KR20200128761A - Glass Articles Exhibiting Improved Fracture Performance - Google Patents

Abstract

Specific examples of the present disclosure include: a first surface and a second surface opposing the first surface, defining a thickness (t) of about 1.1 mm or less; A tempered glass article comprising a compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; When the glass article is broken, the glass article is broken into a plurality of fragments having an aspect ratio of about 5 or less. In some embodiments, the glass article exhibits a coaxial flexural strength of at least about 20 kgf after being polished with 90-grit SiC particles for 5 seconds at a pressure of 25 psi. Devices comprising the glass articles described herein and methods of making the same are also disclosed.

Description

Glass Articles Exhibiting Improved Fracture Performance {Glass Articles Exhibiting Improved Fracture Performance}

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

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

Consumer electronic devices, including portable devices, such as smartphones, tablets, e-book readers, and laptops, often incorporate tempered glass products chemically for use as cover glass. Because the cover glass is directly bonded to the substrate, such as a touch-panel, display or other structure, when a tempered glass product breaks, such product is stored by the combination of surface compressive stress and tensile stress under the surface of the glass. The energy can release small debris or particles from the free surface. As used herein, the term fracture includes cracking and/or the formation of cracks. Such small debris, in particular, when fracture occurs in a delayed manner very close to the user's face (i.e. eyes and ears), and if the user continues to use and touch the fractured surface, in particular, cracks. When the distance is relatively long and debris with sharp edges and edges is present, it is thus sensitive to minor wounds or abrasions, which is a potential concern for the device user.

Thus, when the glass article breaks, glass exhibiting a deformed fragmentation behavior, e.g. to exhibit improved dicing behavior, such as a dicing effect resulting in shorter crack lengths and fewer released particles. There is a need for a product. In addition, there is also a need for a glass article that, upon breaking, releases less debris and debris with less kinetic energy and momentum.

A first aspect of the present disclosure is a first surface and a second surface opposing the first surface, defining a thickness (t) of about 1.1 mm or less, of compression exceeding about 0.11·t from the first surface. It relates to a tempered glass article comprising a compressive stress layer extending to a depth (DOC). In some embodiments, after the glass article is broken, the glass article comprises a plurality of shards, wherein at least 90% of the plurality of shards, as measured by a Fragibility Test, is about Having an aspect ratio of 5 or less, the glass article is broken into a plurality of fragments in less than 1 second.

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

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

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

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

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

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

Hereinafter, reference will be made in great detail to various embodiments, embodiments of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals will be used throughout the drawings to indicate the same or similar parts. The embodiments disclosed herein are merely representative, and each should be understood to incorporate certain advantages of the present invention. With reference to the drawings in general, it will be understood that the illustration is for the purpose of describing specific embodiments, and is not intended to limit the disclosure or the claims appended thereto. The drawings are not necessarily to scale, and certain features and perspectives of the drawings may be shown schematically or exaggerated to scale for clarity and conciseness.

In the following detailed description, the same reference numerals designate the same or corresponding parts in several of the provinces shown in the figures. In addition, unless otherwise stated, terms such as “top”, “bottom”, “outside”, “inside”, and the like are understood to be words of convenience and not to be construed as limiting terms. Additionally, when a group is described as comprising at least one of a group of elements and combinations thereof, the group includes, consists essentially of, or consists of any number of these elements recited individually or in combination with each other. , Or can be made. Similarly, when a group is described as consisting of at least one of a group of elements and combinations thereof, it is understood that the groups may consist of any number of these recited elements, individually or in combination with each other. Unless otherwise stated, when recited, ranges of values include both the upper and lower limits of the range as well as any arbitrary ranges therebetween. As used herein, “singular” and “plural” are used without particular distinction, and unless otherwise stated, both “singular” and “plural” mean “at least one” or “one or more”. It is further understood that the various features disclosed in the specification and drawings may be used in any one and all combinations.

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

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

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

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

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

In one or more embodiments, at least 50% (e.g., at least about 60%, at least about 70%, at least about 80%, or at least about 90%) of the plurality of fragments is 5·t or less, 4·t or less, Or it has a maximum dimension of 3·t or less. In some instances, at least 50% (e.g., at least about 60%, at least about 70%, at least about 80%, or at least about 90%) of the plurality of fragments comprises a maximum dimension that is less than twice the minimum dimension. In some embodiments, the maximum dimension is about 1.8 times the minimum dimension, about 1.6 times the minimum dimension, about 1.5 times the minimum dimension, about 1.4 times the minimum dimension, about 1.2 times the minimum dimension, or It is almost the same as the minimum dimension.

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

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

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

Thermal tempering is a thick glass article (i.e., about 3 millimeters or more), since a sufficient thermal gradient must be formed between the core and the surface of these articles to achieve the thermal strengthening and desired residual stresses. It is currently limited to glass articles with thickness (t ₁ )). Products of this thickness are for display (e.g., consumer electronics, including cell phones, tablets, computers, navigation systems, and the like), architectural (e.g., windows, shower panels, countertops, Etc.), for transportation (e.g., automobiles, trains, aircraft, marine vessels, etc.), household appliances, packaging materials, or any application that requires good fracture resistance but thin and light-weight products. It is not desirable or feasible in the application.

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

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

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

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

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

Fmax = 7.854*D*h

here:

Fmax = Newton's force

D = diameter of the disk

h = thickness of the optical path.

For each applied force, the stress is calculated as follows:

σ _MPa = 8F/(π*D*h)

here:

F　 = Newton's force

D = diameter of the disk

h = thickness of the optical path.

