KR20180035836A - Glass products with improved breaking performance - Google Patents

Abstract

Embodiments 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; And a compressive stress layer extending from the first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; When the glass product is broken, the glass product is broken by a plurality of pieces having an aspect ratio of about 5 or less. In some embodiments, the glass article exhibits axial flexural strength of about 20 kgf or more after polishing to 90-grit SiC particles for 5 seconds at a pressure of 25 psi. Devices comprising the glass articles described herein and methods of making them are also disclosed.

Description

Glass products with improved breaking performance

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

This disclosure relates to glass articles exhibiting improved fracture performance and, more particularly, to glass articles exhibiting improved rupture pattern and dicing behavior.

Consumer electronic devices, including portable devices, such as smart phones, tablets, e-book readers and laptops, often incorporate chemically tempered glass products for use as cover glasses. Since the cover glass is directly bonded to the substrate, such as a touch-panel, display or other structure, when the tempered glass product is broken, such product is stored and stored by a combination of surface compressive stress and tensile stress beneath the surface of the glass Energy can release small debris or particles from the free surface. As used herein, the term fracture includes the formation of cracks and / or cracks. These small fragments are particularly important when breaks occur in a very delayed manner very close to the user's face (i.e., the eyes and ears), and when the user continues to use and touch the fractured surface, When the distance is relatively long and there are debris with sharp edges and edges, it is therefore susceptible to minor scratches or abrasions, which is a potential concern to the device user.

Thus, glass that exhibits a modified fragmentation behavior, such as an improved dicing behavior, such as a dicing effect that produces short crack lengths and less emissive particles when the glass product is broken, There is a need for products. In addition, there is also a need for a glass product that, upon fracture, emits debris with less debris and less kinetic energy and momentum.

A first aspect of the present disclosure is directed to a method of forming a surface having a first surface and a second surface opposing the first surface defining a thickness t of about 1.1 mm or less, To a tempered glass product comprising a compressive stress layer extending in depth (DOC). In some embodiments, after the glass product is broken, the glass product comprises a plurality of fragments, wherein at least 90% of the plurality of fragments are measured by a Frangibility Test, The glass product has an aspect ratio of 5 or less, and the glass product is broken into a plurality of fragments in 1 second or less.

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

A third aspect of the present disclosure is directed to a toughened glass substrate, a containment layer, as described herein; 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.

According to a fourth aspect of the present disclosure, there is provided a semiconductor device comprising: a housing having a front surface; An electrical component at least partially provided within the housing and including at least a controller, a memory, and a display; And a cover glass disposed on the front of the housing and on the display and including a tempered glass article as described herein.

Additional features and advantages will be set forth in the description which follows, and in part will be apparent to those skilled in the art from the following detailed description, or may be learned by practice of the embodiments described herein, including the following detailed description, It will be easily recognized.

It is to be understood that both the foregoing background and the following detailed description are exemplary only 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 further understanding and are incorporated in and constitute a part of this specification. The drawings are provided to illustrate one or more embodiments (s) and to explain the principles and operation of the various embodiments in conjunction with the detailed description.

IA is a side view of a glass article according to one or more embodiments;
1B is a side view of the glass article of FIG. 1A after fracture;
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 reinforced glass-based article;
4 is a cross-sectional view across the thickness of an enhanced 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 for the sandpaper described in this disclosure;
Figure 7 is a schematic cross-sectional view of the main mechanism for failure due to bending as well as damage introduction that typically occurs in glass-based products used in mobile or portable electronic devices;
8 is a flow chart of a method for performing an IBoS test in the apparatus described herein;
FIG. 9A is a side view of the glass article of FIG. 1A including a sealing layer; FIG.
Figure 9b is a side view of the glass article of Figure 9a comprising 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 results of the AROR test of Example 1;
12 is a graph showing the drop test results of Example 2;
13 is a plot showing the concentration of K ₂ O as a function of ion exchange depth for Example 4;
14 is a plot showing the stress profile of Example 4G;
15A to 15D are broken-away images of Embodiment 5;
Figures 16A-16D are images showing the readability of Example 6 after fracture at different viewing angles;
17 is a plot of the stored tensile energy calculated according to a function of ion-exchange time for Example 7;
18 is a plot of the center tension calculated for a function of ion-exchange time for Example 7; And
19 is a plot showing the stress profile of Example 6 with plotted compressive and tensile stresses as a function of depth.

