CN112299707A

CN112299707A - Glass articles exhibiting improved breakage performance

Info

Publication number: CN112299707A
Application number: CN202011285770.7A
Authority: CN
Inventors: S·E·德马蒂诺; M·D·法比安; J·T·科利; J·L·莱昂; C·M·史密斯; 唐中帜
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2016-05-31
Filing date: 2016-07-22
Publication date: 2021-02-02
Also published as: KR102601153B1; CN107848870A; KR20190075175A; KR102411111B1; KR20200128761A; KR20180035836A

Abstract

The present application relates to glass articles exhibiting improved breakage performance. Embodiments of the present disclosure pertain to a strengthened glass article that includes a first surface and a second surface opposite the first surface that define a thickness (t) of less than about 1.1mm, a compressive stress layer extending from the first surface to a depth of compression (DOC) of greater than or equal to about 0.1t, such that when the glass article fractures, it fractures into multiple fragments having an aspect ratio of less than or equal to about 5. In some embodiments, the glass article exhibits an equibiaxial flexural strength of greater than or equal to about 20kgf after 5 seconds of abrasion with 90 mesh SiC particles at a pressure of 25 psi. Devices incorporating the glass articles described herein and methods of making the same are also disclosed.

Description

Glass articles exhibiting improved breakage performance

The patent application of the invention is a divisional application of an invention patent application with the international application number of PCT/US2016/043610, the international application date of 2016, 7, month, 22, and the application number of 201680040729.9, entering the national phase of China, entitled "glass product exhibiting improved breaking performance".

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from united states provisional application serial No. 62/343,320 filed 2016, 05, 31, 2016, based on which application is hereby incorporated by reference in its entirety, in accordance with 35u.s.c. § 119.

Background

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

Consumer electronics, including handheld devices (e.g., smartphones, tablets, e-book readers, and laptops) typically incorporate chemically strengthened glass articles for use as cover glass. Because cover glass is bonded directly to a substrate such as a touch panel, display, or other structure, when a strengthened glass article is broken, such article may emit small fragments or particles from the free surface due to stored energy created by a combination of surface compressive stress and tensile stress below the glass surface. As used herein, the term fracture includes cracking and/or the formation of cracks. These small fragments are potential considerations for the device user, particularly when the fracture occurs close to the user's face (i.e., eyes and ears) in a delayed manner, and when the user continues to use and touch the fractured surface (and is therefore susceptible to small cuts or abrasions), particularly when the fracture distance is long and there are fragments with sharp corners and edges.

Thus, there is a need for glass articles exhibiting modified fracture behavior such that when such articles break, they exhibit enhanced cutting behavior, e.g., a cutting effect that produces short crack lengths and fewer emitted particles. Further, there is a need for glass articles that, when broken, emit less debris and the debris has less kinetic energy and momentum.

Disclosure of Invention

A first aspect of the present disclosure pertains to a strengthened glass article comprising: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1mm, and a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t. In some embodiments, after the glass article fractures, the glass article comprises a plurality of fragments, wherein at least 90% of the plurality of fragments have an aspect ratio of less than or equal to about 5, and the glass article fractures into the plurality of fragments in less than or equal to 1 second, as measured by the frangibility test.

In some embodiments, the strengthened glass article exhibits an equibiaxial flexural strength of greater than or equal to about 20kgf after 5 seconds of abrasion with 90 mesh SiC particles at a pressure of 25 psi. In some embodiments, after the glass article is broken, the strengthened glass article can include the following breaking conditions: such that greater than or equal to 50% of the fractures extend only partially through the thickness.

A third aspect of the present disclosure pertains to an apparatus comprising a strengthened glass substrate, a confinement layer, and a support as described herein, wherein the apparatus comprises: a tablet, a transparent display, a cell 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 pertains to a consumer electronics product, comprising: a housing having a front surface; an electronic assembly provided at least partially inside the housing, the electronic assembly comprising at least: a controller, a memory and a display; and a cover glass disposed at the front surface of the housing and over the display, the cover glass comprising a strengthened glass article as described herein.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the various embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary 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 embodiments and, together with the description, serve to explain the principles and operations of the various embodiments.

Drawings

Fig. 1A is a side view of a glass article according to one or more embodiments;

FIG. 1B is a side view of the glass article of FIG. 1A after breakage;

FIG. 2 is a cross-sectional view through the thickness of a known thermally tempered-based glass article;

FIG. 3 is a cross-sectional view through the thickness of a known chemically strengthened glass-based article;

FIG. 4 is a cross-sectional view through a thickness of a strengthened glass-based article according to one or more embodiments;

FIG. 5 is a schematic cross-sectional view of the ring-on-ring apparatus;

FIG. 6 is a schematic cross-sectional view of one embodiment of an apparatus for performing an inverted ball on sandpaper (IBoS) test as described herein;

FIG. 7 is a schematic cross-sectional view showing the primary mechanism of failure due to break introduction plus bending common in glass-based articles used in mobile or handheld electronic devices;

FIG. 8 is a flow chart of a method of performing an Ibos test in the apparatus described herein; and

FIG. 9A is a side view of the glass article of FIG. 1A including a confinement layer;

FIG. 9B is a side view of the glass article of FIG. 9A including a second confinement layer;

FIG. 10 is a schematic front plan view of an electronic device incorporating one or more embodiments of glass articles described herein;

FIG. 11 is a graph showing the results of AROR test of example 1;

FIG. 12 is a graph showing the results of the drop test of example 2;

FIG. 13 shows K in example 4₂A graph of O concentration versus ion exchange depth;

FIG. 14 shows the stress distribution of example 4G;

FIGS. 15A-15D are fracture images of example 5;

figures 16A-16D show the readability of example 6 at different viewing angles after rupture;

FIG. 17 is a graph showing the calculated stored tensile energy versus ion exchange time for example 7; and

FIG. 18 is a graph showing the calculated central tension versus ion exchange time for example 7; and

figure 19 shows the stress distribution of example 6, plotting compressive and tensile stress against depth.

Detailed Description

Reference will now be made in detail to the various embodiments, examples of which are illustrated in the accompanying drawings. With respect to the drawings in general, it is to be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or the appended claims. The figures are not necessarily to scale and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

In the description below, like reference numerals designate similar or corresponding parts throughout the several views shown in the drawings. It should also be understood that terms such as "top," "bottom," "outward," "inward," and the like are words of convenience and are not to be construed as limiting terms unless otherwise specified. Further, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or a combination thereof, it is understood that the group may consist of any number of those listed elements, either individually or in combination with each other. Unless otherwise indicated, a range of numerical values set forth includes both the upper and lower limits of the range, as well as any range between the stated ranges. As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean "at least one" or "one or more", unless otherwise indicated. It should also be understood that the various features disclosed in the specification and drawings may be used in any and all combinations.

It should be noted that the terms "substantially" and "about" may be used herein to represent the degree of inherent uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms "comprises," "comprising," and any other variation thereof, are intended to cover a non-exclusive inclusion, such that a non-exclusive inclusion does not imply that all of the features and functions of the subject matter claimed herein are in fact, or even wholly, essential to the subject matter.

As used herein, the term "glass article" is used in its broadest sense to include any object made in whole 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). All compositions are expressed as mole percent (mol%) unless otherwise indicated.

As described herein, embodiments of glass articles may include strengthened glass or glass-ceramic materials that exhibit improved mechanical properties and reliability as compared to known glass articles (particularly known coated glass articles). Embodiments of the glass articles described herein may exhibit fracture behavior not exhibited by known coated glass articles. In the present disclosure, glass-based substrates are typically unreinforced, and glass-based articles are typically referred to as glass-based substrates that have been strengthened (e.g., by ion exchange).

A first aspect of the present disclosure pertains to strengthened glass articles that exhibit the ability to break into a dense break pattern with a cutting effect (dicing effect) similar to fully thermally tempered glass used for shower panels or window panels. In some embodiments, the fragments are intended to be less damaging to the human body. Such articles exhibit this behavior despite being chemically strengthened and of a thickness significantly less than that achievable by prior known hot tempering processes. In some embodiments, the fragments are even smaller or finer than observed with known thermally tempered glass. For example, some embodiments of the glass article exhibit a "cut" effect in which, when the glass article is broken, the "cut" pieces have a small aspect ratio, and the surface of the broken product forms a larger angle (i.e., a smaller blade or knife angle) with the just-formed surface (as-formed surface), such that the pieces are more like cubes rather than splits, as described in more detail below with respect to fig. 1A. In some cases, the cutting chips are limited to a maximum or longest dimension of less than or equal to 2 millimeters (mm) in any direction of the major plane of the glass article. In some cases, the glass article includes a plurality of fragments having an average aspect ratio of less than or equal to about 10 or less than or equal to about 5 (e.g., less than or equal to about 4.5, less than or equal to about 4, less than or equal to about 3.5, less than or equal to about 3, less than or equal to about 2.5, less than or equal to about 2) when or after the glass article is broken. In some embodiments, the plurality of fragments has an average aspect ratio of about 1 to about 2. In some cases, greater than or equal to about 90% or greater than or equal to about 80% of the plurality of fragments exhibit an average aspect ratio as 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, thickness, diagonal or thickness. Glass articles exhibiting such fragments after fracture may be characterized herein as exhibiting "cutting" behavior.

Referring to fig. 1A and 1B, in one or more embodiments, the glass article 10 described herein can have the following sheet configuration: having opposing

major surfaces

12, 14 and opposing

minor surfaces

16, 18. At least one major surface 12 forms a "as-formed" surface of the glass article. When broken, a new surface is formed, which is created by the breaking of the glass article (i.e., a "broken" surface), indicated by reference numeral 19 in fig. 1B. The angle alpha between the surface created by the break and the surface just formed (after the glass article is broken) is about 85 to 95 degrees or about 88 to 92 degrees. In one or more embodiments, after the glass article fractures, greater than or equal to about 90% of the plurality of fragments in the glass article exhibit the angle between the as-formed surface and all fracture-generated surfaces.

In one or more embodiments, at least 50% (e.g., greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, or greater than or equal to about 90%) of the plurality of fragments have a maximum dimension of less than or equal to 5t, less than or equal to 3t, or less than or equal to 3 t. In some cases, at least 50% (e.g., greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, or greater than or equal to about 90%) of the plurality of fragments comprise a largest dimension that is less than 2 times the smallest dimension. In some embodiments, the maximum dimension is less than or equal to about 1.8 times the minimum dimension, the maximum dimension is less than or equal to about 1.6 times the minimum dimension, the maximum dimension is less than or equal to about 1.5 times the minimum dimension, the maximum dimension is less than or equal to about 1.4 times the minimum dimension, the maximum dimension is less than or equal to about 1.2 times the minimum dimension, or the maximum dimension is about equal to the minimum dimension.

In one or more embodiments, at least 50% (e.g., greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, or greater than or equal to about 90%) of the plurality of pieces of debrisIncluding less than or equal to about 10mm³The volume of (a). In some embodiments, the volume may be less than or equal to about 8mm³Less than or equal to about 5mm³Or less than or equal to about 4mm³. In some embodiments, the volume may be about 0.1 to 1.5mm³。

As used herein, the expression "reinforced article" includes articles that are chemically reinforced or chemically and thermally reinforced, but excludes articles that are only thermally reinforced. As shown in fig. 4, the strengthened glass article exhibits a stress profile that can be characterized in terms of surface Compressive Stress (CS), Center Tension (CT), and depth of compression (DOC).

The strengthened glass articles of one or more embodiments exhibit a stress profile that is distinguishable from stress profiles exhibited by known thermally tempered glass articles and known chemically strengthened glass articles. Generally, thermally tempered glass has been used to prevent breakage due to the possibility of such flaws being introduced into the glass, because thermally tempered glass typically exhibits a large CS layer (e.g., about 21% of the total thickness of the glass), which can prevent flaws from propagating and thus can prevent breakage. An example of the stress distribution produced by thermal tempering is shown in fig. 2. In fig. 2, heat-treated glass article 100 includes a first surface 101, a thickness t₁And surface CS 110. The glass article 100 exhibits a decrease in CS from the first surface 101 to the DOC 130, as defined herein, at which depth the stress changes from compressive to tensile and reaches the CT 120.

Thermal tempering is currently limited to thick glass articles (i.e., thickness t)₁Glass articles greater than or equal to about 3 mm) because a sufficient thermal gradient must be established between the core and the surface of such articles in order to achieve thermal strengthening and the desired residual stress. In many applications, such as displays (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, etc.), buildings (e.g., windows, shower panels, countertops, etc.), vehicles (e.g., vehicles, trains, spacecraft, seagoing vessels, etc.), appliances, enclosures, or devices requiring excellent resistance to cracking but being thin and thinAny application where articles are lightweight, such thick articles are undesirable or impractical.

Although chemical strengthening is not limited by the thickness of the glass article as is the case with thermal tempering, known chemically strengthened glass articles fail to exhibit the stress distribution of the thermally tempered glass article. An example of a stress profile generated by chemical strengthening (e.g., ion exchange process) is shown in fig. 3. In fig. 3, a chemically strengthened glass article 200 includes a first surface 201, a thickness t₂And a surface CS 210. The glass article 200 exhibits a decrease in CS from the first surface 201 to the DOC 230, as defined herein, at which depth the stress changes from compressive to tensile and reaches the CT 220. As shown in fig. 3, such a profile exhibits a flat CT area or CT area with constant or nearly constant tensile stress, and generally, a CT value lower than the CTE value shown in fig. 2.

The glass article of one or more embodiments of the present disclosure exhibits a thickness t of less than or equal to about 3mm (e.g., less than or equal to about 2mm, less than or equal to about 1.5mm, or less than or equal to about 1.1mm), and a compressive stress layer extending from the first surface to a DOC of greater than or equal to about 0.1 t. As used herein, DOC refers to the depth at which the stress within the glass article changes from compressive to tensile. At the DOC, the stress transitions from a positive (compressive) stress to a negative (tensile) stress (e.g., 130 in fig. 2), thus exhibiting a zero stress value.

According to common practice in the art, compression is expressed as negative stress (<0) and tension as positive stress (> 0). However, throughout this specification, CS is expressed as a positive value or an absolute value, i.e., CS ═ CS |, as set forth herein.