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

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

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

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

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

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

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

The ion exchange process is typically performed by immersing the glass article in a molten salt bath (or two or more molten salt baths) containing the larger ions to be exchanged for the smaller ions in the glass article. It should be noted that aqueous salt baths can also be utilized. Additionally, the composition of the bath(s) may include one or more types of larger ions (eg, Na+ and K+) or a single larger ion. Including, but not limited to, additional steps such as bath composition and temperature, immersion time, number of immersions of the glass article in the salt bath (or baths), the use of multiple salt baths, annealing, washing, and the like. The parameters for the ion exchange process are generally determined by the composition of the glass article (including the structure of the article and any crystalline phases present) and the desired DOC and CS of the glass article resulting from the strengthening operation. Will be recognized by those skilled in the art. By way of example, ion exchange of the glass article can be achieved by immersing the glass article in at least one molten bath containing salts, such as, but not limited to, nitrates, sulfates, and chlorides of larger alkali metal ions. . Typical nitrates include KNO ₃ , NaNO ₃ , LiNO ₃ , NaSO ₄ and combinations thereof. The temperature of the molten salt bath typically ranges from about 380° C. to about 450° C., while the immersion time ranges from about 15 minutes to about 100 hours depending on the glass thickness, bath temperature and glass diffusion rate. However, 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 a molten salt bath of 100% NaNO ₃ having a temperature of about 370°C to about 480°C. In some embodiments, the glass substrate may be immersed in a molten mixed salt bath comprising about 5% to about 90% KNO ₃ and about 10% to about 95% NaNO ₃ . In some embodiments, the glass substrate may be immersed in a molten mixed salt bath comprising Na ₂ SO ₄ and NaNO ₃ and may have a wider temperature range (eg, about 500° C. or less). In one or more embodiments, the glass article may be immersed in the second bath after being immersed in the first bath. The immersion in the second bath may include immersion for 15 minutes to 8 hours in a molten salt bath containing 100% KNO ₃ .

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

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

Ion exchange conditions can be adjusted to increase the slope of the stress profile at or near the surface of the resulting glass-based product or to provide a “spike”. This spike can be achieved by a single bath or multiple baths, using bath(s) with a single or mixed composition, due to the inherent properties of the glass composition used in the glass-based products described herein.

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

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

The stress profile 312 is a CS layer 315 (with 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 DOC 330 to a central portion of the product.

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

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

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

CT 320 is about 25 MPa or more, about 50 MPa or more, about 75 MPa or more, about 85 MPa or more, or about 100 MPa or more (e.g., about 150 MPa or more, about 200 MPa or more 250 MPa or more, or about 300 MPa or more. Or more). In some embodiments, the CT 320 ranges from about 50 MPa to about 400 MPa (e.g., about 75 MPa to about 400 MPa, about 100 MPa to about 400 MPa, about 150 MPa to about 400 MPa, about 50 MPa to about 350 MPa, about 50 MPa to about 300 MPa, about 50 MPa to about 250 MPa, about 50 MPa to about 200 MPa, about 100 MPa to about 400 MPa, about 100 MPa about 300 MPa, about 150 MPa to About 250 MPa). CT, as used herein, is the largest magnitude central tension in a 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 0.8 mm may have a CT of about 100 MPa or more. In one or more embodiments, a glass article having a thickness of about 0.4 mm may have a CT of at least about 130 MPa. In some embodiments, the CT can be expressed in terms of the thickness (t) of the glass article. For example, in one or more embodiments, the CT can be greater than or equal to about (100 MPa)/√(t/1 mm), where t is the thickness in mm. In some embodiments, the CT is (105 MPa)/√(t/1 mm) or more, (110 MPa)/√(t/1 mm) or more, (115 MPa)/√(t/1 mm) or more, (120 MPa)/√( t/1mm) or more or (125MPa)/√(t/1mm) or more.

CT 320 may be positioned in a range of about 0.3·t to about 0.7·t, about 0.4·t to about 0.6·t, or about 0.45·t to about 0.55·t. 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-based product. For example, a glass-based article having a thickness of about 0.8 mm may have a CT of about 75 MPa or less. If the thickness of the glass-based product decreases, the CT can increase. In other words, CT increases as the thickness decreases (or as the glass-based product becomes thinner).

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

In some embodiments, the ratio of CT 320 to surface CS ranges from about 0.05 to about 1 (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, in the range of about 0.3 to about 0.5). In known chemically strengthened glass articles, the ratio of CT 320 to surface CS is 0.1 or less. In some embodiments, the surface CS may be at least 1.5 times (or 2 times or 2.5 times) the CT. In some embodiments, the surface CS can be no more than about 20 times the CT.

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

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

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

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

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

In one or more embodiments, the glass article exhibits a maximum chemical depth of at least about 0.4·t, at least 0.5·t, at least about 0.55·t, or at least about 0.6·t. As used herein, the term "chemical depth" means the depth at which ions of a metal oxide or alkali metal oxide (e.g., metal ions or alkali metal ions) diffuse into the glass article and the concentration of the ions, EPMA ( Electron Probe Micro-Analysis), which means the depth to reach the minimum value. These ions are ions that have diffused into a chemically strengthened glass article as a result of ion exchange. The maximum chemical depth refers to the maximum diffusion depth of any ion exchanged glass article chemically strengthened by an ion exchange process. For example, in the case of a molten salt bath with one or more diffusing ionic species (i.e., a molten salt bath of NaNO ₃ and KNO ₃ ), different ionic species may be at different depths into the chemically strengthened glass article. It can spread. The maximum chemical depth is the greatest depth of diffusion of all ionic species that are ion-exchanged into the chemically strengthened glass article.