Hereinafter, the description will be made in great detail with respect to various embodiments, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. It is to be understood that the embodiments disclosed herein are merely representative and each incorporates certain advantages of the present invention. In general, with reference to the drawings, it is to be understood that the illustration is for the purpose of describing particular embodiments and is not intended to limit the disclosure or the appended claims. The drawings are not necessarily to scale, and certain features and certain views of the drawings may be exaggerated schematically or exaggeratedly for clarity and brevity.

In the following detailed description, like reference characters designate the same or corresponding parts throughout the several views shown in the drawings. Also, unless expressly stated otherwise, terms such as "upper," " lower, "" outer," " inner, "and the like are to be construed as convenience, Additionally, where a group is described as comprising at least one of a group of elements and combinations thereof, the group may comprise any number of these elements, either individually or in combination with one another, , ≪ / RTI > Similarly, where a group is described as consisting of at least one of a group of elements and combinations thereof, it is understood that the groups may be made of any number of these elements, either individually or in combination with each other. Unless otherwise stated, the ranges of values, when quoted, include both upper and lower limits of the range as well as any arbitrary range between them. As used herein, the terms " singular "and" plural "are used interchangeably and, unless stated otherwise, both the singular and the plural refer to at least one or more than one. It is also understood that the various features disclosed in this specification and the drawings may be used in combination with any and all of these.

It is noted that the terms " substantially "and" about "can be used herein to indicate the degree of inherent uncertainty that may result from any quantitative comparison, value, measurement, or other expression. These terms are also used herein to indicate the extent to which quantitative expressions can vary from stated standards without resulting in a change in the underlying function of the subject matter in question.

As used herein, the term "glass article" is used in a broad sense to include any article made entirely 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%).

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

A first aspect of the present disclosure is to provide a method of forming a dense fracture pattern having a dicing effect similar to a fully thermally tempered glass used in shower panels or automotive window panels, Reinforced glass products. In some embodiments, debris is less harmful to a person. Such products have a thickness that is significantly less than the thickness achievable by presently known thermal tempering processes and exhibit this behavior despite being chemically strengthened. In some embodiments, the debris is even smaller or finer than the debris observed in a known thermally tempered glass. For example, an embodiment of a glass product may be used to provide a " dicing "effect when the glass product is broken, such that the debris resembles a cube rather than a splinter, , "Diced" fragments have small aspect ratios, and the fractured surfaces and formed-in-surface surfaces form larger angles (i.e., less blade-like or knife- 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 product. In some instances, when broken or after the glass product breaks, the glass product may have a glass transition temperature of less than about 10 or less than about 5 (e.g., less than about 4.5, less than about 4, less than about 3.5, or less than about 3, About 2 or less). ≪ / RTI > In some embodiments, the average aspect ratio of the plurality of debris ranges from about 1 to about 2. In some instances, about 90% or more, or about 80% or more of the plurality of debris represent the average aspect ratio described herein. As used herein, the term "aspect ratio" refers to the ratio of the longest or largest dimension of the debris to the shortest or smallest dimension of the debris. The term "dimension" may include length, width, diagonal, or thickness. A glass product exhibiting such debris after fracture may be characterized as exhibiting "dicing" behavior here.