In particular, the glass articles described herein are thin and exhibit stress profiles that can generally only be achieved by tempering thick glass articles (e.g., having a thickness of about 2mm or 3mm or greater). In some cases, the glass article exhibits a surface CS that is greater than the tempered glass article. In one or more embodiments, the glass article exhibits a greater depth of compressive layer (where the decrease and increase in CS is more gradual than known chemically strengthened glass articles), such that the glass article exhibits significantly improved resistance to breakage, even when the glass article or a device comprising the same is dropped onto a hard, rough surface. The glass article of one or more embodiments exhibits CT values greater than some known chemically strengthened glass substrates.

CS is measured by a surface stress meter (FSM) using a commercial instrument such as FSM-6000, for example, manufactured by Orihara Industrial co. Surface stress measurement relies on the accurate measurement of the Stress Optical Coefficient (SOC), which is related to the birefringence of the glass. The SOC was then measured according to a modified version of protocol C described in ASTM Standard C770-98(2013), entitled "Standard Test Method for measuring Glass Stress-Optical Coefficient", which is incorporated herein by reference in its entirety. The improvement comprises using as a test specimen a glass dish having a thickness of 5-10mm and a diameter of 12.7mm, wherein the dish is isotropic and uniform and is core drilled, both sides polished and parallel. The improvement further comprises calculating a maximum force F to be applied_{Maximum value}. The force should be sufficient to produce a compressive stress of at least 20 MPa. F_{Maximum value}The calculation is as follows:

F_{maximum value}＝7.854*D*h

Wherein:

F_{maximum value}Force in newtons

D is the diameter of the disc

h is the thickness of the optical path

For each force application, the stress was calculated as follows:

σ_MPa＝8F/(π*D*h)

wherein:

f is the applied force in newtons

D is the diameter of the disc

h is the thickness of the optical path

The CT values were measured using a diffuse light polarizer ("scapp", model SCALP-04) supplied by glass stress ltd, located in Tallinn, Estonia, and techniques known in the art. SCALP can also be used to measure DOC, as described in further detail below.

In some embodiments, the glass article may also exhibit a depth of penetration of potassium ions ("potassium DOL") that is different from DOC. The degree of difference between DOC and potassium DOL depends on the glass substrate composition and the ion exchange treatment that creates the stress in the resulting glass article. When stress is created in the glass article by exchanging potassium ions into the glass article, the potassium DOL is measured using FSM (as described above with respect to CS). When stress is generated by exchanging sodium ions into the glass article, DOC is measured using scapp (as described above with respect to CT), and the resulting glass article will not have potassium DOL because there is no potassium ion penetration. When stress is created in the glass article by exchanging both potassium and sodium ions into the glass, the exchange depth of sodium represents the DOC, and the exchange depth of potassium ions represents the change in magnitude of the compressive stress (however, this is not a change in stress from compressive to tensile); in such embodiments, DOC is measured by scap, and potassium DOL is measured by FSM. When both potassium DOL and DOC are present in the glass article, the potassium DOL is generally less than the DOC.

The stress distribution in the glass articles described herein (regardless of whether the stress is generated by sodium ion exchange and/or potassium ion exchange) can be measured using a Refracted Near Field (RNF) method or a SCALP. When the RNF method is employed, the CT values provided by SCALP are employed. In particular, the stress distribution measured by RNF is force balanced and calibrated with CT values provided by the SCALP measurements. The RNF method is described in U.S. Pat. No. 8,854,623 entitled "Systems and methods for measuring a profile characterization of a glass sample," which is incorporated herein by reference in its entirety. Specifically, the RNF method includes placing a glass-based article proximate to a reference block, generating a polarization-switched light beam (which switches between orthogonal polarizations at a rate of 1-50 Hz), measuring an amount of power in the polarization-switched light beam, and generating a polarization-switched reference signal, wherein the measured amounts of power in each of the orthogonal polarizations are within 50% of each other. The method further includes passing the polarization-switched beam through the glass sample and the reference block into the glass sample at different depths, and then delaying the passed polarization-switched beam with a delay optical system to a signal photodetector that generates a polarization-switched detector signal. The method further comprises the following steps: dividing the detector signal by the reference signal to form a normalized detector signal, and determining the 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 solely by potassium Ion exchange And the potassium DOL is equal to DOC, the Stress Profile may also be obtained by the method disclosed in U.S. patent application No. 13/463,322 (hereinafter "Roussev I") entitled "Systems And Methods for Measuring the Stress Profile of Ion-Exchanged Glass," filed on 3.5.2012 by Rostislav v. Roussev I discloses a method for extracting a detailed and precise stress profile (stress versus depth) of chemically strengthened glass using FSM. In particular, spectra of combined optical modes of TM and TE polarization are collected via prism coupling techniques and used in their entirety to obtain detailed and accurate TM and TE refractive index curves n_TM(z) and n_TE(z). The entire contents of the above application are incorporated herein by reference. The detailed refractive index profile is obtained by: obtaining a mode spectrum using an inverse Wentzel-Kramers-Brillouin (IWKB) method, fitting the measured mode spectrum to a numerically calculated spectrum of a predetermined functional form describing the shape of the refractive index profile, and obtaining parameters of the functional form from the best fit. The detailed stress profile s (z) is calculated from the difference of the recovered TM and TE refractive index profiles by using known stress-optical coefficient (SOC) values:

S(z)＝[n_TM(z)-n_TE(z)]/SOC (2).

birefringence n at arbitrary depth z due to small SOC value_TM(z)-n_TE(z) is the refractive index n_TM(z) and n_TE(z) a small fraction (typically about 1%) of any one of (z). Obtaining a stress curve that is not significantly distorted by noise in the measurement pattern spectra requires that the determination of the pattern effective index have an accuracy of about 0.00001 RIU. The method disclosed by Roussev I also includes techniques for raw data to ensure high accuracy of measured modal index despite noisy and/or poor contrast in TE and TM mode spectra or images collected in the modal spectra. Such techniques include noise averaging, filtering, and curve fitting to obtain the locations of the extrema corresponding to the modes with sub-pixel resolution.

As described above, the glass articles described herein can be chemically strengthened by ion exchange and exhibit stress profiles that are different from those exhibited by known strengthened glasses. In this process, ions at or near the surface of the glass are replaced or exchanged with larger ions having the same valence or oxidation state. In those embodiments where the glass article comprises an alkali aluminosilicate glass, the ions in the surface layer of the glass, as well as the larger ions, are monovalent alkali metal cations, such as Li⁺When present in the glass article, Na⁺、K⁺、Rb⁺And Cs⁺. Alternatively, the monovalent cation in the surface layer may be a monovalent cation other than an alkali metal cation, such as Ag⁺And so on.

The ion exchange process is typically performed by immersing the glass articles in a molten salt bath (or two or more molten salt baths) containing larger ions to be exchanged with smaller ions in the glass articles. It should be noted that an aqueous salt bath may also be employed. In addition, the bath composition may include more than one type of larger ion (e.g., Na)⁺And K⁺) Or a single larger ion. As will be appreciated by those skilled in the art, the parameters of the ion exchange process include, but are not limited to, bath composition and temperature, immersion time, number of immersions of the glass articles in the salt bath (or baths), use of multiple salt baths, other steps (e.g., annealing and washing, etc.), which are generally determined by the following factors: composition of glass articles (including makingThe structure of the article and any crystalline phases present), as well as the DOC and CS required for the glass article resulting from the strengthening operation. For example, ion exchange of the glass article can be achieved by: the glass article is immersed in at least one molten salt bath comprising salts such as, but not limited to, nitrates, sulfates, and chlorides of larger alkali metal ions. Typical nitrates include KNO₃、NaNO₃、LiNO₃、NaSO₄And combinations thereof. The temperature of the molten salt bath is typically about 380 ℃ up to about 450 ℃ and the immersion time is about 15 minutes up to 100 hours, depending on the glass thickness, bath temperature and glass diffusion coefficient. However, temperatures and immersion times other than those described above may also be used.

In one or more embodiments, the glass article may be immersed in 100% NaNO at a temperature of about 370 ℃ and 480 ℃₃In the molten salt bath. In some embodiments, the glass substrate may be dipped to contain about 5-90% KNO₃And about 10 to 95NaNO₃In the mixed molten salt bath of (1). In some embodiments, the glass substrate may be dipped to contain Na₂SO₄And NaNO₃And a mixed molten salt bath having a broader temperature range (e.g., up to about 500 c). In one or more embodiments, the glass article may be immersed in the second bath after immersion in the first bath. Immersing in the second bath may include immersing in a bath containing 100% KNO₃For 15 minutes to 8 hours in the molten salt bath.

The ion exchange conditions may be modified based on the glass composition and thickness of the glass substrate. For example, a glass substrate having a nominal composition as in example 1 below and having a thickness of 0.4mm may be immersed in 80-100% KNO at a temperature of about 460 deg.C₃(the remainder is NaNO)₃) The molten salt bath of (2) for a time period of about 10 to 20 hours. The same substrate with a thickness of about 0.55mm can be immersed in 70-100% KNO at a temperature of about 460 deg.C₃(the remainder is NaNO)₃) The molten salt bath of (2) for a time period of about 20 to 40 hours. The same substrate with a thickness of about 0.8mm can be immersed in 60-100% KNO at about 460 deg.C₃(the remainder is NaNO)₃) The molten salt bath of (2) for a time period of about 40 to 80 hours.

In one or more embodiments, the glass-based substrate may be immersed in a mixed molten salt bath comprising NaNO₃And KNO₃(e.g., 49%/51%, 50%/50%, 51%/49%), a temperature of less than about 420 ℃ (e.g., about 400 ℃ or about 380 ℃) for less than about 5 hours or even less than or equal to about 4 hours.

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. Due to the unique properties of the glass compositions used in the glass-based articles described herein, this spike may be achieved by a single bath or multiple baths, the baths having a single composition or mixed compositions.

As shown in fig. 4, one or more embodiments of a glass article 300 include a first surface 302 and a second surface 304 opposite the first surface that define a thickness t. In one or more embodiments, the thickness t may be less than about 3mm, less than or equal to about 2mm, less than or equal to about 1.5mm, less than or equal to about 1.1mm, or less than or equal to about 1mm (e.g., about 0.01mm to about 1.5mm, about 0.1mm to about 1.5mm, about 0.3mm to about 1.5mm, about 0.4mm to about 1.5mm, about 0.01mm to about 1.1mm, about 0.1mm to about 1.1mm, about 0.2mm to about 1.1mm, about 0.3mm to about 1.1mm, about 0.4mm to about 1.1mm, about 0.01mm to about 1.4mm, about 0.01mm to about 1.2mm, about 0.01mm to about 1.1mm, about 0.01mm to about 1mm, about 0.01mm to about 0.01mm, about 0.01mm to about 0.1mm, about 0.01mm to about 0.5mm, about 0.01mm, about 0.1mm, about 0.01mm, about 0.0 mm to about 0.5mm, about 0.1mm, or about 0.1 mm).

Fig. 4 is a cross-sectional view of a stress distribution of a chemically strengthened glass article 300 along its thickness 330 (shown along the x-axis). The magnitude of the stress is shown on the y-axis, with line 301 representing zero stress.

The stress distribution 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 the central portion of the article.

As used herein, DOC refers to the depth at which the stress within the glass article changes from compression to tension. At the DOC, the stress transitions from a positive (compressive) stress to a negative (tensile) stress (e.g., 330 in fig. 5), thus exhibiting a zero stress value.

The CS layer has an associated depth or length 317 that extends from the

major surfaces

302, 304 to the DOC 330. The CT layer 325 also has an associated length or depth 327(CT area or layer).

The surface CS 310 can be greater than or equal to about 150MPa or greater than or equal to about 200MPa (e.g., greater than or equal to about 250MPa, greater than or equal to about 300MPa, greater than or equal to about 400MPa, greater than or equal to about 450MPa, greater than or equal to about 500MPa, or greater than or equal to about 550 MPa). Surface CS 310 may be up to about 900MPa, up to about 1000MPa, up to about 1100MPa, or up to about 1200 MPa. In one or more embodiments, surface CS 310 may be in the following ranges: from about 150MPa to about 1200MPa, from about 200MPa to about 1200MPa, from about 250MPa to about 1200MPa, from about 300MPa to about 1200MPa, from about 350MPa to about 1200MPa, from about 400MPa to about 1200MPa, from about 450MPa to about 1200MPa, from about 500MPa to about 1200MPa, from about 200MPa to about 1100MPa, from about 200MPa to about 1000MPa, from about 200MPa to about 900MPa, from about 200MPa to about 800MPa, from about 200MPa to about 700MPa, from about 200MPa to about 600MPa, from about 200MPa to about 500MPa, from about 300MPa to about 900MPa, or from about 400MPa to 600 MPa.

The CT 320 can be greater than or equal to about 25MPa, greater than or equal to about 50MPa, greater than or equal to about 75MPa, or greater than or equal to about 85MPa, or greater than or equal to about 100MPa (e.g., greater than or equal to about 150MPa, greater than or equal to about 200MPa, greater than or equal to about 250MPa, or greater than or equal to about 300 MPa). In some embodiments, the CT 320 can be about 50-400MPa (e.g., about 75MPa to about 400MPa, about 100MPa to about 400MPa, about 150MPa to about 400MPa, about 50MPa to about 350MPa, about 50MPa to about 300MPa, about 50MPa to about 250MPa, about 50MPa to about 200MPa, about 100MPa to about 400MPa, about 100MPa to about 300MPa, about 150MPa to about 250 MPa). As used herein, CT is the maximum value of the central tension in the glass article.

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

The CT 320 may be placed in a range of about 0.3t to about 0.7t, about 0.4t to about 0.6t, or about 0.45t 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 0.8mm can have a CT of less than or equal to about 75 MPa. As the thickness of the glass-based article decreases, CT may increase. In other words, CT increases with decreasing thickness (or as the glass-based article becomes thinner).

The young's modulus of a glass article can affect the CT of the strengthened glass article described herein. In particular, for a given thickness, as the young's modulus of the glass article decreases, the glass article can be strengthened to have a lower CT and still exhibit the fracture behavior described herein. For example, when comparing a 1mm glass article having a lower young's modulus to another 1mm thick glass article having a higher young's modulus, the lower young's modulus glass article may be strengthened to a lower degree (i.e., to a relatively lower CT value) and still exhibit the same fracture behavior as a higher young's modulus glass (which would have a higher CT compared to a CT glass article).