In one or more embodiments, the stress profile 312 may be described as a parabolic-shaped shape. In some embodiments, the stress profile along the depth or area of the glass-based article exhibiting tensile stress exhibits a parabolic-shaped shape. In one or more specific embodiments, the stress profile 312 is devoid of a flat stress (ie, compressive or tensile) portion or portions that exhibit a substantially constant stress (ie, compressive or tensile). In some embodiments, the CT region exhibits a stress profile that is substantially free of flat stresses or substantially constant stresses. In one or more embodiments, all of the stress profiles 312 between a thickness range of about 0·t to about 0.2·t and greater than about 0.8·t (or about 0·t to about 0.3·t and greater than 0.7·t). The point includes a tangent less than about -0.1 MPa/micrometers or greater than about 0.1 MPa/micrometers. In some embodiments, the tangent line can be less than about -0.2 MPa/micrometers or greater than about 0.2 MPa/micrometers. In some more specific embodiments, the tangent can be less than about -0.3 MPa/micrometers or greater than about 0.3 MPa/micrometers. In an even more specific embodiment, the tangent can be less than about -0.5 MPa/micrometers or greater than about 0.5 MPa/micrometers. In other words, the stress profiles of one or more embodiments according to these thickness ranges (i.e., from 0 t to about 2 t and greater than 0.8 t, or from about 0 t to 0.3 t and 0.7 t or more) are, Points with tangent lines, as described in, are excluded. While not wishing to be bound by theory, the known error function or quasi-linear stress profiles (as shown in Figure 3, representing a flat or zero slope stress profile, depending on the thickness range, 220) about -0.1 MPa/micrometers to about 0.1 MPa/micrometers, about -0.2 MPa/micrometers to about 0.2 MPa/micrometers, about -0.3 MPa/micrometers to about 0.3 MPa/micrometers, or about -0.5 MPa/micrometers to about In these thickness ranges (i.e., from about 0 t to about 0.2 t and greater than 0.8 t, or from about 0 t to about 0.3 t and 0.7 t or more), having a tangent line in the range of 0.5 MPa/micrometers. Has a point along the way. The glass-based articles of one or more embodiments of the present disclosure do not exhibit stress profiles with flat or zero slope stress profiles along these thickness ranges, as shown in FIG. 4.

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

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

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

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

[Equation 1]

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

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

In one or more embodiments, the CTn can be less than MaxT if there is a compressive stress spike on one or both of the major surfaces of the glass-based article. In one or more embodiments, CTn is equal to MaxT if there are no compressive stress spikes on one or both of the major surfaces of the glass-based article.

In some embodiments, the stress profile can be altered by heat treatment. In this embodiment, the heat treatment can occur before any ion-exchange process, between ion-exchange processes, or after all ion-exchange processes. In some embodiments, heat treatment can result in a reduction in the slope of the stress profile at or near the surface. In some embodiments, if a steeper or greater slope is desired at the surface, an ion-exchange process after heat treatment can be utilized to provide a “spike” or to increase the slope of the stress profile at or near the surface.

In one or more embodiments, the stress profile 312 (and/or the estimated stress profile 340) is caused by a non-zero concentration of metal oxide(s) that varies along a portion of the thickness. The change in concentration can 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 of about 0·t to about 0.3·t. In some embodiments, the concentration of the metal oxide is non-zero, and from about 0·t to about 0.35·t, about 0·t to about 0.4·t, about 0·t to about 0.45·t, or about 0·t to It varies along the thickness range of about 0.48·t. Metal oxides can be described as creating stresses in glass-based products. The change in concentration can be continuous along the above-mentioned thickness range. The change in concentration may include a change in metal oxide concentration of about 0.2 mol% along a segment of thickness of about 100 micrometers. This change can be measured by a method known in the art, including a microprobe, as shown in Example 1. Metal oxides whose concentration is not zero and varies along part of the thickness can be described as generating stress in the glass-based product.

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

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

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

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

In one or more embodiments, the glass-based product comprises a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is about 0 along a first thickness range of about 0 tons to about 0.5 tons. mol% to about 15 mol%, and the second metal oxide concentration is from about 0 mol% to about 10 mol% from the second thickness range of about 0 micrometers to about 25 micrometers (or about 0 micrometers to about 12 micrometers). Range; However, the concentration of one or both of the first metal oxide and the second metal oxide is not zero along the entire thickness or substantial portion of the glass-based product. The glass-based product may include an optional third metal oxide concentration. The first metal oxide includes Na ₂ O, but the second metal oxide may include K ₂ O.

The concentration of the metal oxide can be determined from the reference amount of the metal oxide in the glass-based product prior to being changed to include the concentration gradient of this metal oxide.

In some embodiments, the stress profile can be modified by heat treatment. In this embodiment, the heat treatment may occur before any ion exchange process, between ion-exchange processes, or after all ion-exchange processes. In some embodiments, heat treatment can result in a reduction in the slope of the stress profile at or near the surface. In some embodiments, if a steeper or greater slope is desired at the surface, an ion-exchange process after heat treatment can be utilized to provide a “spike” or to increase the slope of the stress profile at or near the surface. .

In one or more embodiments, the stress profile 312 is generated due to a non-zero concentration of metal oxide(s) that varies along a portion of the thickness. The change in concentration can be referred to here as a gradient. In some embodiments, the concentration of the metal oxide is non-zero and varies along a thickness range of about 0·t to about 0.3·t. In some embodiments, the concentration of the metal oxide is non-zero, and from about 0·t to about 0.35·t, about 0·t to about 0.4·t, about 0·t to about 0.45·t, or about 0·t to It varies with the thickness range of about 0.48·t. Metal oxides can be described as creating stresses in glass-based products. The change in concentration can be continuous along the above-mentioned thickness range. The change in concentration may include a change in metal oxide concentration of about 0.2 mol% along a segment of thickness of about 100 micrometers. This change can be measured by a method known in the art, including a microprobe, as shown in Example 1. Metal oxides that are not zero in concentration and vary along part of the thickness can be described as generating stress in the glass-based product.

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

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

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

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

In one or more embodiments, the glass-based product comprises a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is about 0 mol, depending on the first thickness range of about 0 t to about 0.5 t. % To about 15 mol%, and the second metal oxide concentration ranges from about 0 mol% to about 10 mol% from the second thickness range of about 0 micrometers to about 25 micrometers (or about 0 micrometers to about 12 micrometers). as; However, the concentration of one or both of the first metal oxide and the second metal oxide is not zero depending on the total thickness or a substantial portion of the glass-based product. The glass-based product may include an optional third metal oxide concentration. The first metal oxide may include Na ₂ O, while the second metal oxide may include K ₂ O.