1A and 1B, in one or more embodiments, the glass article 10 described herein has a sheet shape having opposed major surfaces 12, 14 and opposed minor surfaces 16, 18 . At least one major surface 12 forms a "formed-like" surface of the glass product. If broken, a new surface generated by fracture of the glass article is formed (i.e., a "fracture-generated" surface), as indicated by reference numeral 19 in FIG. The angle alpha between the fractured surface and the formed surface of the furnace (after the glass article is broken) ranges from about 85 degrees to about 95 degrees or from about 88 degrees to about 92 degrees. In at least one embodiment, at least about 90% of the plurality of debris in the glass product exhibits an angle between the surface of the formed-bar and all the fractured surfaces after the glass product is broken.

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

In at least one embodiment, at least 50% (e.g., greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90%) of the plurality of debris includes a volume of about 10 psi or less. In some embodiments, the volume may be less than or equal to about 8 psi, less than or equal to about 5 psi, or less than or equal to about 4 psi. In some embodiments, the volume may range from about 0.1 microns to about 1.5 microns.

As used herein, the phrase " reinforced product "includes products that are chemically reinforced or chemically reinforced and thermally enhanced, but excluding products that are only thermally reinforced. As shown in Fig. 4, tempered glass articles exhibit stress profiles that can be characterized in terms of surface compressive stress (CS), center 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 known thermally tempered glass articles and known chemically tempered glass articles. 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 spreading flaws, (E.g., about 21% of the total thickness of the glass), which can be avoided. An example of the stress profile generated by thermal tempering is shown in Fig. 2, the heat treated glass product 100 includes a first surface 101, a thickness t ₁ , and a surface CS 110. The glass article 100 exhibits a CS decreasing from the first surface 101 to the DOC 130 as defined herein wherein the stress changes from compression to tensile stress, Lt; / RTI >

Thermal tempering can be achieved by forming a thick glass product (i. E., About 3 millimeters or more), since a sufficient thermal gradient must be formed between the core and the surface of such product to achieve heat strengthening and desired residual stresses It is limited to a current of glass) having a thickness (t _1). Products of this thickness may be used for displays (e.g., consumer electronics including cellular phones, tablets, computers, navigation systems, and the like), architectural (e.g., windows, panels for shower booths, Such as, for example, automobiles, trains, etc.), transport (e.g., automobiles, trains, aircraft, marine vessels, etc.), household appliances, packaging materials, or any application requiring a high impact resistance but thin and light- It is undesirable or not feasible in application.

Known chemically reinforced glass articles do not exhibit the stress profile of the thermally tempered glass article, even though the chemical strengthening is not limited by the thickness of the glass article in the same manner as thermal tempering. An example of a stress profile generated by chemical strengthening (e.g., by an ion exchange process) is shown in FIG. 3, the chemically tempered glass product 200 comprises a first surface 201, a thickness t ₂ and a surface CS 210. The glass article 200 exhibits a CS decreasing from the first surface 201 to the DOC 230 as defined herein wherein the stress changes from compression to tensile stress and is applied to the CT 220 . As shown in Fig. 3, this profile represents a CT region or a flat CT region with a constant or near constant tensile stress and, often, a lower CT value, as compared to the CT value shown in Fig.

The glass article of one or more embodiments of the disclosure may have 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 a thickness t Lt; RTI ID = 0.0 > DOC. ≪ / RTI > As used herein, DOC refers to the depth at which stress in a glass product changes from compression to tensile stress. In the DOC, the stress crosses negative (tensile) stresses (e.g., 130 in FIG. 2) at positive (compressive) stresses and therefore exhibits a stress value of zero.

According to the convention commonly used in the art, compression is expressed as negative (< 0) stresses and tensile forces are expressed as positive (> 0) stresses. However, in the present description as a whole, CS is expressed as a positive value or an absolute value - that is, CS = | CS | as enumerated here.

