and the difference between the first weight and the second weight is equal to one of the first weight. %to be.

Aspect (8) of the present disclosure provides that, in the tempered glass article of any one of aspects (1) to (7), as measured by a fragility test, the probability that the glass article will break into a plurality of fragments in 1 second or less is More than 99%.

Aspect (9) of the present disclosure is the tempered glass article of any one of aspects (1) to (8), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (10) of the present disclosure provides that the strengthened glass article of any one of aspects (1) to (9), wherein the glass article comprises a surface compressive stress and a central tension, wherein a central tension to surface compressive stress The ratio of is in the range of about 0.1 to about 1.

Aspect (11) of the present disclosure, in the tempered glass article of aspect (10), wherein the central tension is 100 MPa/√(t/1 mm) or more (in units of MPa), where t is mm.

Aspect (12) of the present disclosure, wherein the tempered glass article of any one of aspects (10) to (11), wherein the central tension is at least 50 MPa.

Aspect (13) of the present disclosure, in the tempered glass article of any one of aspects (10) to (12), wherein the surface compressive stress is at least 150 MPa.

Aspect (14) of the present disclosure is the tempered glass article of any one of aspects (10) to (13), wherein the surface compressive stress is at least 400 MPa.

Aspect (15) of the present disclosure, in the tempered glass article of any one of aspects (10) to (14), wherein the DOC comprises at least about 0.2 t.

Aspect (16) of the present disclosure provides that the tempered glass article of any one of aspects (1) to (15), wherein the glass article comprises: alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali aluminophosphosilicate glass or alkali aluminoborosilicate glass.

Aspect (17) of the present disclosure is the tempered glass article of any one of aspects (1) to (16), wherein the glass article is disposed on the hermetic layer.

Aspect 18 of the present disclosure includes a first surface defining a thickness t of about 1.1 mm or less and a second surface opposing the first surface; a tempered glass article comprising a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; Here, the glass article, after being polished with 90-grit SiC particles at a pressure of 25 psi for 5 seconds, exhibits a breaking load of about 10 kgf or more.

Aspect (19) of the present disclosure is the strengthened glass article of aspect (18), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (20) of the present disclosure provides that the strengthened glass article of any one of aspects (18) or (19), wherein the glass article comprises a surface compressive stress and a central tension, wherein the center for surface compressive stress is The ratio of tension ranges from about 0.1 to about 1.

Aspect (21) of the present disclosure, in the tempered glass article of aspect (20), wherein the central tension (CT) is at least 50 MPa.

Aspect (22) of the present disclosure is the tempered glass article of aspect (20) or (21), wherein the surface compressive stress is at least 150 MPa.

Aspect (23) of the present disclosure is the tempered glass article of any one of aspects (20) to (22), wherein the surface compressive stress is 400 MPa or more.

Aspect (24) of the present disclosure, in the tempered glass article of any one of aspects (20)-(23), wherein the DOC comprises at least about 0.2 tons.

Aspect (25) provides, in the tempered glass article of any one of aspects (18) to (24), wherein the glass article comprises alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminophosphosilicate glass or alkali alumina. noborosilicate glass.

Aspect (26) of the present disclosure provides the tempered glass article of any one of aspects (20) to (25), wherein the glass article is attached to a substrate.

Aspect 27 of the present disclosure includes a tempered glass substrate; hermetic layer; and a support, wherein the tempered glass substrate has a first surface defining a thickness t of about 1.1 mm or less and a second surface opposite the first surface, the first surface a compressive stress layer extending from a depth of compression (DOC) greater than about 0.11 t, and a central tension (CT) greater than or equal to 50 MPa, wherein the device comprises a tablet, transparent display, mobile phone, video player, information terminal devices, electronic-readers, laptop computers, or non-transparent displays.

Aspect (28) is the apparatus of aspect (27), wherein after the glass article is ruptured according to the fragility test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less.

Perspective (29), the apparatus of aspect (27) or (28), wherein the glass article breaks into a plurality of fragments in less than 1 second, as measured by a fragility test.

Aspect (30) is the apparatus of aspect (28) or (29), wherein at least 80% of the plurality of fragments have a maximum dimension of 5·t or less.

Aspect (31), in the device of any one of aspects (28) to (30), wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less.