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

The glass articles described herein may exhibit a stored tensile energy in the range of 15 J/m 2 or more (eg, about 15 J/m 2 to about 50 J/m 2 ). For example, in some embodiments, the stored tensile energy can range from about 20 J/m 2 to about 150 J/m 2. In some instances, the stored tensile energy is about 25 J/m 2 to about 150 J/m 2, about 30 J/m 2 to about 150 J/m 2, about 35 J/m 2 to about 150 J/m 2, about 40 J/m 2 To about 150 J/m2, about 45 J/m2 to about 150 J/m2, about 50 J/m2 to about 150 J/m2, about 55 J/m2 to about 150 J/m2, about 60 J/m2 to about 150 J/m2, about 65 J/m2 to about 150 J/m2, about 25 J/m2 to about 140 J/m2, about 25 J/m2 to about 130 J/m2, about 25 J/m2 to about 120 J /M2, about 25 J/m2 to about 110 J/m2, about 30 J/m2 to about 140 J/m2, about 35 J/m2 to about 130 J/m2, about 40 J/m2 to about 120 J/m2 , Or from about 40 J/m2 to about 100 J/m2. Thermally and chemically strengthened glass-based products of one or more embodiments are stored at least about 40 J/m2, at least about 45 J/m2, at least about 50 J/m2, about 60 J/m2, or at least about 70 J/m2. It can represent tensile energy.

The stored tensile energy is calculated using Equation 2:

[Equation 2]

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

Where v is the Poisson's ratio, E is the Young's modulus, and the integral is calculated only for the tensile region. Equation 2, Suresh T. Gulati, Frangibility of Tempered Soda-Lime Glass Sheet, GLASS PROCESSING DAYS, The Fifth International Conference on Architectural and Automotive Glass, 13-15 Sept. In 1997, it is described as Equation No. 4.

The glass articles of some embodiments exhibit superior mechanical performance, as demonstrated by device drop tests or component level testing, compared to known tempered glass articles. In one or more embodiments, the glass article exhibits improved surface strength when subjected to a worn ring-on-ring (AROR) test. The strength of a material is defined as the stress at which fracture occurs. The AROR test is a measurement of surface strength for testing a flat glass specimen, and ASTM C1499-09 (2013), named "Standard Test Method for Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperature", is a ring described herein. Serves as the basis for the on-ring worn ROR test methodology. The content of ASTM C1499-09 is incorporated herein by reference in its entirety. In one embodiment, the glass specimen is in Annex A2 of ASTM C158-02 (2012), entitled "Standard Test Methods for Strength of Glass by Flexure (Determination of Modulus of Rupture)", without "abrasion Procedures" 90 grit silicon carbide (SiC) particles transferred to a glass sample using the method and apparatus described as are abraded prior to the ring-on-ring test. The content of ASTM C158-02 and, in particular, Annex 2, is incorporated herein by reference in its entirety.

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

During the ring-on-ring test, the glass article with at least one worn surface 112 as shown in FIG. 5, as also shown in FIG. 5, was subjected to a coaxial flexural strength or failure load (i.e. It is placed between two concentric rings of different sizes to determine the maximum stress that can be sustained, if applied to bending between the two concentric rings. In the worn ring-on-ring structure 100, the worn glass article 110 is supported by a support ring 120 having a diameter D2. The force F is applied by a load cell (not shown) to the surface of the glass article by means of a loading ring 130 having a diameter D1.

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

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

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

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

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

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

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

In one or more embodiments, the glass article herein is, if the glass article is directly bonded to the substrate (i.e., the display unit), after the glass article is broken, at least 50% of the cracks are sub-surface cracks, wherein the crack is It exhibits the breaking behavior so that it extends only partially through the thickness and is impeded below the surface). For example, in some cases, the crack may extend partially through the thickness (t) of the glass article, for example 0.05t to 0.95t. The percentage of cracks in the glass article extending only partially through the thickness t may be at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

In some embodiments, the reinforced glass-based products described herein can be demonstrated in terms of performance in an inverse ball on sandpaper (IBoS) test. The IBoS test, as schematically shown in FIG. 6, is a dynamic component level test that mimics the main mechanism for damage due to bending plus damage introduction commonly occurring in glass-based products used in mobile or portable electronic devices. In the field, the introduction of damage (Fig. 7a) occurs at the top surface of the glass-based product. Fracture begins at the upper surface of the glass-based product and damage penetrates the glass-based product (Fig. 7b) or the fracture is from bending of the upper surface of the glass-based product or from the inner part of the glass-based product ( It propagates from c) in FIG. 7. The IBoS test is designed to simultaneously introduce damage to the glass surface and to apply bending under dynamic loads. In some instances, the glass-based product exhibits improved drop performance when it contains compressive stress, than when the same glass-based product does not contain compressive stress.

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

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

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

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

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

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

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

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

When applied to the inverse ball (IBoS) test on sandpaper described above, the embodiment of the glass-based product described herein has a survival rate of at least about 60% when the ball falls on a glass surface from a height of 100 cm. . For example, a glass-based product may contain five identical (or approximately identical) samples (i.e., approximately the same composition, as described herein, and approximately equal compressive stress and depth of compression or compressive stress layer, if strengthened). 3 of) are described as having a 60% survival rate upon dropping from a given height if they survive the IBoS drop test without breakage if they fall from the stated height (here 100 cm). In other embodiments, the survival rate in a 100 cm IBoS test of the tempered glass-based product is at least 70%, in other embodiments at least about 80%, and in other embodiments at least about 90%. In another embodiment, the viability of a tempered glass-based product dropped from a height of 100 cm in the IBoS test is at least about 60%, in another embodiment at least about 70%, in another embodiment at least about 80%. , And in other embodiments, at least about 90%. In one or more embodiments, the viability of a tempered glass-based product dropped from a height of 150 cm in an IBoS test is at least about 60%, in another embodiment, at least about 70%, in another embodiment, at least about 80%, And in other embodiments, at least about 90%.

In order to determine the survival rate of the glass-based product when dropped from a predetermined height using the IBoS test method and apparatus described above, although a larger number (e.g., 10, 20, 30, etc.) of samples At least five identical (or approximately identical) (i.e. approximately identical compositions) of glass-based products, and, if strengthened, approximately equal compressive stresses and compressive or layers, although they may be applied to the test to increase the confidence level of the test results. (With a depth of) the sample is tested. Each sample is dropped once at a predetermined height (e.g., 100 cm or 150 cm) or, optionally, gradually falling from a higher height until a predetermined height is reached without breaking, and Evidence (crack formation and propagation across the entire thickness and/or entire surface of the sample) is examined visually (ie, visually). The sample is considered "survival" in the drop test if there is no observed fracture after falling from a predetermined height, and "broken" (or "survival" if a fracture is observed if the sample is dropped from a height below the predetermined height. Is considered to be "). The survival rate is determined as the percentage of the sample population that survived the drop test. For example, if 7 samples out of 10 groups were dropped from a predetermined height and not broken, the viability of the glass would be 70%.