In particular, the glass articles described herein are thin and exhibit only achievable stress profiles through tempering of thick glass articles typically (e.g., having a thickness of about 2 mm or more). In some cases, the glass product exhibits a larger surface CS than the tempered glass product. In at least one embodiment, the glass article exhibits a depth of a larger compressive layer (where CS is gradually decreased and increases than known chemically reinforced glass articles) so that the glass article or device containing it is rigid , Even when falling onto a rough surface, the glass article exhibits substantially improved rupture resistance. Glass articles of one or more embodiments exhibit larger CT values than some known chemically tempered glass substrates.

CS, Orihara Industrial Co. , Ltd. (FSM) using a commercially available instrument, such as the FSM-6000, manufactured by Fuji Photo Film Co., Ltd. (Japan). The surface stress measurement relies on an accurate measurement of the stress optical modulus (SOC) associated with the birefringence of the glass. The SOC is measured in accordance with a revised version of procedure C, which is ultimately referred to in the ASTM standard C770-98 (2013), whose designation is "Standard Test Method for Glass Stress-Optical Coefficient" &Lt; / RTI &gt; Wherein said revision comprises 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 in both parallel and polished faces, Core drilling. The revision also includes calculating a maximum force, Fmax, to be applied. The force should be sufficient to produce a compressive stress of at least 20 MPa. Fmax is calculated as follows:

Fmax = 7.854 * D * h

here:

Fmax = Newton's power

D = diameter of the disk

h = thickness of the optical path.

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

σ _MPa = 8F / (? * D * h)

here:

F = Newton's power

D = diameter of the disk

h = thickness of the optical path.

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

In some embodiments, the glass article may also exhibit a depth of penetration of potassium ions ("potassium DOL") that is different from DOC. The degree of difference between the DOC and the potassium DOL depends on the ion exchange process which causes stress in the glass substrate composition and the resultant glass product. In glassware, when stress is generated by the exchange of potassium ions into the glass product, FSM (as described above in relation to CS) is used to measure potassium DOL. When stress is generated by exchanging sodium ions into the glass product, SCALP (as described above in connection with CT) is used to measure the DOC, and the resulting glass product has a potassium DOL Lt; / RTI &gt; In glassware, when the stress is generated by exchanging both potassium and sodium ions into the glass, the exchange depth of sodium represents the DOC and the exchange depth of potassium ions represents a change in the magnitude of the compressive stress (however, Lt; / RTI &gt; to tensile); In this embodiment, the DOC is measured by SCALP, and the potassium DOL is measured by FSM. When both potassium DOL and DOC are present in the glass product, the potassium DOL is typically below the DOC.

The refracted near-field (RNF) method or SCALP can be used to measure the stress profile in the glass article described herein (regardless of whether the stress is generated by sodium ion exchange and / or potassium ion exchange) . If the RNF method is utilized, the CT value provided by SCALP is utilized. In particular, the stress profile measured by RNF is balanced and adjusted to the CT value provided by the SCALP measurement. The RNF method is described in U.S. Patent No. 8,854,623 entitled " Systems and Methods for Measuring Profile Profile of a Glass Sample ", the entire contents of which are incorporated herein by reference. In particular, the RNF method includes positioning a glass-based article adjacent a reference block, measuring a polarization-switched light beam, which is switched at a rate of 1 Hz to 50 Hz between orthogonal polarizations , Measuring the amount of power in the polarization-switched light beam, and generating a polarization-switched reference signal, wherein the amount of power measured in each orthogonal polarization is within 50% of each other to be. The method comprises the steps of transmitting a polarization-switched light beam through a reference block and a glass sample for different depths into a glass sample and then using a relay optical system having a signal photodetector to generate a polarization- and relaying the polarization-switched light beam transmitted to the signal photodetector using the system. 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 in which the stresses in the glass product are generated only by potassium ion exchange and the potassium DOL is equivalent to DOC, the stress profile also has the priority of U.S. Provisional Patent Application No. 61 / 489,800, filed May 25, 2011 Filed on May 3, 2012 by Rostislav V. Roussev et al., Entitled " Systems and Methods for Measuring the Stress Profile of Ion-Exchanged Glass (Roussev I) " 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 (stresses as a function of depth) of chemically reinforced glass using FSM. Specifically, the spectrum of the bound optical mode for TM and TE polarized light is collected through a prism coupling technique and the detailed and accurate TM and TE refractive index profiles _nTM (z) and _nTe (z) Lt; / RTI &gt; The contents of which are incorporated herein by reference in their entirety. Detailed index profiles can be generated using the inverse Wentzel-Kramers-Brillouin (IWKB) method, and a step of fitting the measured mode spectrum to a numerically calculated spectrum of a pre-defined functional form describing the shape of the exponential profile And obtaining the functional form of the parameter from the best fit. The detailed stress profile S (z) is calculated from the difference of the recovered TM and TE exponential profiles using known stress-optical modulus (SOC) values, as follows:

_{S (z) = [n TM} (z) -n TE (z)] / SOC.

Due to the small value of the SOC, double refraction n _TM (z) -n _TE (z) at any depth z is the exponential n _TM small portion (typically about 1%) of the (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 effectiveness index is required with an accuracy of about 0.00001 RIU. The method disclosed in Roussev I provides a technique applied to raw data to ensure high accuracy for measured mode indexes in spite of noise and / or poor contrast in images of collected TE and TM mode spectra or mode spectra . This technique finds extreme positions corresponding to modes with sub-pixel resolution, including noise-averaging, filtering, and curve fitting.

As described above, the glass articles described herein can be chemically reinforced by ion exchange and exhibit a stress profile distinct from that exhibited by known tempered glass. In this process, ions at 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, the ions and larger ions in the surface layer of the glass are selected from Li ⁺ (when present in the glass product), Na ⁺ , K ⁺ , Rb ⁺ , and Cs ⁺ The same is a monovalent alkali metal cation. Alternatively, monovalent cations in the surface layer can be replaced by monovalent cations other than alkali metal cations, such as Ag ⁺ or the like.

The ion exchange process is usually carried out by immersing the glass article in a molten salt bath (or two or more molten salt baths) containing larger ions to be exchanged for smaller ions in the glass product. It should be noted that an aqueous salt bath can also be utilized. Additionally, the composition of the bath (s) may comprise one or more types of larger ions (e.g., Na + and K +) or a single larger ion. Including but not limited to, bath composition and temperature, immersion time, number of immersions of the glass product in a bath (or bathtubs), use of multi-bath baths, annealing, washing, , The parameters for the ion exchange process can be determined by the composition of the glass product (including the structure of the product and any crystalline phase present) and the desired DOC and CS of the glass product resulting from the consolidation operation, As will be appreciated by those skilled in the art. By way of example, ion exchange of a glass product 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 the larger alkali metal ions . Conventional nitrates include _{KNO 3, NaNO 3, LiNO 3} , NaSO 4 , and combinations thereof. The temperature of the molten salt bath is typically in the range of 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 diffusivity. However, other temperatures and immersion times than those described above may also be used.

In one or more embodiments, the glass article may be immersed in a molten salt bath of 100% NaNO ₃ having a temperature of from about 370 ° C to about 480 ° C. In some embodiments, the glass substrate may be immersed in a melt-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, below about 500 ° C.). In at least one embodiment, the glass article may be immersed in the second bath after immersion in the first bath. In the second immersion bath it is located in a molten salt bath containing 100% KNO ₃ may comprise an immersion for 15 minutes to 8 hours.

The ion exchange conditions can be varied based on the thickness of the glass composition and the glass substrate. For example, a glass substrate having a nominal composition (nominal composition) as shown in Example 1 to a thickness of 0.4㎜ is, for about 10 hours to about 20 hours with a temperature of about 460 ℃ (NaNO ₃ and balance forming a can) may be immersed in a molten salt bath of 80-100% KNO _3. The same substrate having a thickness of about 0.55 mm has a temperature of about 460 DEG C for a period of about 20 hours to about 40 hours May be (NaNO ₃ and a balance) is immersed in a molten salt bath of 70-100% KNO _3. The same substrate having a thickness of about 0.8 mm can be immersed in a molten salt bath of 60-100% KNO ₃ (in balance with NaNO ₃ ) at a temperature of about 460 ° C for a period of about 40 hours to about 80 hours have.