In some embodiments, the ratio of CT 320 to surface CS is in the following range: about 0.05 to about 1 (e.g., 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 less than or equal to 0.1. In some embodiments, the surface CS may be 1.5 times (or 2 times or 2.5 times) the CT or greater. In some embodiments, the surface CS may be up to about 20 times CT.

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

In one or more embodiments, the glass-based article includes potassium DOL in a range from about 6 microns to about 20 microns. 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 can be about 0.005t to about 0.05 t. In some embodiments, the potassium DOL can be in the following range: from about 0.005t to about 0.05t, from about 0.005t to about 0.045t, from about 0.005t to about 0.04t, from about 0.005t to about 0.035t, from about 0.005t to about 0.03t, from about 0.005t to about 0.025t, from about 0.005t to about 0.02t, from about 0.005t to about 0.015t, from about 0.005t to about 0.01t, from about 0.006t to about 0.05t, from about 0.008t to about 0.05t, from about 0.01t to about 0.05t, from about 0.015t to about 0.05t, from about 0.02t to about 0.05t, from about 0.025t to about 0.05t, from about 0.03t to about 0.05t, or from about 0.01t to about 0.02 t.

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

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

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

In one or more embodiments, the glass article exhibits a maximum chemical depth of greater than or equal to about 0.4t, greater than or equal to about 0.5t, greater than or equal to about 55t, or greater than or equal to about 0.6 t. As used herein, the term "chemical depth" refers to the depth to which ions of a metal oxide or alkali metal oxide (e.g., metal ions or alkali metal ions) diffuse into a glass article, and the depth to which the concentration of the ions reaches a minimum, as determined by Electron Probe Microanalysis (EPMA). As a result of the ion exchange, ions diffuse into the chemically strengthened glass article. The maximum chemical depth refers to the maximum diffusion depth at which any ions are exchanged into the chemically strengthened glass article by the ion exchange process. For example, when the molten salt bath has more than one diffusing ionic species (i.e., with both NaNO's)₃And KNO₃Molten salt bath) different ionic species may diffuse into different depths of the chemically strengthened glass article. The maximum chemical depth is all ions exchanged into the chemically strengthened glass articleMaximum diffusion depth of the sub-species.

In one or more embodiments, the stress distribution 312 may be described as having a parabolic shape. In some embodiments, the stress profile along the region or depth of the glass-based article exhibiting tensile stress exhibits a parabolic shape. In one or more specific embodiments, the stress profile 312 is free of flat stress (i.e., compressive or tensile) portions, or portions that exhibit substantially constant stress (i.e., compressive or tensile). In some embodiments, the CT region exhibits a stress profile that is substantially free of flat stress or free of substantially constant stress. In one or more embodiments, the stress profile 312 includes a tangent that is less than about-0.1 MPa/micron or greater than about 0.1 MPa/micron at all points between about 0t up to about 0.2t and greater than 0.8t (or from about 0t to about 0.3t and greater than 0.7 t). In some embodiments, the tangent may be less than about-0.2 MPa/micron or greater than about 0.2 MPa/micron. In some more specific embodiments, the tangent may be less than about-0.3 MPa/micron or greater than about 0.3 MPa/micron. In even more particular embodiments, the tangent can be less than about-0.5 MPa/micron or greater than about 0.5 MPa/micron. In other words, the stress distribution of one or more embodiments excludes points having tangents (tan) along these thickness ranges (i.e., 0t up to about 2t and greater than 0.8t, or about 0t to about 0.3t and greater than or equal to 0.7t), as described herein. Without being bound by theory, the points of known error functions or quasi-linear stress distributions have tangents along the points of these thickness ranges (i.e., from about 0t up to about 2t and greater than 0.8t, or from about 0t to about 0.3t and greater than or equal to 0.7t) in the following ranges: from about-0.1 MPa/micron to about 0.1 MPa/micron, from about-0.2 MPa/micron to about 0.2 MPa/micron, from about-0.3 MPa/micron to about 0.3 MPa/micron, or from about-0.5 MPa/micron to about 0.5 MPa/micron (indicating a flat or zero slope stress profile along such thickness range, 220 as shown in fig. 3). Such stress profiles of glass-based articles of one or more embodiments of the present disclosure do not exhibit a stress profile with 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 distribution including a maximum tangent and a minimum tangent in a thickness range of about 0.1t to 0.3t and about 0.7t to 0.9 t. In some cases, the difference between the maximum tangent and the minimum tangent is less than or equal to about 3.5 MPa/micron, less than or equal to about 3 MPa/micron, less than or equal to about 2.5 MPa/micron, or less than or equal to about 2 MPa/micron.

In one or more embodiments, the glass-based article includes a stress profile 312 that is substantially free of any linear segments extending in the depth direction or along at least a portion of the thickness t of the glass-based article. In other words, the stress distribution 312 substantially continuously increases or decreases along the thickness t. In some embodiments, the stress profile is substantially free of any linear segments in a depth direction having a length of greater than or equal to about 10 microns, greater than or equal to about 50 microns, or greater than or equal to about 100 microns, or greater than or equal to about 200 microns. As used herein, the term "linear" refers to a slope magnitude along a linear segment of less than about 5 MPa/micron, or less than about 2 MPa/micron. In some embodiments, one or more portions of the stress distribution that are substantially free of any linear segments in the depth direction are present within the glass-based article at a depth of greater than or equal to about 5 microns (e.g., greater than or equal to 10 microns or greater than or equal to 15 microns) from one or both of the first surface or the second surface. For example, the stress profile can include linear segments along a depth from the first surface of about 0 microns to less than about 5 microns, but the stress profile is substantially free of linear segments beginning at a depth from the first surface of greater than or equal to about 5 microns.

In some embodiments, the stress profile may include linear segments at depths from about 0t up to about 0.1t, and may be substantially free of linear segments at depths from about 0.1t to about 0.4 t. In some embodiments, the stress profile may have a slope from about 20 MPa/micron to about 200 MPa/micron, ranging from about 0t to about 0.1t of thickness. As will be described herein, such embodiments may be formed by a single ion exchange process (the bath comprises two or more basic salts, or the bath is a mixed basic salt bath) or by multiple (e.g., 2 or more) ion exchange processes.

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

stress (x) ═ max T- (((CT)_n·(n+1))/0.5ⁿ)·|(x/t)-0.5|ⁿ) (1)

In equation (1), the stress (x) is a stress value at the x position. Here, the stress is positive (tensile). In equation (1), the maximum T is the maximum stretching value, and CT_nIs the stretch value at n, which is less than or equal to the maximum T. Maximum T and CT_nAre all positive values in MPa. The value of x is the position along the thickness (t) in microns, ranging from 0 to t; x-0 is one surface (302 in fig. 4), x-0.5 t is the center of the glass-based article, stress (x) max CT, and x-t is the opposite surface (304 in fig. 4). The maximum T used in equation (1) is equivalent to CT, which may be less than about 71.5/√ (T). In some embodiments, the maximum T used in equation (1) can be a fitting parameter of about 50 to 80MPa (e.g., about 60MPa to about 80MPa, about 70MPa to about 80MPa, about 50MPa to about 75MPa, about 50MPa to about 70MPa, or about 50MPa to about 65MPa), and n is 1.5 to 5 (e.g., 2 to 4, 2 to 3, or 1.8 to 2.2) or about 1.5 to 2. In one or more embodiments, n-2 may provide a parabolic stress profile that approximates a parabolic stress profile off of the stress profile provided by the index n-2. Fig. 5 shows various stress distributions based on the variation of the fitting parameter n, according to one or more embodiments of the present disclosure.

In one or more embodiments, CTn can be less than the maximum T, where a compressive stress spike is present on one or both major surfaces of the glass-based article. In one or more embodiments, CTn is equal to the maximum T when there is no compressive stress spike on one or both major surfaces of the glass-based article.

In some embodiments, the stress profile may be modified by heat treatment. In such embodiments, the heat treatment may be performed 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, when a steeper or greater slope is desired at the surface, an ion exchange process may be performed after the heat treatment to provide a "spike" or to increase the slope of the stress profile at or near the surface.

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

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

The concentration of metal oxide may include more than oneMetal oxides (e.g., Na)₂O and K₂A combination of O). In some embodiments, when two metal oxides are used and when the radii of the ions are different from each other, at a shallow depth, the concentration of the ions having the larger radius is greater than the concentration of the ions having the smaller radius, and at a deeper depth, the concentration of the ions having the smaller radius is greater than the concentration of the ions having the larger radius. For example, when a single bath containing Na and K is used in the ion exchange process, K is present in the glass-based article at a shallower depth⁺The concentration of the ion is more than Na⁺Concentration of ions, and at deeper depths, Na⁺The concentration of ions being greater than K⁺The concentration of the ions. This is due in part to the size of the ions. In such glass-based articles, the larger ions (i.e., K) are present at or near the surface due to the greater amount⁺Ions), the region at or near the surface includes a larger CS. Stress profiles with steeper slopes at or near the surface (i.e., spikes in the stress profile at the surface) may exhibit this larger CS.

As described above, by chemically strengthening the glass-based substrate, a concentration gradient or change in the one or more metal oxides is created, wherein the plurality of first metal ions are exchanged with the plurality of second metal ions in the glass-based substrate. The first ions may be ions of lithium, sodium, potassium and rubidium. The second metal ion may be an ion of one of sodium, potassium, rubidium, and cesium, provided that the ionic radius of the second alkali metal ion is larger than the ionic radius of the first alkali metal ion. The second metal ion is present as its oxide (e.g., Na) in the glass-based substrate₂O、K₂O、Rb₂O、Cs₂O, or a combination thereof).

In one or more embodiments, the metal oxide concentration gradient extends through most of the thickness t or the entire thickness t of the glass-based article, including the CT layer 327. In one or more embodiments, the concentration of metal oxide is greater than or equal to about 0.5 mol% in CT layer 327. In some embodiments, the concentration of the metal oxide can be greater than or equal to about 0.5 mol% (e.g., greater than or equal to about 1 mol%) along the entire thickness of the glass-based article and is greatest at the first surface 302 and/or 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 along the entire thickness t; however, the concentration is also non-zero at this point. In other words, the non-zero concentration of the particular metal oxide extends along a majority of the thickness t (as described herein) or along the entire thickness t. In some embodiments, the lowest concentration of a particular metal oxide is in CT layer 327. The total concentration of the particular metal oxide in the glass-based article may be from about 1 to about 20 mole percent.

In one or more embodiments, the glass-based article includes a first metal oxide concentration and a second metal oxide concentration such that the first metal oxide concentration is about 0-15 mole% along a first thickness range of about 0t to about 0.5t, and the second metal oxide concentration is about 0-10 mole% along a second thickness range of about 0 microns to about 25 microns (or about 0-12 microns); however, the concentration of one or both of the first metal oxide and the second metal oxide is non-zero along a majority of the thickness or the entire thickness of the glass-based article. The glass-based article may include an optional third metal oxide concentration. The first metal oxide may include Na₂O and the second metal oxide may include K₂O。

The concentration of the metal oxide can be determined by a baseline amount of the metal oxide in the glass-based article prior to modification to include the metal oxide concentration gradient.

In one or more embodiments, the stress profile 312 is due to a non-zero concentration of metal oxide that varies along a thickness of a portion. The change in concentration may be referred to herein as a gradient. In some embodiments, the concentration of the metal oxide is non-zero and varies along a thickness range from about 0t to about 0.3 t. In some embodiments, the concentration of the metal oxide is non-zero and varies along a thickness range from about 0t to about 0.35t, from about 0t to about 0.4t, from about 0t to about 0.45t, or from about 0t to about 0.48 t. Metal oxides can be described as creating stress in a glass-based article. The variation in concentration may be continuous along the thickness range described above. The concentration variation may include a metal oxide concentration variation of about 0.2 mole% along a thickness segment of about 100 microns. This change can be measured by methods known in the art, including microprobes, as shown in example 1. A metal oxide that is non-zero in concentration and varies along the thickness of a portion may be described as creating a stress in the glass-based article.

The concentration of metal oxide may include more than one metal oxide (e.g., Na)₂O and K₂A combination of O). In some embodiments, when two metal oxides are used and when the radii of the ions are different from each other, at a shallow depth, the concentration of the ions having the larger radius is greater than the concentration of the ions having the smaller radius, and at a deeper depth, the concentration of the ions having the smaller radius is greater than the concentration of the ions having the larger radius. For example, when a single bath containing Na and K is used in the ion exchange process, K is present in the glass-based article at a shallower depth⁺The concentration of the ion is more than Na⁺Concentration of ionsAnd at greater depths, Na⁺The concentration of ions being greater than K⁺The concentration of the ions. This is due in part to the size of the ions. In such glass-based articles, the larger ions (i.e., K) are present at or near the surface due to the greater amount⁺Ions), the region at or near the surface includes a larger CS. Stress profiles with steeper slopes at or near the surface (i.e., spikes in the stress profile at the surface) may exhibit this larger CS.

The concentration of the metal oxide can be determined by a baseline amount of the metal oxide in the glass article prior to modification to include the metal oxide concentration gradient.

The glass articles described herein can exhibit a composition of greater than or equal to 15J/m²(e.g., about 15-50J/m²) Stored tensile energy. For example, in some embodiments, the stored tensile energy may be from about 20 to about 150J/m². In some cases, the stored tensile energy may be in the following ranges: about 25J/m²To about 150J/m²About 30J/m²To about 150J/m²About 35J/m²To about 150J/m²About 40J/m²To about 150J/m²About 45J/m²To about 150J/m²About 50J/m²To about 150J/m²About 55J/m²To about 150J/m²About 60J/m²To about 150J/m²About 65J/m²To about 150J/m²About 25J/m²To about 140J/m²About 25J/m²To about 130J/m²About 25J/m²To about 120J/m²About 25J/m²To about 110J/m²About 30J/m²To about 140J/m²About 35J/m²To about 130J/m²About 40J/m²To about 120J/m²Or about 40J/m²To about 100J/m². The thermally and chemically strengthened glass-based article of one or more embodiments may exhibit a thickness of about 40J/m or greater²Stored tensile energy of greater than or equal to about 45J/m²Stored tensile energy of greater than or equal to about 50J/m²Stored tensile energy of greater than or equal to about 60J/m²Or greater than or equal to about 70J/m²Stored tensile energy.