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

In one or more embodiments, upon fracture, the glass article emits less and less debris, which is a potential concern to the user than is exhibited by known glass articles currently used in portable electronic devices. As used herein, the term "released" or "released" refers to fragments that move from their original position or placement in the glass article after it is broken. In some embodiments, after the glass article is broken and a plurality of fragments is formed, no more than about 10% (eg, no more than about 8%, no more than about 6%, or no more than about 5%) of the plurality of fragments is released. In some embodiments, after the glass article is broken and the plurality of fragments is formed, at least about 50% of the ejected portion of the plurality of fragments has a greatest dimension of less than 0.5 mm. In some embodiments, the number or amount of debris released can be characterized by weight, relative to the glass article before and after fracture. For example, the difference between the weight of the glass article before rupture (including the total weight of the released portion of the plurality of fragments and the non-released portion of the fragments) and the weight of the non-released portion of the fragments is , It may be about 1% or less of the weight before impact. In some instances, the difference between the weight of the glass article before fracture and the weight of the non-emitted portion of the debris (including, after fracture, the total weight of the released portion of the plurality of debris and the non-emitted portion of the debris) is , Less than about 0.0005 g (eg, 0.0004 g or less, 0.0003 g or less, 0.0002 g or less, or 0.0001 g or less).

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

In one or more embodiments, the glass article (directly bonded to the substrate, ie the display unit) exhibits a haze after breaking due to the high density breaking pattern. Readability depends on the viewing angle and thickness of the glass-based product. At a viewing angle of 90 degrees to the major surface of the glass article, or at normal incidence, the broken glass article exhibits a low haze so that the underlying image or text is visible to the naked eye. At a viewing angle of 70 degrees or less (or at least 30 degrees away from normal incidence) with respect to the major surface of the glass article, the broken glass article exhibits a haze that prevents the underlying image or text from being visible to the naked eye. It should be understood that such haze is present if the fragments of the glass article are still gathered together or if less than 10% of the fragments are released from the glass article. While not wishing to be bound by theory, it is believed that after rupture a glass article can provide privacy screen functionality due to 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 when the user uses or touches the glass article even after the glass article is broken, whereby cuts and abrasions to the user are minimized or reduced.

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

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

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

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

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

In one or more embodiments, the glass article may comprise a stress profile including spikes, as described herein, such that the surface CS ranges from about 400 MPa to about 1200 MPa, and (as shown in FIG. Likewise) a sealing material 20 on one major surface 14, and a second sealing material 22 on two minor surfaces 16, 18. In one or more embodiments, the glass article may comprise a spike-free stress profile, such that the surface CS ranges from about 150 MPa to about 500 MPa, and on the major surface 14 (as shown in FIG. 9A ). Contains only 20 sealing materials. The glass products described herein can be incorporated into a variety of products and products, such as consumer electronic products or devices (eg, cover glass for portable electronic devices and touch-enabled displays). The glass article can also be used as a display (or display article) (e.g., billboards, point of sale systems, computers, navigation systems, and the like), architectural products (walls, fixtures, panels, windows, etc.) , Transportation products (e.g. automotive applications, trains, aircraft, marine vessels, etc.), household appliances (e.g. washing machines, dryers, dishwashers, refrigerators and the like), packaging (e.g. For example, it can be used for pharmaceutical packaging or containers) or any product that requires some resistance to breakage.

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

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

In one or more embodiments, the glass articles described herein can be used for packaging. For example, the packaging may include a glass article in the form of bottles, vials or containers containing liquid, solid or gaseous substances. In one or more embodiments, the glass article is a vial containing a chemical, such as a pharmaceutical substance. In one or more embodiments, the packaging includes a housing comprising an opening, an outer surface, and an inner surface defining an enclosure. The housing can be formed from the glass articles described herein. The glass article contains a sealing layer. In some embodiments, the enclosure is filled with a chemical or pharmaceutical substance. In one or more embodiments, the opening of the housing may be closed or sealed by a cap. In other words, the cap can be placed in the opening to close or seal the enclosure.

The glass article may comprise an amorphous substrate, a crystalline substrate, or a combination thereof (eg, a glass-ceramic substrate). The glass article may include 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) comprises SiO ₂ in the range of about 40 to about 80, Al ₂ O ₃ in the range of about 10 to about 30, about 0 A glass having a composition comprising B ₂ O ₃ in the range of about 10 to B ₂ O ₃ , R ₂ O in the range of about 0 to about 20, and RO in the range of about 0 to about 15, in mole percent. Can include. In some instances, the composition may comprise one or both of ZrO ₂ in the range of about 0 mol% to about 5 mol% and P ₂ O ₅ in the range of about 0 mol% to about 15 mol %. TiO ₂ may be present in about 0 mol% to about 2 mol%.

In some embodiments, the glass composition contains SiO ₂ in mol %, 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 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 65.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Other representative compositions of glass articles prior to being chemically strengthened, as described herein, are shown in Table 1.

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

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

[Table 1A]

Typical composition before chemical strengthening.

[Table 1B]

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

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

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

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

The glass article can be characterized by the way it is formed. For example, the glass article is float-formable (i.e. formed by a float process), down-drawable, and in particular, fusion-formable or slot-drawable (i.e., fusion draw process or slot draw process and Molded by the same down drawing process).

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

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

The fusion drawing process uses, for example, a drawing tank having a channel for receiving a molten glass raw material. The channel has weirs with openings at the top along the length of the channel on both sides of the channel. When the channels are filled with molten material, molten glass overflows the weir. Due to gravity, the molten glass flows down the outer surface of the drawing tank as two flowing glass films. These outer surfaces of the drawing tank extend below and inward so that they engage at the edge below the drawing tank. The two flowing glass films join at this edge to fuse and form a single flowing glass article. The fusion drawing method offers the advantage that no part of the outer surface of the resulting glass article comes into contact with any part of the device, since the two glass films overflowing the channel fuse together. Therefore, the surface properties of the fusion drawn glass article are not affected by such contact. When the glass article is a glass ceramic, the glass article formed from the fusion process may be subjected to a ceramization process in which one or more crystalline phases are generated.