In one or more embodiments, the glass-based substrate is made from about NaNO ₃ and KNO 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 less than about 4 hours containing the ₃ (for example, 49% / 51%, 50% / 50%, 51% / 49%) can be immersed in the melt, a 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 article or to provide a "spike ". This spike can be achieved by a single bath or multi-bath using a bath or bath (s) with a single composition or mixed composition due to the inherent characteristics of the glass composition used in the glass-based products described herein.

As illustrated in Figure 4, the glass product 300 of one or more embodiments includes a first surface 302 defining a thickness t and a second surface 304 opposing the first surface . In one or more embodiments, the thickness t may 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 From about 0.1 mm to about 1.5 mm, from about 0.2 mm to about 1.5 mm, from about 0.3 mm to about 1.5 mm, from about 0.4 mm to about 1.5 mm, from about 0.01 mm to about 1.1 mm, from about 0.1 mm to about 1.1 mm, From about 0.1 mm to about 1.1 mm, from about 0.3 mm to about 1.1 mm, from about 0.4 mm to about 1.1 mm, from about 0.01 mm to about 1.4 mm, from about 0.01 mm to about 1.2 mm, from about 0.01 mm to about 1.1 mm, From about 0.01 mm to about 0.6 mm, from about 0.01 mm to about 0.5 mm, from about 0.1 mm to about 1.0 mm, from about 0.01 mm to about 0.9 mm, from about 0.01 mm to about 0.8 mm, from about 0.01 mm to about 0.7 mm, 0.5 mm, or from about 0.3 mm to about 0.5 mm).

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

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

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

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

The surface CS 310 can be at least about 150 MPa or at least about 200 MPa (e.g., at least about 250 MPa, at least about 300 MPa, at least about 400 MPa, at least about 450 MPa, at least about 500 MPa, or at least about 550 MPa). 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 has a surface roughness of from about 150 MPa to about 1200 MPa, from about 200 MPa to about 1200 MPa, from about 250 MPa to about 1200 MPa, from about 300 MPa to about 1200 MPa, From about 400 MPa to about 1200 MPa, from about 450 MPa to about 1200 MPa, from about 500 MPa to about 1200 MPa, from about 200 MPa to about 1100 MPa, from about 200 MPa to about 1000 MPa, from about 200 MPa to about 900 MPa , From about 200 MPa to about 800 MPa, from about 200 MPa to about 700 MPa, from about 200 MPa to about 600 MPa, from about 200 MPa to about 500 MPa, from about 300 MPa to about 900 MPa, or from about 400 MPa to about 600 MPa Lt; / RTI &gt;

The CT 320 may have a pressure of at least about 25 MPa, at least about 50 MPa, at least about 75 MPa, at least about 85 MPa, or at least about 100 MPa (eg, at least about 150 MPa, at least about 200 MPa, Or more). In some embodiments, the CT 320 may be in the range of about 50 MPa to about 400 MPa (e.g., about 75 MPa to about 400 MPa, about 100 MPa to about 400 MPa, about 150 MPa to about 400 MPa, From about 50 MPa to about 300 MPa, from about 50 MPa to about 300 MPa, from about 50 MPa to about 250 MPa, from about 50 MPa to about 200 MPa, from about 100 MPa to about 400 MPa, from about 100 MPa to about 300 MPa, About 250 MPa). As used herein, CT is the largest central tensile force in a glass product.