The stored tensile energy was calculated using equation (2) as follows:

stored tensile energy (J/m)²)＝[1-ν]/E∫σ^2dt(2)

Where σ is the poisson's ratio, E is the young's modulus, and the integral is calculated only for the tensile region. Equation (2) see Frangienclosure of sampled Soda-Lime Glass Sheet, GLASS PROCESSING DAYS by Suresh T.Gulati (Frangienclosure of Tempered Soda-Lime Glass Sheet, Glass PROCESSING date), fifth International conference on architectural and automotive Glass, 9/month-13-15/1997, as described in equation 4.

The glass articles of some embodiments exhibit superior mechanical properties as compared to known strengthened glass articles, as evidenced by device drop tests or component level tests. In one or more embodiments, the glass article exhibits improved surface strength when subjected to Abraded Ring On Ring (AROR) testing. The strength of a material is defined as the stress at which cracking 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 equivalent Flexual Strength of Advanced Ceramics at Ambient Temperature" is used as the basis for the Ring abrasion ROR Test Method described herein. ASTM C1499-09 is incorporated herein by reference in its entirety. In one embodiment, prior to ring-on-ring testing, Glass specimens were abraded with 90 mesh silicon carbide (SiC) particles, which were transferred to Glass samples using the Methods and apparatus described in ASTM C158-02(2012) appendix a2 (entitled "abrasion products") entitled "Standard Test Methods for Strength of Glass by deflection" (Determination of flexural Modulus) ". ASTM C158-09, particularly appendix A2, is incorporated herein by reference in its entirety.

Prior to ring-on-ring testing, the surface of the glass article was abraded as described in ASTM C158-02, appendix 2, to normalize and/or control the surface defect status of the sample, using the equipment shown in ASTM C158-02, fig. a 2.1. The abrasive material is typically blasted onto the surface 110 of the glass article using an air pressure of 304kPa (44psi), with a load or pressure of 15psi or greater. In some embodiments, the abrasive material may be blasted onto the surface 110 at a load of 20psi, 25psi, or even 45 psi. After establishing the air flow, 5cm³The abrasive material of (a) was poured into the funnel and after introducing the abrasive material, the sample was sandblasted for 5 seconds.

For the ring-on-ring test, a glass article having at least one wear surface 112 as shown in fig. 5 is placed between two concentric rings of different sizes to determine the equibiaxial flexural strength or failure load (i.e., the maximum stress that the material can sustain when subjected to flexure between the two concentric rings), as also schematically shown in fig. 5. In the wear ring upper ring arrangement 10, the pass diameter is D₂To support the worn glass article 110. By means of a force-measuring cell (not shown) via a diameter D₁The load ring 130 applies a force F to the surface of the glass article.

Diameter ratio D of load ring to support ring₁/D₂And may be about 0.2 to about 0.5. In some embodiments, D₁/D₂About 0.5. The load ring and support rings 130, 120 should be concentrically aligned to lie at a support ring diameter D₂Within 0.5%. At any load, the force gauge used for the test should be accurate to within ± 1% of the selected range. In some embodiments, the test is performed at a temperature of 23 ± 2 ℃ and a relative humidity of 40 ± 10%.

For the fixture design, the radius r of the projected surface of the load ring 430 is h/2. ltoreq. r.ltoreq.3h/2, wherein h is the thickness of the glass article 110. The load and support rings 130, 120 are generally formed of a hardness HR_c>40 of hardened steel. ROR fixation devices are commercially available.

The target failure mechanism for the ROR test is to observe cracking of the glass article 110 originating from the surface 130a within the load ring 130. For data analysis, failures that exist outside of this region (i.e., between the load ring 130 and the support ring 120) were ignored. However, due to the thinness and high strength of the glass article 110, large deflections exceeding the thickness h of the 1/2 sample are sometimes observed. Thus, a high percentage of failures originating below the load ring 130 are often observed. The stress cannot be accurately calculated without knowledge of the sources of stress development and failure within and below the loop (collectively referred to as strain gauge analysis) for each sample. Thus, the AROR test focuses on the peak load of failure when measuring the response.

The strength of the glass article depends on the presence of surface flaws. However, the likelihood of the presence of a flaw of a given size cannot be accurately predicted, since the strength of the glass is naturally statistically significant. Therefore, probability distributions are often used as statistical representations of the obtained data.

In some embodiments, the strengthened glass articles described herein exhibit an equibiaxial flexural strength or failure load of greater than or equal to 20kgf and up to about 45kgf as determined by the AROR test with a load of 25psi or even 45psi to abrade the surface. In other embodiments, the surface strength is at least 25kgf, and in other embodiments, at least 30 kgf.

In some embodiments, the strengthened glass article can exhibit improved drop performance. As used herein, drop performance is evaluated by assembling the glass article into a mobile phone device. In some cases, multiple glass articles can be assembled to the same mobile phone device and the same test performed. The glass-assembled mobile phone device was then dropped onto sandpaper (which may include Al)₂O₃Particles or other abrasives) were continuously dropped to a starting height of 50 cm. When each sample survived after dropping from a height,the mobile phone device with the sample was dropped again from the increased height until the glass article broke, at which point the failure height of the sample was taken as the maximum failure height.

In some embodiments, the glass article exhibits a maximum failure height of greater than or equal to about 100cm when the thickness is about 1 mm. In some embodiments, at a thickness of about 1mm, the glass article exhibits a maximum failure height of greater than or equal to about 120cm, greater than or equal to about 140cm, greater than or equal to about 150cm, greater than or equal to about 160cm, greater than or equal to about 180cm, or greater than or equal to about 200 cm. The glass articles of one or more embodiments exhibit a cut fracture pattern after failure at a failure height. The cut break pattern comprises exhibiting an aspect ratio as described herein.

In one or more embodiments, the glass articles herein exhibit fracture behavior such that when the glass article is directly bonded to a substrate (i.e., a display unit), greater than or equal to 50% of the cracks are subsurface cracks (where the cracks only extend partially through the thickness and are trapped subsurface) after the glass article fractures. For example, in some cases, the crack may extend partially through the thickness t of the glass article, e.g., from 0.05t to 0.95 t. The percentage of cracks in the glass article that extend only partially through the thickness t may be greater than or equal to 50%, greater than or equal to 60%, greater than or equal to 70%, greater than or equal to 80%, or greater than or equal to 90%.

In some embodiments, the strengthened glass-based articles described herein can be described in terms of performance using an inverted ball on sand (IBoS) test. The IBoS test is a dynamic component level test that simulates the primary mechanism of failure due to damage introduction plus bending common in glass-based articles used for mobile or handheld electronic devices, as schematically illustrated in fig. 6. In the field, a damage introduction (a in fig. 7) occurs on the top surface of the glass-based article. The fracture starts at the top surface of the glass-based article and the damage penetrates the glass-based article (b in fig. 7) or the fracture propagates from a bend on the top surface or from an interior portion of the glass-based article (c in fig. 7). The IBoS test is designed to simultaneously introduce damage to the surface of the glass and apply bending under dynamic loading. In some cases, the glass-based article exhibits improved drop performance when it includes compressive stress as compared to the same glass-based article that does not include compressive stress.

The IBoS test equipment is schematically shown in fig. 6. The apparatus 500 includes a test rack 510 and a ball 530. Ball 530 is a rigid ball or a solid ball, such as a stainless steel ball or the like. In one embodiment, ball 530 is a 4.2 gram stainless steel ball having a diameter of 10 mm. The ball 530 falls directly onto the glass-based article sample 518 from a predetermined height h. The test rack 510 includes a solid base 512 comprising a hard rigid material, such as granite or the like. A sheet 514 of abrasive material disposed on a surface is placed on the upper surface of the solid base 512 so that the surface with the abrasive material faces upward. In some embodiments, sheet 514 is sandpaper having a 30 mesh surface (and in other embodiments, a 180 mesh surface). The glass-based article sample 518 is fixed in place on the sheet 515 by the sample holder 515 such that an air gap 516 exists between the glass-based article sample 518 and the sheet 514. The air gap 516 between the sheet 514 and the glass-based article sample 518 allows the glass-based article sample 518 to bend and bend onto the abrasive surface of the sheet 514 after being impacted by the ball 530. In one embodiment, the glass-based article sample 218 is clamped at all corners to maintain the inclusion of bending only at the ball impact point and to ensure repeatability. In some embodiments, sample holder 514 and test rack 510 are adapted to accommodate sample thicknesses up to about 2 mm. The air gap 516 is about 50-100 μm. For differences in material stiffness (Young's modulus, E)_{Modulus of elasticity}) (but also including the young's modulus and thickness of the sample), an air gap 516 is adjusted. The upper surface of the glass-based article sample may be covered with an adhesive tape 520 to collect debris from the glass-based article sample 518 in the event of a fracture after impact of the ball 530.

Various materials can be used as the abrasive surface. In a particular embodiment, the abrasive surface is sandpaper, such as silicon carbide or alumina sandpaper, engineered sandpaper, or any abrasive material known to those skilled in the art having a comparable hardness and/or sharpness. In some embodiments, a 30-mesh sandpaper may be used because its surface topography is more consistent than concrete or asphalt, and its particle size and sharpness produce the desired level of specimen surface damage.

In one aspect, fig. 8 shows a method 600 of performing an IBoS test using the apparatus 500 described above. In step 610, a glass-based article sample (218 in fig. 6) is placed in the test rack 510 described above and held in the sample holder 515 such that an air gap 516 is formed between the glass-based article sample 518 and the sheet 514 having an abrasive surface. The method 600 assumes that a sheet 514 having an abrasive surface has been placed in the test rack 510. However, in some embodiments, the method may include placing the sheet 514 into the test rack 510 such that the surface with the abrasive material is facing upward. In some embodiments (step 610a), an adhesive strip 520 is applied to the upper surface of the glass-based article sample 518 prior to securing the glass-based article sample 518 in the sample holder 510.

In step 520, a solid sphere 530 having a predetermined mass and size is dropped from a predetermined height h onto the upper surface of the glass-based article sample 518 such that the sphere 530 impacts the upper surface (or the adhesive strip 520 adhered to the upper surface) at approximately the center of the upper surface (e.g., within 1mm, or within 3mm, or within 5mm, or within 10mm of the center). After the impact of step 520, a degree of damage to the glass-based article sample 518 is determined (step 630). As noted above, the term "fracture" herein refers to the propagation of a crack through the entire thickness and/or the entire surface of a substrate when an object is dropped or impacted against the substrate.

In method 600, sheet 518 with an abrasive surface may be replaced after each drop to avoid "aging" effects that have been observed in repeated use of other types of drop test surfaces (e.g., concrete or asphalt).

Various predetermined drop heights h and increments are typically used in method 600. For example, a minimum drop height (e.g., about 10-20cm) may be used at the beginning of the test. The height can then be increased in fixed or varying increments for successive drops. Once the glass-based article sample 518 is broken or fractured, the testing described in method 600 is stopped (step 631). Alternatively, if the drop height h reaches a maximum drop height (e.g., about 100cm) without rupture, the drop test of method 300 can also be stopped, or step 520 can be repeated at the maximum height until rupture occurs.

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

If the glass-based article sample 518 is cracked (step 631 in FIG. 7), the IBoS test according to the method 600 is stopped (step 640). If no ball drop induced breakage at the predetermined drop height is observed (step 632), the drop height is increased in predetermined increments (step 634), e.g., 5, 10, or 20cm, and steps 620 and 630 are repeated until sample breakage is observed (631) or the maximum test height is reached (636) without sample breakage occurring. When

step

631 or 636 is reached, the test according to method 600 is terminated.

Embodiments of the glass-based articles described herein have a survival rate of at least about 60% when balls are dropped onto a glass surface from a height of 100cm when subjected to the inverted ball on sandpaper (IBoS) test described above. For example, a strengthened glass article is described as having a 60% survival rate when dropped from a given height when 3 of 5 identical (or nearly identical) samples (i.e., having approximately the same composition and when strengthened to have approximately the same compressive stress and depth of compression or compressive stress layer, as described herein) pass the IBoS drop test without breaking after being dropped from the predetermined height (here 100 cm). In other embodiments, the strengthened glass-based article has a viability of at least about 70%, in other embodiments, at least about 80%, and in other embodiments, at least about 90% when tested by a 100cm IBoS test. In other embodiments, the strengthened glass-based article survives at least about 60%, in other embodiments, at least about 70%, in other embodiments, at least about 80%, and in other embodiments, at least about 90% of a drop from a height of 100cm in an IBoS test. In one or more embodiments, the strengthened glass-based article survives at least about 60%, in other embodiments, at least about 70%, in other embodiments, at least about 80%, and in other embodiments, at least about 90% of a drop from a height of 150cm in an IBoS test.

To determine the survivability of a glass-based article when dropped from a predetermined height using the IBoS testing methods and apparatus described above, at least 5 identical (or nearly identical) samples (i.e., nearly identical composition, and if strengthened, nearly identical compressive stress and depth of compression or depth of layer) of the glass-based article may be tested, but a greater number (e.g., 10, 20, 30, etc.) of samples may also be subjected to the test to increase the confidence level of the test results. Each sample is dropped from a predetermined height (e.g., 100cm or 150cm) a single time, or from progressively higher heights without cracking until the predetermined height is reached, and visually (i.e., with the naked eye) inspected for evidence of cracking (formation of cracks and propagation through the entire thickness and/or entire surface of the sample). A sample is considered to "pass" the drop test if no rupture is observed after dropping from the predetermined height, and is considered to "fail" (or not "pass") if rupture is observed when the sample is dropped from a height less than or equal to the predetermined height. Survivability was determined as a percentage of the number of samples that passed the drop test. For example, if 7 samples in a set of 10 samples did not break when dropped from a predetermined height, the survivability of the glass would be 70%.