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

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

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

The glass article can be acid polished or separately treated to eliminate or reduce the effect of surface flaws.

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

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

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

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

Example

Various embodiments will become more apparent by the following examples.

Example 1

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

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

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

Example 2

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

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

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

Comparative Example 2D (measured with Roussev I with IWKB analysis) is ion exchanged to show an error function stress profile with a DOC in excess of 75 micrometers. The resulting glass article is then remounted to the same mobile device housing and subjected to a drop test as described above on 30 grit sandpaper. 12 shows the maximum breakage height for the embodiment. As shown in Fig. 12, Examples 2A-2C exhibit significantly larger maximum break heights (i.e., 212 cm, 220 cm and 220 cm, respectively) and dicing behavior. Comparative Example 2F, having the same composition, does not exhibit the same dicing behavior, and a lower maximum break height, compared to Examples 2A-2C.

Example 3

The 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 substrate used in Examples 3A-3D has the same composition as in Example 1, and the substrate used in Comparative Example 3L-3X is 69 mol% SiO ₂ , 10.3 mol% Al ₂ O ₃ , 15.2 mol% Na ₂ O, 5.4 mol% MgO, and 0.2 mol% SnO ₂ .

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

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

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

*DNB = not broken

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

*DNB = Not fractured As shown in Table 4-5, compared to a glass product chemically strengthened under the dicing/fragmentation conditions of the height that occurs at the time of fracture (i.e., Examples 3A-3K), the limit of fragility limit) chemically strengthened glass articles (i.e. Comparative Examples 3L-3X) are much more likely to experience delayed failure. Specifically, more than 80% of Comparative Examples 3L-3X were damaged in a delayed manner, whereas in Table 4 the samples were immediately broken or not broken. In addition, Comparative Examples 3L-3X exhibited fewer, larger, more debris debris than Examples 3A-4K, which were broken with high dicing and exhibited debris with a low aspect ratio.

Example 4

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

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

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

14 is a view of Example 4G formed by providing the same substrate as Examples 4A and 4B and immersing in a molten salt bath of 70% KNO ₃ and 30% KNO ₃ having a temperature of 460° C. for 12 hours. , As measured by Roussev I to which IWKB analysis was applied, and shows the stress profile.

Example 5

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

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

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

Comparative Examples 5C and 5D were not constrained by the adhesive and were broken. The resulting broken glass article is evaluated. 15C and 15D show fracture images of Comparative Example 5C and Example 5D, respectively. As shown in Fig. 15C, Comparative Example 5C shows a larger fragment. As shown in Fig. 15D, Example 5D results in fragments representing dicing. It is believed that the sub-fragments (not shown) do not extend through the thickness of the glass article.

Example 6

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

Example 7

The glass articles according to Examples 7A-7C were made by providing a glass substrate having a 2.5-dimensional shape but each having a different thickness (i.e. Example 7A had a thickness of 1 mm, Example 7B had a thickness of 0.8 mm. Thickness, and Example 7C had a thickness of 0.5 mm). The 2.5-dimensional shape includes a flat major surface and an opposite curved major surface. The composition of the glass substrate was the same as in Examples 2A-2C. The storage tensile energy of each substrate is calculated as a function of ion exchange time using a molten bath having a temperature of 430°C. The stored tensile energy is calculated using the total positive stress across the CT area (327 in Figure 4) as measured by SCALP. The calculated stored tensile energy is plotted as a function of ion exchange time in FIG. 17. For illustrative purposes, the dotted line at a stored tensile energy value of 10 J/m2 is drawn to indicate an approximate threshold for fragility. The highlighted area represents the ion-exchange conditions for a single portion with a thickness range of 0.5-1.0 mm representing the behavior described here. Specifically, this range allows for optimal mechanical performance and a similar degree of dicing across the region of the part if the part is broken.

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

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

Example 8

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

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

The viewpoint (2) of the present disclosure is the tempered glass product of the viewpoint (1), which is measured by a fragility test, and is broken into a plurality of fragments in one second or less.

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

The viewpoint (4) of the present disclosure is the tempered glass product in any one of the viewpoints (1) to (3), and at least 50% of the plurality of fragments contains an aspect ratio of 2 or less.

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

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

Aspect (7) of the present disclosure is a tempered glass article according to any one of aspects (1) to (6), wherein the glass article contains a first weight before rupture, and wherein the plurality of fragments is a fragment And a non-released portion of the fragment, wherein the non-released portion of the fragment has a second weight, and the difference between the first weight and the second weight is 1 of the first weight. %to be.

The viewpoint (8) of the present disclosure is measured by the fragility test in the tempered glass product of any one of the viewpoints (1) to (7), and the probability that the glass product is broken into a plurality of fragments in less than 1 second is It is more than 99%.

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

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

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

Aspect (12) of the present disclosure is the tempered glass product in any one of viewpoints (10) to (11), and the central tension is 50 MPa or more.

Aspect (13) of the present disclosure is the tempered glass product of any one of viewpoints (10) to (12), and the surface compressive stress is 150 MPa or more.

Aspect (14) of the present disclosure is the tempered glass product of any one of viewpoints (10) to (13), and the surface compressive stress is 400 MPa or more.

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

The viewpoint (16) of the present disclosure is the tempered glass product of any one of viewpoints (1) to (15), wherein the glass product is an alkali aluminosilicate glass, an alkali-containing borosilicate glass, and an alkali aluminophosphosilicate glass. Or alkali aluminoborosilicate glass.

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

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

Aspect (19) of the present disclosure, in the tempered glass article of aspect (18), the glass article comprises a stored tensile energy of 20 J/m2 or more.

Aspect (20) of the present disclosure is, in the tempered glass article of either aspect (18) or aspect (19), wherein the glass article includes a surface compressive stress and a central tension, wherein the center of the surface compressive stress The ratio of tension is in the range of about 0.1 to about 1.