Aspect (32), in the device of any one of aspects (28)-(31), wherein at least 50% of the plurality of fragments comprise a volume of about 10 mm 3 or less.

Aspect (33) includes, in the device of any one of aspects (28) to (32), wherein the plurality of fragments comprises an ejected portion of the fragment, wherein the ejected portion of the fragment comprises: Contains no more than 10% of the fragments.

Aspect (34) provides, in the apparatus of any one of aspects (28) to (33), wherein the glass article comprises a first weight prior to breaking, and wherein the plurality of fragments comprises: an ejected portion of the fragments; a non-released portion of the debris, wherein the non-released portion of the debris has a second weight, and the difference between the first weight and the second weight is 1% of the first weight.

Aspect (35) is the apparatus of any one of aspects (28)-(34), wherein the probability that the glass article will break into a plurality of fragments in 1 second or less is at least 99%, as measured by a fragility test .

Aspect (36), the apparatus of any one of aspects (28)-(35), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (37) relates to the apparatus of any one of aspects (27) to (36), wherein the glass article comprises a surface compressive stress and a central tension, wherein the ratio of the central tension to the surface compressive stress is: It ranges from about 0.1 to about 1.

Aspect (38) is the apparatus of aspect (37), wherein the surface compressive stress is at least 150 MPa.

Aspect (39), the apparatus of any one of aspects (27)-(38), wherein the DOC comprises at least about 0.2 t.

Aspect (40) provides, in the apparatus of any one of aspects (27) to (39), wherein the glass article comprises alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminophosphosilicate glass or alkali aluminoboro. silicate glass.

Aspect (41) is the apparatus of any one of aspects (27) to (40), wherein the glass article is disposed on the hermetic layer.

Perspective 42 includes a first surface defining a thickness t of about 1.1 mm or less and a second surface opposing the first surface; a tempered glass article comprising a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; wherein after the glass article is laminated to the hermetic layer and ruptures according to the fragility test, the glass article comprises a break, and wherein at least 5% of the break extends only partially through the thickness.

Perspective (43) is the tempered glass article of aspect (42), wherein the glass article breaks into a plurality of fragments in less than 1 second, as measured by a fragility test.

Aspect (44) is the tempered glass article of aspect (42) or (43), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (45) relates to the strengthened glass article of any one of aspects (44) to (44), wherein the glass article comprises a surface compressive stress and a central tension, wherein a ratio of central tension to surface compressive stress is in the range of about 0.1 to about 1.

Aspect (46) is the tempered glass article of aspect (45), wherein the central tension is 50 MPa or more.

Aspect (47) is the tempered glass article of aspect (45) or (46), wherein the surface compressive stress is 150 MPa or more.

Aspect (48), the tempered glass article of any one of aspects (42)-(47), wherein the DOC comprises at least about 0.2 t.

Aspect (49), the tempered glass article of any one of aspects (42) to (48), wherein the glass article comprises alkali aluminosilicate glass, alkali containing borosilicate glass, or alkali aluminoborosilicate glass .

Aspect (50) is the tempered glass article of any one of aspects (42)-(49), wherein the glass article is disposed on the hermetic layer. Perspective 51 includes a housing having a front face; an electrical component provided at least partially within the housing and comprising at least a controller, a memory, and a display; and a cover glass disposed on the front side of the housing and over the display, the cover glass comprising a tempered glass article, wherein the tempered glass article: defines a thickness t of about 1.1 mm or less; a first surface and a second surface opposite the first surface; a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; and a central tension (CT) of at least about 50 MPa.

Aspect 52, the consumer electronic device of aspect 51, wherein after the glass article is ruptured according to a fragility test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less.

Perspective (53), the consumer electronic device of aspect (52), wherein the glass article ruptures into a plurality of fragments in less than one second, as measured by a fragility test.

Aspect (54) is the consumer electronic device of aspect (52) or (53), wherein at least 80% of the plurality of fragments have a maximum dimension of 2·t or less.

Aspect (55), wherein the consumer electronic device of any one of aspects (52)-(54), wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less.

Aspect (56), wherein the consumer electronic device of any one of aspects (52)-(55), wherein at least 50% of the plurality of fragments comprise a volume of about 10 mm 3 or less.