In one or more embodiments, the glass article exhibits a lower delayed fracture rate (i.e., when fractured, the glass article fractures rapidly or even immediately). In some embodiments, this fracture rate may be attributed to a deep DOC and a high level of CT. In particular, shortly after an attack on the glass article to induce cracking or to fail, the glass article is less likely to spontaneously crack. In one or more embodiments, when the glass article fractures, it is within 2 seconds or within 1 second or less after the impactInternal breakage into multiple fragments was measured by "Frangibility test" as described in z. tang et al, "Automated Apparatus for Measuring Frangibility and breakage of Strengthened Glass," Experimental Mechanics (2014)54: 903-912. Friability testing A50 mm stylus drop height was used and the stylus had a tungsten carbide tip (available from Fisher Scientific Industries, Inc.) under the trade name Fisher Scientific Industries

Manufacturer #13-378 with 60 degree conical spherical tip) weighing 40 g. In some embodiments, the primary fracture (or the first fracture to produce 2 fragments visible to the naked eye) occurs immediately after the impact causes the glass article to fracture, or within zero seconds or 0.1 seconds thereof. In one or more embodiments, the likelihood that the primary rupture occurs within the time period described herein (as measured by the frangibility test) is greater than or equal to about 90%. In some embodiments, the secondary rupture occurs in less than or equal to 5 seconds (e.g., less than or equal to 4 seconds, less than or equal to 3 seconds, less than or equal to 2 seconds, or less than or equal to 1 second). As used herein, "secondary rupture" refers to a rupture that occurs after a primary rupture. In one or more embodiments, the likelihood that this secondary rupture occurs within the time period described herein (as measured by the frangibility test) is greater than or equal to about 90%.

In one or more embodiments, the glass article emits less and smaller fragments after breakage than what is exhibited by known glass articles currently used with handheld electronic devices, which is a potential consideration for users. As used herein, the term "launch" or "launch" refers to the movement of fragments from their original position or orientation within a glass article after the glass article is broken. In some embodiments, less than or equal to about 10% (e.g., less than or equal to about 8%, less than or equal to about 6%, or less than or equal to about 5%) of the plurality of fragments are emitted after the glass article fractures and forms the plurality of fragments. In some embodiments, after the glass article fractures and forms a plurality of fragments, greater than or equal to about 50% of the emitted portion has a maximum dimension less than 0.5 mm. In some embodiments, the amount or quantity of fragments emitted can be characterized by a weight associated with the glass article before and after breakage. For example, the difference between the weight of the glass article prior to fracture (including the total weight of the portion of the plurality of fragments that were ejected and the portion of the glass article that was not ejected after fracture) and the weight of the portion of the glass article that was not ejected may be less than about 1% of the weight prior to impact or less. In some cases, the difference between the weight of the glass article prior to fracture (including the total weight of the portion of the plurality of fragments that were emitted and the portion of the fragments that were not emitted after fracture) and the weight of the portion of the glass article that was not emitted may be less than about 0.0005g (e.g., 0.0004g or less, 0.0003g or less, 0.0002g or less, or 0.0001g or less). To determine the weight of the non-emitted portion.

In one or more embodiments, the glass article exhibits a more uniform pattern of high cuts across its surface and volume. In some embodiments, glass articles having non-uniform thickness (i.e., shaped to have a three-dimensional or 2.5-dimensional shape) exhibit such high cut and uniformity. Without being bound by theory, this achieves strengthening the thinnest portions of the glass article to a sufficient degree without having some portions of the glass article exhibit brittleness while other portions are not, as defined by existing industry specifications.

In one or more embodiments, the glass article (directly bonded to the substrate, i.e., the display unit) exhibits haze after breakage due to the dense breakage pattern. Readability depends on the viewing angle and the thickness of the glass-based article. At a viewing angle of 90 degrees or normal incidence relative to the major surface of the glass article, the broken glass article exhibits low haze such that the underlying image or text is visible to the naked eye. At viewing angles of less than or equal to 70 degrees (or greater than or equal to 30 degrees from normal incidence) relative to the major surfaces of the glass article, the broken glass article exhibits haze that prevents underlying images or text from being seen by the naked eye. It is understood that such haze exists when the pieces of the glass article remain together, or when less than 10% of the pieces are emitted from the glass article. Without being bound by theory, it is believed that the glass article after breaking can provide privacy screen functionality due to its low haze at 90 degrees and 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 broken. This property is desirable in situations where the glass article may be used or touched by a user even after the glass article has broken, thereby minimizing or eliminating scratches and gouges to the user.

In one or more embodiments, the glass articles described herein can be combined with a confinement layer. The confinement layer is a material capable of containing fragments of the glass article when broken. For example, the confinement layer may comprise a polymeric material. In one or more embodiments, the restriction layer can include an adhesive material (e.g., a pressure sensitive adhesive material). In one or more embodiments, the constraining layer may have a Young's modulus of about 0.5 to 1.2 MPa. In one or more embodiments, the confinement layer can include a filled epoxy, an unfilled epoxy, a filled urethane, or an unfilled urethane.

Examples of filled epoxies include: a UV-induced conjugated (catalitic) epoxide which is the polymerization product of: 70.69 wt% Nanopox C620 colloidal silica sol (40% silica nanoparticles in cycloaliphatic epoxide resin), 23.56 wt% Nanopox C680 (50% silica nanoparticles in 3-ethyl-3-hydroxymethyl-oxetane), 3 wt% Coocosil MP-200 epoxy functional silane (adhesion promoter), 2.5 wt% Cyracril UVI-6976 (cationic photoinitiator, comprising triarylsulfonium hexafluoroantimonate in propylene carbonate), 0.25 wt% Tinuvine 292 amine stabilizer (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -sebacate and 1- (methyl) -8- (1,2,2,6, 6-pentamethyl-4-piperidinyl) -sebacate),

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

In some embodiments, a low modulus urethane acrylate may be used in the confinement layer. In some embodiments, the material may include a silica fill. One example of a low modulus urethane acrylate includes: 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. -acryloyloxyethyl hydrogen succinate), 10 wt.% Sartomer SR3392 (phenoxyethyl acrylate), 4 wt.% Irgacure 2022 (photoinitiator, acylphosphine oxide/alpha hydroxy ketone), 3 wt.% adhesion promoter (e.g., Silquest A-189, gamma-mercaptopropyl trimethoxysilane). To form the filled urethane, 4 wt% silica powder (e.g., Hi Sil 233) may be added.

In one or more embodiments, the glass article can be combined with a constraint layer, with or without the constraint layer adhered thereto. In some embodiments, the glass article can be disposed on and adhered to the containment layer. The glass article may be temporarily adhered or permanently adhered to the constraint layer. As shown in fig. 9A, a confinement layer 20 is disposed on at least one major surface (e.g., 12, 14 of fig. 1A) of the glass article. In fig. 9A, the confinement layer 20 is not disposed on any portion of the

minor surfaces

16, 18; however, the constraining layer 20 may extend from the major surface at least partially along one or both minor surfaces (16, 18) or along the entire length of one or both minor surfaces (16, 18). In such embodiments, the confinement layer may be formed from the same material. In one or more alternative embodiments, the confinement layer formed on the major surface may be different from the confinement layer formed on any portion of the minor surface. Fig. 9B shows an embodiment in which a confinement layer 20 is disposed on the major surface 14 and a second confinement layer 22 is disposed on both

minor surfaces

16, 18. In one or more embodiments, the confinement layer 20 is different in composition from the second confinement layer 22.

In one or more embodiments, the glass article may include a stress profile including spikes as described herein such that the surface CS is in the range of about 400-. In one or more embodiments, the glass article may include a stress distribution without spikes such that the surface CS is in the range of approximately 150-500MPa and the confinement material 20 is included only on the primary surface 14 (as shown in fig. 9A). The glass articles described herein can be incorporated into a variety of products and articles, for example, consumer electronics products or devices (e.g., cover glasses for hand-held electronic devices and touch-enabled display screens). The glass article may also be used in a restraint (or as a display article) (e.g., a billboard, a point-of-sale system, a computer and navigation system, etc.), a construction article (wall, fixture, panel, window, etc.), a transportation article (e.g., an automotive application, train, airplane, marine vehicle, etc.), an appliance (e.g., a washing machine, dryer, dishwasher, refrigerator, etc.), a package (e.g., a pharmaceutical package or container), or any article that requires some resistance to breakage.

As shown in fig. 10, an electronic device 1000 may include a glass-based article 100 according to one or more embodiments described herein. The device 1000 comprises: a housing 1020 having a front surface 1040, a back surface 1060, and side surfaces 1080; an electronic assembly (not shown) at least partially or completely within the housing and including at least a controller, a memory; and a display 1120 located at or adjacent to the front surface of the housing. The display glass-based article 100 is disposed as a cover at or on a front surface of the housing such that it covers the display 1120. In some embodiments, the glass-based article may be used as a back cover.

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

In one or more embodiments, the glass articles described herein can be used for packaging. For example, a package may include a glass article in the form of a bottle, vial, or container containing a liquid, solid, or gaseous material. In one or more embodiments, the glass article is a vial containing a chemical, such as a pharmaceutical material. In one or more embodiments, the enclosure includes a housing including an opening, an outer surface, and an inner surface, which defines an enclosed space. The housing may be formed from a glass article as described herein. The glass article includes a confinement layer. In some embodiments, the confined space is filled with a chemical or pharmaceutical material. In one or more embodiments, the opening of the housing may be closed or may be sealed with a lid. In other words, a lid may be arranged in the opening to close or enclose the confined space.

The glass article can include an amorphous substrate, a crystalline substrate, or a combination thereof (e.g., a glass-ceramic substrate). The glass article may comprise an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali aluminoborosilicate glass. In one or more embodiments, the glass article substrate (prior to being chemically strengthened as described herein) can include a glass having a composition comprising, in mole percent (mol%): about 40-80 SiO₂About 10 to 30 Al₂O₃About 0 to about 10 of B₂O₃About 0 to about 20 of R₂O, and RO of about 0 to about 15. In some cases, the composition may include any one or both of: about 0-5 mol% of ZrO₂And about 0-15 mole% of P₂O₅. About 0-2 mole% TiO may be present₂。

In some embodiments, the glass composition may include SiO in the following amounts, in mole percent₂: about 45 to about 80, about 45 to about 75, about 45 to about 70, about 45 to about 65, about 45 to about 60, about 45 to about 65, about 50 to about 70, about 55 to about 70, about 60 to about 70, about 70 to about 75, or about 50 to about 50About 65.

In some embodiments, the glass composition may include Al in mole percent amounts₂O₃: about 5 to about 28, about 5 to about 26, about 5 to about 25, about 5 to about 24, 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.

In some embodiments, the glass composition may include B in the following amounts, in mole percent₂O₃: about 0 to about 8, about 0 to about 6, about 0 to about 4, about 0.1 to about 8, about 0.1 to about 6, about 0.1 to about 4, about 1 to about 10, about 2 to about 10, about 4 to about 10, about 2 to about 8, about 0.1 to about 5, or about 1 to about 3. In some cases, the glass composition may be substantially free of B₂O₃. As used herein, the term "substantially free" with respect to a component of a composition means that the component is not actively or intentionally added to the composition in the initial formulation, but may be present as an impurity in an amount of less than about 0.001 mole%.

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

Alkali metal oxide R in the glass composition in mol%₂The total amount of O may be in the following range: 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, about 6 to about 13, or about 8 to about 12.

In one or more embodiments, the glass composition includes Na in the following amounts₂O: from about 0 mol% to about 18 mol%, from about 0 mol% to about 16 mol%, or from about 0 mol% to about 14 mol%, from about 0 mol% to about 10 mol%, from about 0 mol% to about 5 mol%, from about 0 mol% to about 2 mol%, from about 0.1 mol% to about 6 mol%, from about 0.1 mol% to about 5 mol%, from about 1 mol% to about 5 mol%, from about 2 mol% to about 5 mol%, or from about 10 mol% to about 20 mol%.

In some embodiments, Li is substituted with one or more substituents selected from the group consisting of alkyl, alkenyl, alkynyl, and alkynyl₂O and Na₂The amount of O is controlled to a specific amount or ratio to balance formability and ion exchangeable properties. For example, with Li₂The amount of O increases and the liquidus viscosity may decrease, preventing the use of some forming processes; however, such glass compositions are ion exchanged to deeper DOC levels as described herein. Na (Na)₂The amount of O may improve the liquidus viscosity but may inhibit ion exchange at deeper DOC levels.

In one or more embodiments, the glass composition may comprise K₂O，K₂The amount of O is less than about 5 mole%, less than about 4 mole%, less thanAbout 2 mole%, or less than about 1 mole%. In one or more alternative embodiments, the glass composition may be substantially free of K₂O, as defined herein.

In one or more embodiments, the glass composition may include Li₂O，Li₂The amount of O is about 0 to about 18 mole%, about 0 to about 15 mole%, or about 0 to about 10 mole%, about 0 to about 8 mole%, about 0 to about 6 mole%, about 0 to about 4 mole%, or about 0 to about 2 mole%. In some embodiments, the glass composition may comprise Li₂O，Li₂The amount of O is about 2 to about 10 mole%, about 4 to about 10 mole%, about 6 to about 10 mole%, or about 5 to about 8 mole%. In one or more alternative embodiments, the glass composition may be substantially free of Li₂O, as defined herein.

In one or more embodiments, the glass composition may comprise Fe₂O₃. In such embodiments, Fe₂O₃The amount may be present in an amount less than about 1 mole%, less than about 0.9 mole%, less than about 0.8 mole%, less than about 0.7 mole%, less than about 0.6 mole%, less than about 0.5 mole%, less than about 0.4 mole%, less than about 0.3 mole%, less than about 0.2 mole%, less than about 0.1 mole%, and all ranges and subranges therebetween. In one or more alternative embodiments, the glass composition may be substantially free of Fe₂O₃As defined herein.

In one or more embodiments, the glass composition may include ZrO₂. In such embodiments, ZrO₂The amount may be present in an amount less than about 1 mole%, less than about 0.9 mole%, less than about 0.8 mole%, less than about 0.7 mole%, less than about 0.6 mole%, less than about 0.5 mole%, less than about 0.4 mole%, less than about 0.3 mole%, less than about 0.2 mole%, less than about 0.1 mole%, and all ranges and subranges therebetween. In one or more alternative embodiments, the glass composition may be substantially free of ZrO₂As defined herein.