In the aspect (21) of the present disclosure, in the tempered glass product of the aspect (20), the central tension (CT) is 50 MPa or more.

In the aspect (22) of the present disclosure, in the tempered glass product of the aspect (20) or the aspect (21), the surface compressive stress is 150 MPa or more.

Aspect (23) of the present disclosure is the tempered glass product in any one of viewpoints (20) to (22), and the surface compressive stress is 400 MPa or more.

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

The viewpoint (25) is the tempered glass product of any one of viewpoints (18) to (24), wherein the glass product is an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali alumina. And noborosilicate glass.

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

The viewpoint 27 of the present disclosure is a tempered glass substrate; Sealing layer; And a support, wherein the tempered glass substrate comprises a first surface defining a thickness t of about 1.1 mm or less, and a second surface opposite the first surface, the first surface A compressive stress layer extending from a depth of compression (DOC) of greater than about 0.11 t, and a central tension (CT) of 50 MPa or more, wherein the device comprises a tablet, a transparent display, a mobile phone, a video player, an Terminal devices, e-readers, laptop computers, or non-transparent displays.

Perspective 28, in the device of aspect 27, after the glass article has been broken according to the fragility test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less.

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

Perspective (30), in the device of aspect (28) or aspect (29), at least 80% of the plurality of fragments have a maximum dimension of 5·t or less.

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

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

Perspective (33) is, in the device of any one of perspectives (28) to (32), wherein the plurality of fragments comprises an ejected portion of the fragment, wherein the ejected portion of the fragment comprises the plurality of Contains less than 10% of debris.

Perspective 34 is the device of any one of aspects 28 to 33, wherein the glass article comprises a first weight before rupture, and wherein the plurality of fragments comprises the ejected portion of the fragment and A non-released portion of the fragment, wherein the non-released portion of the fragment has a second weight, and the difference between the first weight and the second weight is 1% of the first weight.

Perspective (35) is measured by a vulnerability test in any one of perspectives (28) to (34), and the probability of breaking the glass article into a plurality of fragments in less than 1 second is 99% or more. .

Aspect 36, in the device of any one of aspects 28 to 35, wherein the glass article comprises a stored tensile energy of 20 J/m2 or more.

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

Aspect (38), in the device of aspect (37), the surface compressive stress is 150 MPa or more.

Aspect 39, in the device of any one of aspects 27 to 38, the DOC comprises at least about 0.2 t.

Aspect (40) is the device in any one of aspects (27) to (39), wherein the glass product is an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminophosphosilicate glass, or an alkali aluminoboro. Includes silicate glass.

The viewpoint 41 is the apparatus in any one of viewpoints 27 to 40, wherein the glass article is disposed on the sealing layer.

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

The viewpoint 43 is the tempered glass product of the viewpoint 42, as measured by the fragility test, and the glass product is broken into a plurality of fragments in 1 second or less.

Perspective 44 is the tempered glass article of aspect 42 or aspect 43, wherein the glass article contains a stored tensile energy of 20 J/m2 or more.

Perspective 45 is the tempered glass article of any one of aspects 44 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 in the range of about 0.1 to about 1.

The viewpoint 46 is the tempered glass product of the viewpoint 45, wherein the central tension is 50 MPa or more.

The viewpoint 47 is the tempered glass product of the viewpoint 45 or the viewpoint 46, wherein the surface compressive stress is 150 MPa or more.

Perspective (48) is the tempered glass product of any one of the aspects (42) to (47), and the DOC contains about 0.2t or more.

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

The viewpoint 50 is the tempered glass article of any one of the viewpoints 42 to 49, wherein the glass article is disposed on the sealing layer. Perspective 51 includes a housing having a front surface; An electrical component provided at least partially inside the housing and including at least a controller, a memory, and a display; And a cover glass disposed on the front side of the housing and over the display and comprising a tempered glass article, wherein the tempered glass article: defines a thickness (t) of about 1.1 mm or less, A first surface and a second surface opposing the first surface; A compressive stress layer extending from the first surface to a depth of compression (DOC) greater than about 0.11·t; And a central tension (CT) of about 50 MPa or more.

Perspective 52, in the consumer electronic device of aspect 51, after the glass article has been broken according to the fragility test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less.

Perspective 53 is, in the consumer electronic device of aspect 52, that the glass article is measured by a fragility test, and is broken into a plurality of fragments in one second or less.

Perspective 54, in the consumer electronic device of perspective 52 or 53, at least 80% of the plurality of fragments has a maximum dimension of 2·t or less.

Perspective 55 is, in the consumer electronic device of any one of perspectives 52 to 54, at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less.

Perspective 56 is, in the consumer electronic device of any one of aspects 52 to 55, wherein at least 50% of the plurality of fragments comprise a volume of about 10 mm 3 or less.

Perspective 57 is, in the consumer electronic device of any one of perspectives 52 to 56, wherein the plurality of fragments includes an ejected portion of the fragment, wherein the ejected portion of the fragment comprises: Contains less than 10% of multiple fragments.

Perspective 58 is the consumer electronic device of any one of aspects 52 to 57, wherein the glass article comprises a first weight before rupture, and wherein the plurality of fragments is the release of fragments And a non-released portion of the fragment, wherein the non-released portion of the fragment has a second weight, and a difference between the first weight and the second weight is 1 of the first weight. %to be.

The viewpoint 59 is measured by a vulnerability test in the consumer electronic device of any one of the viewpoints 53 to 58, and the probability that the glass product is broken into a plurality of fragments in less than 1 second is 99 % Or more.

Aspect 60 is the consumer electronic device of any one of aspects 51 to 59, wherein the glass article contains a stored tensile energy of 20 J/m 2 or more.

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

In the viewpoint 62, in the consumer electronic device of the viewpoint 61, the surface compressive stress is 150 or more.

Aspect 63, in the consumer electronic device of any one of aspects 51 to 62, wherein the DOC comprises at least about 0.2t.

Aspect (64) is a consumer electronic device according to any one of aspects (51) to (63), wherein the glass product is an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminophosphosilicate or an alkali aluminovo. Includes rosilicate glass.