Aspect (57) includes the consumer electronic device of any one of aspects (52)-(56), wherein the plurality of fragments comprises an ejected portion of the fragment, wherein the ejected portion of the fragment comprises: contains no more than 10% of the plurality of fragments.

Aspect (58) is the consumer electronic device of any one of aspects (52) to (57), wherein the glass article comprises a first weight prior to breaking, and wherein the plurality of fragments comprises: ejection of the fragments. and a non-released portion of the debris, wherein the non-released portion of the debris has a second weight, and wherein the difference between the first weight and the second weight is equal to one of the first weight. %to be.

Aspect (59) provides that, in the consumer electronic device of any one of aspects (53) to (58), as measured by a fragility test, the probability that the glass article will break into a plurality of fragments in 1 second or less is 99 % or more

Aspect (60), the consumer electronic device of any one of aspects (51)-(59), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (61) includes, the consumer electronic device of any one of aspects (51) to (60), wherein the glass article comprises a surface compressive stress and a central tension, wherein a ratio of central tension to surface compressive stress is in the range of about 0.1 to about 1.

Aspect (62) is the consumer electronic device of aspect (61), wherein the surface compressive stress is greater than or equal to 150.

Aspect (63), wherein the consumer electronic device of any one of aspects (51)-(62), wherein the DOC comprises greater than or equal to about 0.2 t.

Aspect (64), in the consumer electronic device of any one of aspects (51) to (63), wherein the glass article comprises alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminophosphosilicate or alkali aluminobo rosilicate glass.

Aspect (65) is the consumer electronic device of any one of aspects (51)-(64), wherein the glass article is disposed on the hermetic layer.

Aspect (66) provides, in the consumer electronic device of any one of aspects (51) to (65), wherein the consumer electronic product comprises: a tablet, a transparent display, a mobile phone, a video player, an information terminal device, an electronic-reader, a laptop computer , or a non-transparent display.

Aspect 67 is a packaged article comprising a housing comprising an opening, an outer surface, and an inner surface defining an enclosure; wherein the housing comprises a tempered glass article, wherein the tempered glass article comprises: a first surface defining a thickness t of about 1.1 mm or less and a second surface opposing the first surface; a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; and a central tension (CT) of at least 50 MPa.

Aspect (68) is the packaging article of aspect (67), wherein after the glass article is ruptured according to a fragility test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less, and wherein the glass article comprises: The product, as measured by the fragility test, breaks into multiple fragments in less than 1 second.

Aspect (69), in the packaged product of aspect (68), at least 80% of the plurality of fragments have a maximum dimension of 2·t or less.

Aspect 70, wherein, in the packaged article of aspect 68 or aspect 69, at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less.

Aspect (71), in the packaged article of any one of aspects (68)-(70), wherein at least 50% of the plurality of fragments comprise a volume of about 10 mm 3 or less.

Aspect (72), in the packaged article of any one of aspects (68)-(71), wherein the plurality of fragments comprises an ejected portion of the fragment, wherein the ejected portion of the fragment comprises: contains less than 10% of the fragments of

Aspect (73) provides, in the packaging article of any one of aspects (68)-(72), wherein the glass article comprises a first weight prior to breaking, and wherein the plurality of fragments comprises: a portion and a non-released portion of the debris, wherein the non-released portion of the debris has a second weight, and wherein the difference between the first weight and the second weight is 1% of the first weight to be.

Aspect (74) provides that, in the packaged article of any one of aspects (68)-(73), as measured by a fragility test, the probability that the glass article will break into a plurality of fragments in 1 second or less is 99% More than that.

Aspect (75), the packaging article of any one of aspects (67)-(74), wherein the glass article comprises a stored tensile energy of at least 20 J/m 2 .

Aspect (76) includes, the packaging article of any one of aspects (67) to (75), wherein the glass article comprises a surface compressive stress and a central tension, wherein the ratio of the central tension to the surface compressive stress is: It ranges from about 0.1 to about 1.

Aspect 77, wherein the packaged article of aspect 76, wherein the surface compressive stress is greater than or equal to 150.

Aspect (78), wherein the packaged article of any one of aspects (67)-(77), wherein the DOC comprises at least about 0.2 tons.

Aspect (79) provides, in the packaging article of any one of aspects (67) to (78), wherein the glass article is an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate or an alkali aluminoboro. silicate glass.