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

CT 320 may be located in the range of about 0.3 占 t to about 0.7 占 t, about 0.4 占 to about 0.6 占 t, or about 0.45 占 to about 0.55 占 t. It should be noted that any one or more of surface CS 310 and CT 320 may depend on the thickness of the glass-based product. For example, glass-based articles 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 article decreases, CT can increase. In other words, CT increases as the thickness decreases (or as the glass-based article becomes thinner).

The Young's modulus of the glass product may affect the CT of the tempered glass article described herein. Specifically, as the Young's modulus of the glass product decreases, the glass product can be reinforced to have a lower CT for a given thickness, and still exhibit the fracture behavior described herein. For example, when comparing 1 mm glass products having a relatively lower Young's modulus than another 1 mm-thick glass product having a higher Young's modulus, the lower Young's modulus glass product is less (i.e., Low CT values), and still exhibit the same fracture behavior as the higher Young's modulus glass (which will have a higher CT compared to the CT glass product).

In some embodiments, the ratio of CT 320 to surface CS is in the range of 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 0.1, about 0.5 to about 0.8, about 0.0.5 to about 1, about 0.2 to about 0.5, about 0.3 to about 0.5). In known chemically reinforced glass products, 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 may be less than about 20 times the CT.

In one or more embodiments, the stress profile 312 includes a maximum CS, typically surface CS 310, and may 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 to the DOC 317 and CT 320. In one or more embodiments, the DOC 317 may be greater than or equal to about 0.1 t. For example, the DOC 317 may have a DOC 317 of at least about 0.12 t, at least about 0.14 t, at least about 0.15 t, at least about 0.16 t, at least 0.17 t, at least 0.18 t, at least 0.19 t, · T or more, about 0.21 · t or more, or about 0.25 · t or less. In some embodiments, the DOC 317 is less than the maximum chemical depth 342. The maximum chemical depth 342 may be at least about 0.4 占 t, at least 0.5 占 t, at least about 55 占 t, or at least about 0.6 占 t.

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

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

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

In at least one embodiment, 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 product ranges from about 0.18 t to about 0.21 t.

In one or more embodiments, the glass article exhibits a maximum chemical depth of at least about 0.4 占,, at least 0.5 占,, at least about 0.55 占,, or at least about 0.6 占.. The term "chemical depth &quot;, as used herein, refers to the depth at which a metal oxide or an alkali metal oxide ion (e.g., a metal ion or an alkali metal ion) Electron Probe Micro-Analysis), which means the depth reaching the minimum value. The ion is an ion diffused into a chemically strengthened glass article as a result of ion exchange. The maximum chemical depth refers to any ion-exchanged maximum diffusion depth as a chemically reinforced glass product by an ion exchange process. For example, in the case of a molten salt bath having one or more ionic species (i.e., a molten salt bath of NaNO ₃ and KNO ₃ ), other ion species may be introduced into the chemically tempered glass product at different depths Can be diffused. The maximum chemical depth is the largest diffusion depth of all ion species ion-exchanged into the chemically reinforced glass product.