Perspective 65 is the consumer electronic device of any one of aspects 51 to 64, wherein the glass article is disposed on the sealing layer.

Perspective 66 is the consumer electronic device of any one of viewpoints 51 to 65, wherein the consumer electronic product is a tablet, a transparent display, a mobile phone, a video player, an information terminal device, an electronic-reader, and a laptop computer. , Or a non-transparent display.

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

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

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

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

Perspective 71, in the packaging product of any one of aspects 68 to 70, wherein at least 50% of the plurality of fragments comprises a volume of about 10 mm 3 or less.

Perspective 72 is, in the packaging product of any one of perspectives 68 to 71, wherein the plurality of fragments includes an ejected portion of the fragment, wherein the ejected portion of the fragment comprises the plurality of Contains less than 10% of its fragments.

Perspective 73 is the packaging article of any one of aspects 68 to 72, wherein the glass article comprises a first weight before fracture, and wherein the plurality of fragments is A portion and a non-released portion of the fragment, wherein the non-released portion of the fragment has a second weight, and the difference between the first weight and the second weight is 1% of the first weight to be.

Perspective 74 is measured by a vulnerability test in any one of the packaging products 68 to 73, and the probability that the glass product is broken into a plurality of fragments in less than 1 second is 99%. That's it.

Perspective 75 is the packaging article of any one of aspects 67 to 74, wherein the glass article comprises a stored tensile energy of 20 J/m 2 or more.

Perspective 76 is, in the packaging article of any one of aspects 67 to 75, wherein the glass article comprises a surface compressive stress and a central tension, wherein the ratio of the central tension to the surface compressive stress is: Ranges from about 0.1 to about 1.

Aspect 77, in the packaging product of aspect 76, said surface compressive stress is 150 or more.

Aspect 78, in the packaging product of any one of aspects 67 to 77, wherein the DOC comprises at least about 0.2 t.

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

The viewpoint 80 is the packaging product in any one of viewpoints 67 to 72, wherein the glass product is disposed on the sealing layer.

Aspect 82 further includes a pharmaceutical substance in the packaging product of any one of aspects 67 to 80.

Perspective 83 further includes, in the packaging product of any one of aspects 67 to 81, a cap disposed in the opening.

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

Claims (20)

As a glass-based product,
40 mol% or more and 80 mol% or less of SiO ₂ ;
From 0 mol% to 5 mol% of Na ₂ O;
Less than 2 mol% K ₂ O;
A first surface and a second surface opposing the first surface defining a thickness (t) of the glass-based article;
Glass-based products in the ratio of the R ₂ O Li ₂ O (mol%) of the (mol%) is less than to 1.0 than 0.5, in which R ₂ O is a glass-in Li ₂ O-based product, Na ₂ O, and Is the sum of K ₂ O;
The stress profile includes surface compressive stress (CS) and maximum central tension (CT), wherein:
The maximum CT is 50 MPa or more and 200 MPa or less;
The maximum CT is located within a glass-based product ranging from 0.4·t to 0.6·t;
Surface CS is 200 MPa or more and 500 MPa or less; And
The depth of compression (DOC) is 0.14·t or more and 0.25·t or less, and
Wherein the glass-based product is a glass-ceramic comprising a crystalline phase and an amorphous phase. The method according to claim 1,
The glass-based product, wherein the glass-based product comprises up to 1 mol% Na ₂ O. The method according to claim 1,
Glass-based products in the R ₂ O ratio of Li ₂ O (mol%) of the (mol%) is 0.85 or more to 1.0 or less, a glass-based products. The method according to claim 1,
The glass-based article comprising at least 0 mol% and up to 5 mol% ZrO ₂ . The method according to claim 1,
The glass-based article comprising at least 67 mol% and up to 74 mol% SiO ₂ . The method according to any one of claims 1-5,
The glass-based article is strengthened by an ion exchange process resulting in a stress profile. The method according to any one of claims 1-5,
The glass-based product comprising a maximum CT of 50 MPa or more and 100 MPa or less. The method according to any one of claims 1-5,
The glass-based product comprising a surface CS of 200 MPa or more and 400 MPa or less. The method according to any one of claims 1-5,
The glass-based product comprising a ratio of CT to CS in the range of 0.05 to 1.00. The method according to any one of claims 1-5,
The glass-based article comprising a thickness of about 1 mm or less. As a glass-based product,
Amorphous phase and crystalline phase;
A first surface and a second surface opposing the first surface defining a thickness (t) of the glass-based article;
A stress profile including surface compressive stress (CS) and maximum central tension (CT), wherein:
The maximum CT is 50 MPa or more and 200 MPa or less;
The maximum CT is located within a glass-based product ranging from 0.4·t to 0.6·t;
Surface CS is 200 MPa or more and 500 MPa or less; And
Glass-based products with a depth of compression (DOC) of 0.14·t or more and 0.25·t or less. The method of claim 11,
The glass-based article is strengthened by an ion exchange process resulting in a stress profile. The method of claim 11,
The glass-based product comprising a maximum CT of 50 MPa or more and 100 MPa or less. The method of claim 11,
The glass-based product comprising a surface CS of 200 MPa or more and 400 MPa or less. The method of claim 11,
The glass-based product comprising a ratio of CT to CS in the range of 0.05 to 1.00. The method of claim 11,
The glass-based article comprising a thickness of about 1 mm or less. The method of any one of claims 11-16,
The glass-based product comprises a ratio of Li ₂ O (mol%) to R ₂ O (mol%) in the glass-based product of 0.5 to 1.0, wherein R ₂ O is Li ₂ in the glass-based product A glass-based product, which is the sum of O, Na ₂ O, and K ₂ O. The method of any one of claims 11-16,
The glass-based product is
A glass-based product comprising up to 1 mol% Na ₂ O. The method of any one of claims 11-16,
The glass-based product, wherein the glass-based product comprises less than 1 mol% K ₂ O. The method of any one of claims 11-16,
The glass-based products in the ratio of the R ₂ O Li ₂ O (mol%) of the (mol%) is 0.85 or more to 1.0 or less, a glass-based products.

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