In one or more embodiments, the glass composition may comprise P₂O₅，P₂O₅From about 0 mol% to about 10 mol%, from about 0 mol% to about 8 mol%, from about 0 mol% to about 6 mol%, from about 0 mol% to about 4 mol%, from about 0.1 mol% to about 10 mol%, from about 0.1 mol% to about 8 mol%, from about 4 mol% to about 8 mol%, or from about 2 mol% to about 8 mol%. In some cases, the glass composition may be substantially free of P₂O₅。

In one or more embodiments, the glass composition may comprise TiO₂. In one or more embodiments, the TiO₂Present in an amount less than about 6 mole%, less than about 4 mole%, less than about 2 mole%, or less than about 1 mole%. In one or more alternative embodiments, the glass composition may be substantially free of TiO₂As defined herein. In some embodiments, the TiO₂Is present in an amount of about 0.1 to about 6 mole%, or about 0.1 to about 4 mole%. In some embodiments, the glass may be substantially free of TiO₂。

In some embodiments, the glass composition may include various compositional relationships. For example, the glass composition may include about 0.5 to about 1 Li₂Amount of O (unit, mol%) and R₂Ratio of total amount (unit, mol%) of O. In some embodiments, the glass composition may include an R of about-5 to about 0₂Total amount of O (unit, mol%) and Al₂O₃The difference in the amount (unit, mol%) of (A). In some cases, the glass composition can include an R of about 0 to about 3_xTotal amount of O (unit, mol%) and Al₂O₃The difference in the amount of (c). The glass composition of one or more embodiments may exhibit a ratio of the amount of MgO (in mol%) to the total amount of RO (in mol%) of about 0 to 2.

In some embodiments, the composition for the glass substrate may be formulated with 0-2 mole% of at least one fining agent selected from the group consisting of: na (Na)₂SO₄、NaCl、NaF、NaBr、K₂SO₄KCl, KF, KBr and SnO₂. According to one or more embodiments, the glass composition may further comprise about 0-2, about 0-1,About 0.1 to 2, about 0.1 to 1, or about 1 to 2 SnO₂. The glass compositions disclosed herein may be substantially free of As₂O₃And/or Sb₂O₃。

In one or more embodiments, in particular, the composition may comprise: 62 to 75 mol% SiO₂(ii) a 10.5 mol% to about 17 mol% Al₂O₃(ii) a 5 mol% to about 13 mol% Li₂O; 0 mol% to about 4 mol% ZnO; 0 mol% to about 8 mol% MgO; 2 mol% to about 5 mol% TiO₂(ii) a 0 mol% to about 4 mol% B₂O₃(ii) a 0 mol% to about 5 mol% Na₂O; 0 mol% to about 4 mol% K₂O; 0 mol% to about 2 mol% ZrO₂(ii) a 0 mol% to about 7 mol% P₂O₅(ii) a 0 mol% to about 0.3 mol% Fe₂O₃(ii) a 0 mol% to about 2 mol% MnOx; and 0.05 mol% to about 0.2 mol% SnO₂。

In one or more embodiments, the composition may comprise: 67 mol% to about 74 mol% SiO₂(ii) a 11 mol% to about 15 mol% Al₂O₃(ii) a 5.5 mol% to about 9 mol% Li₂O; 0.5 mol% to about 2 mol% ZnO; 2 mol% to about 4.5 mol% MgO; 3 mol% to about 4.5 mol% TiO₂(ii) a 0 mol% to about 2.2 mol% B₂O₃(ii) a 0 mol% to about 1 mol% Na₂O; 0 mol% to about 1 mol% K₂O; 0 mol% to about 1 mol% ZrO₂(ii) a 0 mol% to about 4 mol% P₂O₅(ii) a 0 mol% to about 0.1 mol% Fe₂O₃(ii) a 0 mol% to about 1.5 mol% MnOx; and 0.08 to about 0.16 mol% SnO₂。

In one or more embodiments, the composition may comprise: 70 to 75 mol% SiO₂(ii) a 10 mol% to about 15 mol% Al₂O₃(ii) a 5 mol% to about 13 mol% Li₂O; 0 mol% to about 4 mol% ZnO; 0.1 mol% to about 8 mol% MgO; 0 mol% to about 5 mol% TiO₂(ii) a 0.1 mol% to about 4 mol%％B₂O₃(ii) a 0.1 mol% to about 5 mol% Na₂O; 0 mol% to about 4 mol% K₂O; 0 mol% to about 2 mol% ZrO₂(ii) a 0 mol% to about 7 mol% P₂O₅(ii) a 0 mol% to about 0.3 mol% Fe₂O₃(ii) a 0 mol% to about 2 mol% MnOx; and 0.05 mol% to about 0.2 mol% SnO₂。

In one or more embodiments, the composition may comprise: 52 mol% to about 63 mol% SiO₂(ii) a 11 mol% to about 15 mol% Al₂O₃(ii) a 5.5 mol% to about 9 mol% Li₂O; 0.5 mol% to about 2 mol% ZnO; 2 mol% to about 4.5 mol% MgO; 3 mol% to about 4.5 mol% TiO₂(ii) a 0 mol% to about 2.2 mol% B₂O₃(ii) a 0 mol% to about 1 mol% Na₂O; 0 mol% to about 1 mol% K₂O; 0 mol% to about 1 mol% ZrO₂(ii) a 0 mol% to about 4 mol% P₂O₅(ii) a 0 mol% to about 0.1 mol% Fe₂O₃(ii) a 0 mol% to about 1.5 mol% MnOx; and 0.08 to about 0.16 mol% SnO₂。

In some embodiments, the composition may be substantially free of B₂O₃、TiO₂、K₂O and ZrO₂Any one or more of them.

In one or more embodiments, the composition may include at least 0.5 mole% of P₂O₅、Na₂O and optionally Li₂O, wherein Li₂O (mol%)/Na₂O (mol%)<1. In addition, these compositions may be essentially free of B₂O₃And K₂And O. In some embodiments, the composition may comprise ZnO, MgO, and SnO₂。

In some embodiments, the composition may comprise: about 58 mol% to about 65 mol% SiO₂(ii) a About 11 mol% to about 19 mol% Al₂O₃(ii) a About 0.5 mol% to about 3 mol% P₂O₅(ii) a About 6 mol% to about 18 mol% Na₂O; 0 mol% to about 6 mol% MgO; and 0 mol% to about 6 mol% ZnO. In certain embodiments, the composition may comprise: about 63-65 mol% SiO₂(ii) a About 11-17 mol% Al₂O₃(ii) a About 1-3 mol% of P₂O₅(ii) a About 9-20 mol% Na₂O; 0 mol% to about 6 mol% MgO; and 0 mol% to about 6 mol% ZnO.

In some embodiments, the composition may comprise the following compositional relationship: r₂O (mol%)/Al₂O₃(mol%)<2, wherein R₂O＝Li₂O+Na₂And O. In some embodiments, 65 mol%<SiO₂(mol%) + P₂O₅(mol%)<67 mol%. In certain embodiments, R₂O (mol%) + R' O (mol%) -Al₂O₃(mol%) + P₂O₅(mol%)>-3 mol%, wherein R₂O＝Li₂O+Na₂O, and R' O are the total amount of divalent metal oxide present in the composition.

Other exemplary compositions of the glass articles prior to chemical strengthening are shown in table 1, as described herein.

Table 1: exemplary compositions prior to chemical strengthening

As described herein, other exemplary compositions of glass-based articles prior to chemical strengthening are shown in table 1A. Table 1B lists selected physical properties determined by the examples listed in table 1A. The physical properties listed in table 1B include: density; low and high temperature CTE; strain point, annealing point and softening point; 10¹¹Poise, 35kP, 200kP, liquidus and zirconium decomposition temperature; zirconium decomposition and liquidus viscosity; poisson ratio(ii) a Young's modulus; a refractive index; and stress optical coefficients. In some embodiments, the glass-based articles and glass substrates described herein have a high temperature CTE of less than or equal to 30ppm/° c and/or a young's modulus of at least 70GPa, and in some embodiments, a young's modulus of up to 80 GPa.

Table 1A: exemplary compositions prior to chemical strengthening

Table 1B: selected physical properties of the glasses listed in Table 1B

When the glass article comprises a glass-ceramic, the crystalline phases can include beta-spodumene, rutile, gahnite, or other known crystalline phases, and combinations thereof.

The glass article may be substantially flat, but other embodiments may employ curved or any other shape or configuration of the substrate. In some cases, the glass article may have a 3D or 2.5D shape. The glass article can be substantially optically clear, transparent, and free of light scattering. The glass article may have a refractive index of about 1.45 to about 1.55. As used herein, refractive index values are relative to 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 along one or more dimensions thereof for aesthetic and/or functional reasons. For example, the edges of the glass article may be thicker than more central regions of the glass article. The length, width, and thickness dimensions of the glass article may also vary depending on the application or use of the article.

The glass article may be characterized by the manner in which it is formed. For example, the glass article may be characterized as being float formable (i.e., formed by a float process), down drawable, specifically, fusion formable, or slot drawable (i.e., formed by a down draw process such as a fusion draw process or a slot draw process).

Float formable glass articles can be characterized as having a smooth surface and uniform thickness produced by floating molten glass on a bed of molten metal, typically tin. In one exemplary process, molten glass is fed onto the surface of a bed of molten tin to form a floating glass ribbon. As the ribbon flows along the tin bath, the temperature is gradually reduced until the ribbon solidifies into a solid glass article that can be lifted from the tin onto the rollers. Once out of 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 by the float process may be subjected to a ceramming process by which one or more crystalline phases are produced.

The downdraw process produces glass articles having a uniform thickness with a relatively pristine surface. Because the average flexural strength of the glass article is controlled by the amount and size of the surface flaws, the pristine surface that is minimally contacted has a higher initial strength. When the high strength glass article is subsequently further strengthened (e.g., chemically strengthened), the resulting strength may be higher than that of a glass article whose surface has been polished and polished. The downdraw glass article may be drawn to a thickness of about less than 2 mm. In addition, the drawn glass article has a very flat, smooth surface that can be used for end applications without costly grinding and polishing. When the glass article is a glass-ceramic, the glass article formed by the downdraw process may be subjected to a ceramming process by which one or more crystalline phases are created.

Fusion draw processes use, for example, draw cans having channels for receiving molten glass raw materials. The channel has weirs that open at the top of both sides of the channel along the length of the channel. As the channel is filled with molten material, the molten glass overflows the weir. Under the influence of gravity, the molten glass flows down from the outer surface of the draw tank as two flowing glass films. The outer surfaces of these drawn cans extend downwardly and inwardly so that they join at the edges below the drawn cans. The two flowing glass films are joined at the edge to fuse and form a single flowing glass article. The fusion drawing method has the advantages that: since the two glass films overflowing the channel fuse together, neither outer surface of the resulting glass article is in contact with any part of the apparatus. 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 by the fusion process may be subjected to a ceramming process by which one or more crystalline phases are produced.

The slit draw process is different from the fusion draw process. In the slot draw process, molten raw material glass is supplied to a draw tank. The bottom of the draw vessel has an open slot with a nozzle extending along the length of the slot. The molten glass flows through the slot/nozzle and is drawn down as a continuous glass article and into an annealing zone. When the glass article is a glass-ceramic, the glass article formed by the slot draw process may be subjected to a ceramming process by which one or more crystalline phases are produced.

In some embodiments, the Glass Articles may be formed using a Thin Roll Process, as described 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, U.S. patent publication No. 20150027169 entitled Methods And Apparatus For Forming Glass ribbons, And U.S. patent publication No. 20050099618 entitled Apparatus And Methods For Forming Thin Glass Articles, the entire contents of which are incorporated herein by reference. More specifically, the glass article may be formed by: the method includes the steps of feeding a vertical stream of molten glass, forming the feed stream of molten glass or glass-ceramic with a pair of forming rolls maintained at a surface temperature of greater than or equal to about 500 ℃ or greater than or equal to about 600 ℃ to form a formed glass ribbon having a formed thickness, and sizing the formed glass ribbon with a pair of sizing rolls maintained at a surface temperature of less than or equal to about 400 ℃ to produce a sized glass ribbon having a desired thickness and a desired thickness uniformity, the desired thickness being less than the formed thickness. An apparatus for forming a glass ribbon may include: a glass feed device for supplying a supply stream of molten glass; a pair of forming rolls maintained at a surface temperature of greater than or equal to about 500 ℃, the forming rolls being closely spaced adjacent to each other defining a glass forming gap between the forming rolls, the glass forming gap being located vertically below the glass feed device for receiving the feed stream of molten glass and thinning the feed stream of molten glass between the forming rolls to form a formed glass ribbon having a formed thickness; and a pair of sizing rolls maintained at a surface temperature of less than or equal to about 400 ℃, the sizing rolls being closely spaced adjacent to each other defining a glass sizing gap between the sizing rolls, the glass sizing gap being located vertically below the forming rolls for receiving and thinning the formed glass ribbon to produce a sized glass ribbon having a desired thickness and thickness uniformity.

In some cases, a thin roll process may be employed when the viscosity of the glass does not permit the use of fusion draw or slot draw methods. For example, when the glass exhibits a liquidus viscosity of less than 100kP, thin rolls may be employed to form the glass article.

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

Another aspect of the present disclosure pertains to a method of forming a fracture-resistant glass article. The method comprises the following steps: providing a glass substrate having a first surface and a second surface defining a thickness of less than or equal to about 1 millimeter, and creating a stress distribution in the glass substrate, as described herein, to provide a fracture-resistant glass article. In one or more embodiments, generating a stress profile includes: a plurality of basic ions are ion exchanged into the glass substrate to form an alkali metal oxide gradient comprising a non-zero concentration of alkali metal oxide extending along the thickness. In one example, generating the stress profile includes immersing the glass substrate in a molten salt bath including Na⁺、K⁺、Rb⁺、Cs⁺Or combinations thereof at a temperature greater than or equal to about 350 deg.c (e.g., about 350 deg.c and 500 deg.c). In one example, the molten bath may contain NaNO₃And the temperature may be about 485 deg.c. In another example, the bath may contain NaNO₃And the temperature may be about 430 deg.c. The glass substrate may be immersed in the bath for greater than or equal to about 2 hours, up to about 48 hours (e.g., about 12-48 hours, about 12-32 hours, about 16-24 hours, or about 24-32 hours).

In some embodiments, the method may comprise employing successive immersion steps in more than one bathThe glass substrate is chemically strengthened or ion exchanged in more than one step. For example, two or more baths may be used in sequence. The composition of the one or more baths may include a single metal (e.g., Ag)⁺、Na⁺、K⁺、Rb⁺Or Cs⁺) Or a combination of metals in the same bath. When more than one bath is used, the baths may have the same or different compositions and/or temperatures from each other. The immersion time in each such bath may be the same or may be varied to provide a desired stress profile.