Aspect (80) is the packaging article of any one of aspects (67)-(72), wherein the glass article is disposed on the hermetic layer.

Aspect (82), in the packaging article of any one of aspects (67)-(80), further comprises a pharmaceutical substance.

Aspect (83) further comprises a cap disposed in the opening, in the packaged article of any one of aspects (67)-(81).

It will be apparent to those skilled in the art that various changes and changes can be made without departing from the spirit or scope of the present invention.

Claims (16)

a first surface and a second surface opposite the first surface defining a thickness t of at least 0.4 mm and no more than 3 mm;
a surface extending from the first surface to a depth of compression (DOC) greater than 0.15 t, as measured by a scattered light polarizer, and greater than 624.5 MPa, as measured by a combination of a scattered light polarizer and a surface stress meter a compressive stress layer comprising a compressive stress, wherein the compressive stress at a depth of the potassium layer is between 120 MPa and 300 MPa;
A tempered glass article comprising a maximum central tension (CT) of at least 200 MPa, as measured by a scattering light polarizer, comprising:
wherein the glass article, after being polished to 90-grit SiC particles at a pressure of 25 psi for 5 seconds, exhibits a breaking load of at least 10 kgf,
The tempered glass article is attached to the substrate by an adhesive,
wherein the glass article comprises a stored tensile energy of at least 40 J/m 2 . delete The method according to claim 1,
wherein the ratio of the maximum central tension to the surface compressive stress is in the range of 0.1 to 1. 4. The method according to claim 3,
A tempered glass article wherein the maximum central tension (CT) is 250 MPa or more. 5. The method according to claim 4,
The DOC is a tempered glass product containing 0.2t or more. The method according to claim 1,
The glass article further comprises a CT region, wherein the CT region is defined by the equation
[Equation]
Stress(x) = MaxCT - (((MaxCT·(n+1))/0.5 ⁿ )·|(x/t)-0.5| ⁿ )
where MaxCT is the maximum CT value, given as a positive value in MPa, x is the position along thickness (t) in micrometers, and n is a tempered glass article from 1.5 to 5. As a consumer electronic product,
a housing having a front face;
an electrical component provided at least partially within the housing and including at least a controller, a memory, and a display; and
a cover glass disposed on the front side of the housing and over the display, or disposed as a back cover, the cover glass comprising a tempered glass article;
Here, the tempered glass product,
a first surface and a second surface opposite the first surface defining a thickness t of at least 0.4 mm and no more than 3 mm;
a surface extending from the first surface to a depth of compression (DOC) greater than 0.17 t, as measured by a scattered light polarizer, and greater than 624.5 MPa, as measured by a combination of a scattered light polarizer and a surface stress meter a compressive stress layer comprising a compressive stress, wherein the compressive stress at a depth of layer of potassium is between 120 MPa and 300 MPa; and
has a maximum central tension (CT) of at least 200 MPa, as measured by a scattering light polarizer,
the tempered glass article is placed on the sealing layer by an adhesive,
wherein the glass article comprises a stored tensile energy of at least 40 J/m 2 . 8. The method of claim 7,
wherein the ratio of maximum central tension to surface compressive stress ranges from 0.1 to 1. 8. The method of claim 7,
The DOC is a consumer electronic product comprising 0.2t or more. 8. The method of claim 7,
The consumer electronic product comprises a tablet, a transparent display, a mobile phone, a video player, an information terminal device, an electronic-reader, a laptop computer, or a non-transparent display. 8. The method of claim 7,
The consumer electronic product further comprises a CT region, wherein the CT region is defined by the equation
[Equation]
Stress(x) = MaxCT - (((MaxCT·(n+1))/0.5 ⁿ )·|(x/t)-0.5| ⁿ )
where MaxCT is the maximum CT value, given as a positive value in MPa, x is the position along thickness (t) in micrometers, and n is a tempered glass article from 1.5 to 5. 7. The method of any one of claims 1, 3-6,
t is not more than 1.1 mm for tempered glass articles. 12. The method of any one of claims 7-11,
t is not more than 1.1 mm for consumer electronic products. 14. The method of claim 13,
wherein the maximum central tension is 250 MPa or more. delete delete

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