In one or more embodiments, a second or subsequent bath may be employed to create the larger surface CS. In some cases, the method comprises: the glass material is immersed in the second or subsequent bath to create a larger surface CS without significantly affecting the chemical depth and/or DOC of the layer. In such embodiments, the second or subsequent bath may include a single metal (e.g., KNO)₃Or NaNO₃) Or mixtures of metals (KNO)₃And NaNO₃). The temperature of the second or subsequent bath may be adjusted to produce a larger surface CS. In some embodiments, the immersion time of the glass material in the second or subsequent bath may be adjusted to produce a larger surface CS without significantly affecting the chemical depth and/or DOC of the layer. For example, the immersion time in the second or subsequent bath may be less than 10 hours (e.g., less than or equal to about 8 hours, less than or equal to about 5 hours, less than or equal to about 4 hours, less than or equal to about 2 hours, less than or equal to about 1 hour, less than or equal to about 30 minutes, less than or equal to about 15 minutes, or less than or equal to about 10 minutes).

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

Examples

Various embodiments are further illustrated by the following examples.

Example 1

Glass articles according to examples 1A-1B and comparative examples 1C-1G were made by: providing a glass having a nominal glass composition of 58 mol% SiO₂16.5 mol% Al₂O₃17 mol% Na₂O, 3 mol% MgO, and 6.5 mol% P₂O₅The glass substrate of (1). The glass substrate had a thickness of 0.4mm and length and width dimensions of 50 mm. The glass substrate is chemically strengthened by an ion exchange process comprising 80% KNO immersed at a temperature of about 420 DEG C₃And 20% NaNO₃The molten salt bath of (2), the duration is shown in table 2. The resulting glass articles were then subjected to the AROR test described above, and the major surface of each sample was abraded with 90 mesh SiC particles at 5psi, 15psi, or 25psi, also as shown in Table 2. Table 2 shows the average equibiaxial flexural strength or failure load of the glass articles.

Table 2: chemical strengthening conditions and AROR results of example 1

The average equibiaxial flexural strength or failure load of the examples after 15psi and 25psi abrasion is plotted in fig. 11. As shown in fig. 11, examples 1A and 1B exhibited maximum average equibiaxial flexural strength after 25psi abrasion. Thus, the AROR performance of examples 1A and 1B demonstrates that these glass articles exhibit a high cut fracture pattern, indicating improved retained strength, particularly for deeper abrasion depths due to higher abrasion pressures.

Example 2

Glasses according to examples 2A-2C and comparative examples 2D-2F were manufactured by providing glass substrates and chemically strengthening the glass substratesAn article of manufacture. The glass substrates used in examples 2A-2C and comparative examples 2D-2F had the following nominal glass compositions: 69.2 mol% SiO₂12.6 mol% Al₂O₃1.8 mol% B₂O₃7.7 mol% Li₂O, 0.4 mol% Na₂O, 2.9 mol% MgO, 1.7 mol% ZnO, 3.5 mol% TiO₂And 0.1 mol% SnO₂. The substrate used in comparative example 2D had the same composition as in example 1.

The glass substrate has a thickness of 1mm and length and width dimensions that allow assembly with known hand held device housings. The glass substrate was chemically strengthened by the ion exchange process shown in table 3. The CT and DOC values for examples 2A-2D were measured by scapp, also as shown in table 3.

Table 3: ion exchange conditions and drop test results for example 2

Comparative example 2D was ion exchanged to exhibit an error function stress profile (measured by Roussev I, using IWKB analysis) with a DOC of over 75 microns. The resulting glass article was then converted into a consistent hand held device housing and subjected to the drop test described above on 30 grit sandpaper. Fig. 12 shows the maximum failure height of the embodiment. As shown in fig. 12, examples 2A-2C exhibited significantly greater maximum failure heights (i.e., 212cm, 220cm, and 220cm, respectively) and exhibited cutting behavior. Example 2F, having the same composition, did not exhibit the same cutting behavior and exhibited a lower maximum failure height than 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 examples 3L-3X had the following nominal glass composition: 69 mol% SiO₂10.3 mol% Al₂O₃15.2 mol% Na₂O, 5.4 mol% MgO, and 0.2 mol% SnO₂。

The glass substrate has a thickness of 0.4mm and length and width dimensions of 50mm by 50 mm. The glass substrate is chemically strengthened by ion exchange. Examples 3A-3L 80% KNO at 460 deg.C₃And 20% NaNO₃Ion-exchanging in the molten salt bath for 12 hours. Comparative examples 3L-3X were ion exchanged such that each of the resulting glass articles exhibited a surface CS of 912MPa and a DOC of 37um, as measured by FSM.

The resulting glass article is then broken by: a single impact with a carbide ball-point scriber (conosidic description) was made on one major surface of each article from a drop height (as shown in tables 4 and 5) and the fracture or crack pattern was evaluated from: how many fragments are generated, the glass article is immediately broken or not broken at all, and the fragility of the glass article.

Table 4: examples 3A-3K failure characteristics and rupture mechanisms

DNB-without fragmentation

Table 5: failure characteristics and rupture mechanisms of comparative examples 3L-3X

DNB-without fragmentation

As shown in tables 4-5, it is clear that glass articles chemically strengthened to near the brittle limit state (i.e., comparative examples 3L-3X) are much more likely to experience delayed failure than glass articles chemically strengthened to the highly cut/chip condition after fracture (i.e., examples 3A-3K). Specifically, over 80% of comparative examples 3L-3X failed in a delayed manner, while the samples in Table 4 failed either immediately or without breakage. In addition, comparative examples 3L-3X exhibited fewer, larger, and more fragmented pieces than examples 3A-4K (failure with high cut and exhibited pieces with low aspect ratio).

Example 4

Glass articles according to examples 4A-4B and comparative examples 4C-4F were made by providing glass substrates having the same nominal composition as example 1 and strengthening the glass substrates. The glass substrate has a thickness of 0.4mm and is chemically strengthened by an ion exchange process, wherein the glass substrate is immersed in 80% KNO at a temperature of 430 ℃₃And 20% NaNO₃The molten salt bath of (4), the duration is shown in table 6.

Table 6: duration of ion exchange of example 5

Measurement of K in glass articles using glow discharge emission spectroscopy (GDOES)₂The O concentration. In FIG. 13, the smaller Na content in the glass substrate⁺Alternative larger K⁺Mol% of ions expressed as K₂O) is plotted on the vertical axis against ion exchange depth. Examples 4A and 4B exhibited higher stored tensile energy (and center tension) than the other distributions, and maximized the magnitude of DOC and surface compression.

FIG. 14 shows the stress distribution of example 4G, as measured by Roussev I using the IWKB analysis, said example 4G being formed by: the same substrates as in examples 4A and 4B are provided, but with an immersion temperature of 460 ℃ in 70% KNO₃And 30% NaNO₃In the molten salt bath of (2), for 12 hours.

Example 5

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

Table 7: ion exchange conditions of example 5

Example 5A and comparative example 5B were adhered to a transparent substrate using a pressure sensitive adhesive supplied by 3M company under the trade name 468MP, applied in the same manner and at a consistent thickness. Example 5A and comparative example 5B were broken, and the resulting broken glass articles were evaluated. Fig. 15A and 15B show burst images of example 5A and comparative example 5B, respectively. As shown in fig. 15A, example 5A exhibited higher cutting behavior and yielded chips with an aspect ratio of less than about 2. As shown in fig. 15B, comparative example 5B yielded chips with a higher aspect ratio.

Comparative examples 5C and 5D were not restricted with adhesive and underwent fracture. The resulting broken glass article was evaluated. Fig. 15C and 15D show fracture images of example 5C and example 5D, respectively. As shown in fig. 15C, comparative example 5C exhibited a larger fragment. As shown in fig. 15D, example 5D produced chips indicating cutting. It is believed that the subfragments (not shown) do not extend through the thickness of the glass article.

Example 6

A glass article according to example 6 was made by providing a glass substrate having the same nominal composition as examples 3A-3k and strengthening in the same manner. After fracture, example 6 was evaluated for haze or readability at different viewing angles. Example 6 exhibited a high degree of cut after fracture, but still exhibited good readability at a viewing angle of 90 ° relative to the surface plane or major surface of the glass article. As the viewing angle decreases, readability decreases, as shown by the images of fig. 16A-16D. Fig. 16A demonstrates that the text behind example 6 is still visible and readable at a viewing angle of 90 degrees relative to the surface plane or major surface of the glass article. Fig. 16B shows that at a viewing angle of 67.5 degrees, the text is slightly visible and readable. According to fig. 16C-16D, the text is unclear or unreadable at viewing angles of 45 degrees and 22.5 degrees relative to the surface plane or major surface of the glass article. Thus, when used for a display, embodiment 6 can function as a privacy screen, so that only a viewer can clearly read or see the display, and others other than the viewer may not be able to clearly read the display.

Example 7

Glass articles according to examples 7A-7C were made by: glass substrates having a 2.5 dimensional shape but different thicknesses were provided (i.e., 1mm thickness for example 7A, 0.8mm thickness for example 7B, and 0.5mm thickness for example 7C). The 2.5-dimensional shape includes a flat major surface and an opposing curved major surface. The composition of the glass substrate was the same as in examples 2A-2C. The stored tensile energy for each substrate was calculated as a function of ion exchange time using a melt bath temperature of 430 ℃. The total amount of stress on the CT region (327 in fig. 4) measured by scapp was used to calculate the stored tensile energy. The calculated stored tensile energy is plotted as a function of ion exchange time in fig. 17. For display purposes, 10J/m is plotted²The dashed line of stored tensile energy values of (a), represents an approximate threshold for friability. The highlighted areas represent ion exchange conditions for individual parts having a thickness in the range of 0.5-1.0mm exhibiting the behavior described herein. In particular, this range achieves optimal mechanical properties and similar cutting levels over the area of the part when and if the part is broken.

If ion exchange parameters are determined for various thicknesses using known friability limits, then at time A (stored tensile energy reaches less than 10J/m)²Ion exchange time) a glass substrate having a thickness of 1mm would be non-brittle, and a glass substrate having a thickness of 0.5mm would have a low CS. At time C, a glass substrate having a thickness of 0.5mm is non-frangible, and a glass substrate having a thickness between the 1mm and 0.8mm regions would be considered frangible. Thus, when using the existing definition of frangibility,figure 17 shows that for thicker parts or areas of non-uniform thickness parts, a significantly longer ion exchange time (as compared to thinner parts or thinner areas of intentionally non-uniform thickness parts) is selected for a given temperature in a given bath. In order to provide a fully finished 2.5D part with significantly improved drop performance and reliability, as well as a more uniform degree of chipping or cutting, it may be desirable to ion exchange the part for a shorter period of time, thereby accommodating a higher degree of stored tensile energy (than would be the case if selected to limit the degree of chipping or cutting).

Fig. 18 shows the sample shown in fig. 17, except that the tensile energy of the arrangement shown at 11 is now shown as the Central Tension (CT), which is used as a more general description of the tensile energy in the tensile zone of the ion exchange specimen.

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 article has a thickness of 0.4mm and is chemically strengthened by a two-step ion exchange process in which the glass substrate is first immersed in 80% KNO at a temperature of 460 ℃₃And 20% NaNO₃Is taken out of the first molten salt bath and immersed in 100% KNO at a temperature of 390 c for 12 hours₃For 12 minutes in the second molten salt bath. The resulting glass article had a compressive stress of 624.5MPa, a DOC of about 83.3 microns (which is equivalent to 0.208t), and a maximum CT of about 152.6MPa, as measured by Roussev I application IWKB analysis. Figure 19 shows compressive stress (shown as negative values) and tensile stress (shown as positive values) versus depth (in microns).

Aspect (1) of the present disclosure pertains to a strengthened glass article comprising: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; wherein, after the glass article fractures according to the frangibility test, the glass article comprises a plurality of fragments, wherein at least 90% of the plurality of fragments have an aspect ratio of less than or equal to about 5.

Aspect (2) of the present disclosure pertains to the strengthened glass article of aspect (1), wherein the glass article fractures into the plurality of fragments in less than or equal to 1 second, as measured by the frangibility test.

Aspect (3) of the present disclosure is the strengthened glass article of aspect (1) or aspect (2), wherein at least 80% of the plurality of fragments have a maximum dimension of less than or equal to 3 t.

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

Aspect (5) of the present disclosure is the strengthened glass article of any one of aspects (1) to (4), wherein at least 50% of the plurality of fragments comprises less than or equal to about 10mm³The volume of (a).

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

Aspect (7) of the present disclosure is the strengthened glass article of any one of aspects (1) through (6), wherein the glass article comprises a first weight prior to fracture, and wherein the plurality of fragments comprises an emitted fragment portion and an unexmitted fragment portion, the unexmitted fragment portion having a second weight, a difference between the first weight and the second weight being 1% of the first weight.

Aspect (8) of the present disclosure pertains to the strengthened glass article of any one of aspects (1) to (7), wherein the glass article has a probability of breaking into the plurality of fragments of greater than or equal to 99% in less than or equal to 1 second, as measured by the frangibility test.

Aspect (9) of the present disclosure is the strengthened glass article of any one of aspects (1) to (8), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

Aspect (10) of the present disclosure pertains to 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 the ratio of the central tension to the surface compressive stress is about 0.1 to about 1.

Aspect (11) of the present disclosure pertains to the strengthened glass article of aspect (10), wherein the central tension is greater than or equal to 100MPa/√ (t/1mm) (in MPa), where t is in mm.

Aspect (12) of the present disclosure pertains to the strengthened glass article of any one of aspects (10) to (11), wherein the central tension is greater than or equal to 50 MPa.

Aspect (13) of the present disclosure pertains to the strengthened glass article of any one of aspects (10) to (12), wherein the surface compressive stress is greater than or equal to 150 MPa.

Aspect (14) of the present disclosure pertains to the strengthened glass article of any one of aspects (10) to (13), wherein the surface compressive stress is greater than or equal to 400 MPa.

Aspect (15) of the present disclosure is the strengthened glass article of any one of aspects (10) to (14), wherein the DOC comprises greater than or equal to about 0.2 t.

Aspect (16) of the present disclosure is the strengthened glass article of any one of aspects (1) through (15), wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali aluminoborosilicate glass.

Aspect (17) of the present disclosure pertains to the strengthened glass article of any one of aspects (1) to (16), wherein the glass article is disposed on a constraint layer.

An aspect (18) of the present disclosure pertains to a strengthened glass article comprising: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; wherein the glass article exhibits a failure load of greater than or equal to about 10kgf after being abraded with 90 mesh SiC particles at a pressure of 25psi for 5 seconds.

Aspect (19) of the present disclosure is the strengthened glass article of aspect (18), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

Aspect (20) of the present disclosure pertains to the strengthened glass article of any one of aspects (18) or (19), the strengthened glass article of claim 18 or (19), 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 about 0.1 to about 1.

Aspect (21) of the present disclosure pertains to the strengthened glass article of aspect (20), wherein the Central Tension (CT) is greater than or equal to 50 MPa.

Aspect (22) of the present disclosure is the strengthened glass article of aspect (20) or aspect (21), wherein the surface compressive stress is greater than or equal to 150 MPa.

Aspect (23) of the present disclosure pertains to the strengthened glass article of any one of aspects (20) to (22), wherein the surface compressive stress is greater than or equal to 400 MPa.

An aspect (24) of the present disclosure is the strengthened glass article of any one of aspects (20) through (23), wherein the DOC comprises greater than or equal to about 0.2 t.

An aspect (25) of the present disclosure is the strengthened glass article of any one of aspects (18) through (24), wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali aluminoborosilicate glass.

Aspect (26) of the present disclosure pertains to the strengthened glass article of any one of aspects (20) to (25), wherein the glass article is adhered to a substrate.

An aspect (27) of the present disclosure pertains to an apparatus, comprising: a strengthened glass substrate; a confinement layer; and a support, wherein the strengthened glass substrate comprises: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; and a Center Tension (CT) of greater than or equal to 50MPa, wherein the device comprises a tablet, a transparent display, a cell phone, a video player, an information terminal device, an e-reader, a laptop computer, or a non-transparent display.

Aspect (29) pertains to the device of aspect (27), wherein the glass article comprises a plurality of fragments having an aspect ratio of less than or equal to about 5 after the glass article has broken according to the frangibility test.

Aspect (29) pertains to the device of aspect (27) or aspect (28), wherein the glass article breaks into the plurality of fragments in less than or equal to 1 second, as measured by the frangibility test.

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

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

Aspect (32) pertains to the apparatus of any one of aspects (28) to (31), wherein at least 50% of the plurality of pieces comprises less than or equal to about 10mm³The volume of (a).

Aspect (33) pertains to the apparatus of any one of aspects (28) to (32), wherein the plurality of fragments comprises an ejected fragment portion, wherein the ejected fragment portion comprises 10% or less of the plurality of fragments.

Aspect (34) pertains to the apparatus of any one of aspects (28) through (33), wherein the glass article comprises a first weight prior to fracturing, and wherein the plurality of fragments comprises an ejected portion of fragments and a non-ejected portion of fragments, the non-ejected portion of fragments having a second weight, a difference between the first weight and the second weight being 1% of the first weight.

Aspect (35) pertains to the device of any one of aspects (28) to (34), wherein the glass article has a likelihood of breaking into the plurality of fragments of greater than or equal to 99% in less than or equal to 1 second, as measured by the frangibility test.

Aspect (36) pertains to the apparatus of any one of aspects (28) to (35), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

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

Aspect (38) pertains to the apparatus of aspect (37), wherein the surface compressive stress is greater than or equal to 150 MPa.

Aspect (39) pertains to the device of any one of aspects (27) through (38), the device of any one of claims 27-38, wherein the DOC comprises greater than or equal to about 0.2 t.

Aspect (40) pertains to the apparatus of any one of aspects (27) through (39), wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali aluminoborosilicate glass.

Aspect (41) pertains to the device of any one of aspects (27) to (40), wherein the glass article is disposed on a confinement layer.

Aspect (42) pertains to a strengthened glass article comprising: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; wherein after the glass article is laminated to the containment layer and broken according to the frangibility test, the glass article comprises a break, wherein at least 5% of the break extends only partially through the thickness.

Aspect (43) is the strengthened glass article of aspect (42), wherein the glass article fractures into the plurality of fragments in less than or equal to 1 second, as measured by the frangibility test.

Aspect (44) is the strengthened glass article of aspect (42) or aspect (43), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

Aspect (45) pertains to the strengthened glass article of any one of aspects (42) to (44), 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 about 0.1 to about 1.

Aspect (46) is the strengthened glass article of aspect (45), wherein the central tension is greater than or equal to 50 MPa.

Aspect (47) is the strengthened glass article of aspect (45) or aspect (46), wherein the surface compressive stress is greater than or equal to 150 MPa.

Aspect (48) pertains to the strengthened glass article of any one of aspects (42) to (47), wherein the DOC comprises greater than or equal to about 0.2 t.

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

Aspect (50) pertains to the strengthened glass article of any one of aspects (42) to (49), wherein the glass article is disposed on a constraint layer.

Aspect (51) pertains to a consumer electronics product, comprising: a housing having a front surface; an electronic assembly at least partially provided within the housing, the electronic assembly including at least a controller, a memory, and a display; and a cover glass disposed at a front surface of the housing and over the display, the cover glass comprising a strengthened glass article, wherein the strengthened glass article comprises: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; and a Central Tension (CT) greater than or equal to 50 MPa.

Aspect (52) pertains to the consumer electronic device of aspect (51), wherein, after the glass article has broken according to the frangibility test, the glass article comprises a plurality of fragments having an aspect ratio of less than or equal to about 5, and

aspect (53) pertains to the consumer electronic device of aspect (52), wherein the glass article breaks into the plurality of fragments in less than or equal to 1 second, as measured by the frangibility test.

Aspect (54) pertains to the consumer electronic device of aspect (52) or aspect (53), wherein at least 80% of the plurality of pieces have a maximum dimension of less than or equal to 2 t.

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

Aspect (56) pertains to any one of aspects (52) to (55)Wherein at least 50% of the plurality of pieces comprise greater than or equal to about 10mm³The volume of (a).

Aspect (57) pertains to the consumer electronic device of any of aspects (52) through (56), wherein the plurality of fragments comprises an emitted fragment portion, wherein the emitted fragment portion comprises 10% or less of the plurality of fragments.

Aspect (58) pertains to the consumer electronic device of any of aspects (52) through (57), wherein the glass article comprises a first weight prior to fracture, and wherein the plurality of fragments comprises an emitted fragment portion and a non-emitted fragment portion, the non-emitted fragment portion having a second weight, a difference between the first weight and the second weight being 1% of the first weight.

Aspect (59) pertains to the consumer electronic device of any one of aspects (53) through (58), wherein the glass article has a likelihood of breaking into the plurality of fragments of greater than or equal to 99% in less than or equal to 1 second, as measured by the frangibility test.

Aspect (60) pertains to the consumer electronic device of any of aspects (51) through (59), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

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

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

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

Aspect (64) pertains to the consumer electronic device of any of aspects (51) through (63), wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate, or an alkali aluminoborosilicate glass.

Aspect (65) pertains to the consumer electronic device of any one of aspects (51) through (64), wherein the glass article is disposed on a constraint layer.

Aspect (66) pertains to the consumer electronics device of any of aspects (51) through (65), wherein the consumer electronics device comprises a tablet, a transparent display, a cell phone, a video player, an information terminal device, an e-reader, a laptop computer, or a non-transparent display.

Aspect (67) pertains to a packaged product, comprising: a housing comprising an opening, an outer surface, and an inner surface, the inner surface defining a confined space; wherein the housing comprises a strengthened glass article, wherein the strengthened glass article comprises: a first surface and a second surface opposite the first surface defining a thickness (t) of less than or equal to about 1.1 mm; a layer of compressive stress extending from the first surface to a depth of compression (DOC) of greater than about 0.11 t; and a Central Tension (CT) greater than or equal to 50 MPa.

Aspect (68) pertains to the packaged product of aspect (67), wherein the glass article comprises a plurality of pieces having an aspect ratio of less than or equal to about 5 after the glass article has broken according to the frangibility test, and wherein the glass article breaks into the plurality of pieces within less than or equal to 1 second as measured by the frangibility test.

Aspect (69) pertains to the packaged product of aspect (68), wherein at least 80% of the plurality of pieces have a maximum dimension of less than or equal to 2 t.

Aspect (70) pertains to the consumer electronic device of aspect (68) or aspect (69), wherein at least 50% of the plurality of fragments each comprise an aspect ratio of less than or equal to 2.

Aspect (71) pertains to the packaged product of any of aspects (68) through (70), wherein at least 50% of the plurality of pieces comprise less than or equal to about 10mm³The volume of (a).

Aspect (72) pertains to the packaged product of any of aspects (68) through (71), wherein the plurality of pieces comprises an ejected piece portion, wherein the ejected piece portion comprises 10% or less of the plurality of pieces.

Aspect (73) pertains to the packaged product of any of aspects (68) to (72), wherein the glass article comprises a first weight prior to fracture, and wherein the plurality of fragments comprises an ejected portion of fragments and a non-ejected portion of fragments, the non-ejected portion of fragments having a second weight, a difference between the first weight and the second weight being 1% of the first weight.

Aspect (74) pertains to the packaged product of any one of aspects (68) through (73), wherein the glass article has a likelihood of breaking into the plurality of pieces in less than or equal to 1 second of greater than or equal to 99%, as measured by the frangibility test.

Aspect (75) is the packaged product of any of aspects (67) to (74), wherein the glass article comprises greater than or equal to 20J/m²Stored tensile energy.

Aspect (76) pertains to the packaged product of any of aspects (67) through (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 about 0.1 to about 1.

Aspect (77) pertains to the packaged product of aspect (76), wherein the surface compressive stress is greater than or equal to 150 MPa.

Aspect (78) pertains to the packaged product of any of aspects (67) through (77), wherein the DOC comprises greater than or equal to about 0.2 t.

Aspect (79) pertains to the packaged product of any of aspects (67) through (78), wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminophosphosilicate, or an alkali aluminoborosilicate glass.

Aspect (80) pertains to the encapsulated product of any of aspects (67) to (72), wherein the glass article is disposed on the constraint layer.

Aspect (82) pertains to the packaged product of any one of aspects (67) to (80), further comprising a pharmaceutical material.

Aspect (83) pertains to the packaged product of any of aspects (67) through (81), further comprising a lid disposed in the opening.

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

Claims

1. A glass-based article, comprising:

greater than or equal to 40 mol% and less than or equal to 80 mol% SiO₂；

0 mol% or more and 5 mol% or less of Na₂O；

Less than 2 mol% K₂O；

A first surface and a second surface opposite the first surface, thereby defining a thickness (t) of the glass-based article;

li in glass-based articles₂O (mol%) and R₂O (mol%) ratio of 0.5 or more and 1.0 or less, wherein R₂O is Li in the glass-based article₂O、Na₂O and K₂The sum of O;

the stress distribution includes a surface Compressive Stress (CS) and a maximum Central Tension (CT), wherein:

maximum CT is greater than or equal to 50MPa and less than or equal to 200 MPa;

a maximum CT in the glass-based article is in a range of greater than or equal to 0.4t and less than or equal to 0.6 t;

the surface CS is greater than or equal to 200MPa and less than or equal to 500 MPa; and

depth of compression (DOC) greater than or equal to 0.14t and less than or equal to 0.25t, and

wherein the glass-based article is a glass-ceramic comprising an amorphous phase and a crystalline phase.

2. The glass-based article of claim 1, wherein the glass-based article comprises less than or equal to 1 mol% Na₂O。

3. The glass-based article of claim 1, wherein Li in the glass-based article₂O (mol%) and R₂O (mol%) ratio of 0.85 or more and less than or equal toEqual to 1.0.

4. The glass-based article of claim 1, wherein the glass-based article comprises greater than or equal to 0 mol.% and less than or equal to 5 mol.% ZrO₂。

5. The glass-based article of claim 1, wherein the glass-based article comprises greater than or equal to 67 mol.% and less than or equal to 74 mol.% SiO₂。

6. The glass-based article of any one of claims 1-5, wherein the glass-based article is strengthened to the stress profile by an ion exchange process.

7. The glass-based article of any one of claims 1-5, wherein the glass-based article comprises a maximum CT of greater than or equal to 50MPa and less than or equal to 100 MPa.

8. The glass-based article of any one of claims 1-5, wherein the glass-based article comprises a surface CS of greater than or equal to 200MPa and less than or equal to 400 MPa.

9. The glass-based article of any one of claims 1-5, wherein the glass-based article comprises a CT to CS ratio of 0.05 to 1.00.

10. The glass-based article of any one of claims 1-5, wherein the glass-based article comprises a thickness of about 1mm or less.

11. A glass-based article, comprising:

an amorphous phase and a crystalline phase;

maximum CT is greater than or equal to 50MPa and less than or equal to 200 MPa;

the depth of compression (DOC) is greater than or equal to 0.14t and less than or equal to 0.25 t.

12. The glass-based article of claim 11, wherein the glass-based article is strengthened by an ion exchange process to obtain the stress profile.

13. The glass-based article of claim 11, wherein the glass-based article comprises a maximum CT of greater than or equal to 50MPa and less than or equal to 100 MPa.

14. The glass-based article of claim 11, wherein the glass-based article comprises a surface CS greater than or equal to 200MPa and less than or equal to 400 MPa.

15. The glass-based article of claim 11, wherein the glass-based article comprises a CT to CS ratio of 0.05 to 1.00.

16. The glass-based article of claim 11, wherein the glass-based article comprises a thickness of about 1mm or less.

17. The glass-based article of any one of claims 11-16, wherein the glass-based article comprises Li in the glass-based article₂O (mol%) and R₂O (mol%) ratio of 0.5 or more and 1.0 or less, wherein R₂O is Li in the glass-based article₂O、Na₂O and K₂And the sum of O.

18. The glass-based article of any one of claims 11-16, wherein the glass-based article comprises less than or equal to 1 mol% Na₂O。

19. The glass-based article of any one of claims 11-16, wherein the glass-based article comprises less than 1 mol.% K₂O。

20. The glass-based article of any one of claims 11-16, wherein Li in the glass-based article₂O (mol%) and R₂The ratio of O (mol%) is 0.85 or more and 1.0 or less.