In one or more embodiments, the stress profile 312 can be described in a parabolic shape. In some embodiments, the stress profile along the region or depth of the glass-based article exhibiting tensile stress exhibits a parabolic shape. In at least one particular embodiment, the stress profile 312 is free of portions that exhibit flat stress (i.e., compressive or tensile) portions or substantially constant stresses (i.e., compressive or tensile). In some embodiments, the CT region exhibits a stress profile that is substantially free of, or substantially constant, flat stress. In one or more embodiments, all of the stress profile 312 between about 0 t to about 0.2 t and a thickness range of greater than about 0.8 t (or between about 0 t to about 0.3 t and 0.7 t) The point includes a tangent of less than about -0.1 MPa / micrometers or greater than about 0.1 MPa / micrometers. In some embodiments, the tangent may be less than about -0.2 MPa / micrometers or greater than about 0.2 MPa / micrometers. In some more particular embodiments, the tangent may be less than about-0.3 MPa / micrometers or greater than about 0.3 MPa / micrometers. In a more particular embodiment, the tangent may be less than about-0.5 MPa / micrometers or greater than about 0.5 MPa / micrometers. In other words, the stress profile of one or more embodiments in accordance with 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) The point having a tangent line is excluded. Although not wishing to be bound by theory, it is believed that known error functions or quasi-linear stress profiles can be used to predict the stress profile of a material (such as shown in FIG. 3, which exhibits a flat or zero slope stress profile, Micrometers, about -0.3 MPa / micrometers to about 0.3 MPa / micrometers, or about-0.5 MPa / micrometers to about 0.2 MPa / micrometers to about 0.2 MPa / micrometers, (I.e., from about 0 t to about 0.2 t and more than 0.8 t, or from about 0 t to about 0.3 t and 0.7 t or more) having a tangent in the range of 0.5 MPa / micrometers . Glass-based articles of one or more embodiments of the present disclosure do not exhibit a stress profile having a flat or zero tilt stress profile along these thickness ranges, as shown in Fig.

In at least one embodiment, the glass-based article exhibits a stress profile in a thickness range of from about 0.1 占 내지 to 0.3 占 포함, including a maximum tangential and a minimum tangent, and from about 0.7 占 내지 to 0.9 占.. In some instances, the difference between the maximum tangential and the minimum tangential is less than about 3.5 MPa / micrometers, less than about 3 MPa / micrometers, less than about 2.5 MPa / micrometers, or less than about 2 MPa / micrometers.

In one or more embodiments, the glass-based article has a stress profile 312 substantially free of any linear segments that extend in at least a portion of the thickness t of the glass- . In other words, the stress profile 312 increases or decreases substantially continuously along the thickness t. In some embodiments, the stress profile is substantially free of any linear segments in the depth direction having a length of at least about 10 micrometers, at least about 50 micrometers, or at least about 100 micrometers, or at least about 200 micrometers. As used herein, the term "linear" refers to a slope along a linear segment of less than about 5 MPa / micrometers, or less than about 2 MPa / micrometers. In some embodiments, one or more portions of the stress profile substantially free of any linear segments in the depth direction can be at least about 5 micrometers (e.g., at least 10 micrometers, or more Lt; RTI ID = 0.0 &gt; 15 micrometers) &lt; / RTI &gt; For example, along a depth of from about 0 micrometers to less than about 5 micrometers from the first surface, the stress profile may comprise a linear segment, but from a depth of at least about 5 micrometers from the first surface, There are no segments.

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

In one or more embodiments, the glass-based article can be described in terms of the shape of the stress profile along the CT region (327 in FIG. 4). For example, in some embodiments, the stress profile along the CT region (where the stress is stretched) can be approximated by a formula. In some embodiments, the stress profile along the CT region can be approximated by: &lt; EMI ID = 1.0 &gt;

[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 (tensile force). In Equation 1, MaxT is the maximum tension values and a CT value of _n is the tension in the n MaxT or less. Both MaxT and CT _n are positive values in MPa. The value x is a position along the thickness t in micrometers, with a range 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. The 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 from about 50 MPa to about 80 MPa (e.g., from about 60 MPa to about 80 MPa, from about 70 MPa to about 80 MPa, from about 50 MPa to about 75 MPa, (E.g., from 50 MPa to about 70 MPa, or from about 50 MPa to about 65 MPa), and n can be in the range of 1.5 to 5 (e.g., 2 to 4, 2 to 3, or 1.8 to 2.2) 2 is a fitting parameter. In one or more embodiments, n = 2 may provide a parabolic stress profile, and an index outside n = 2 provides a stress profile with a muscle 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 fit parameter n.

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

In some embodiments, the stress profile may be altered by heat treatment. In 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, the heat treatment can result in a reduction in the slope of the stress profile at or near the surface. In some embodiments, if a steep or larger slope is desired at the surface, the ion-exchange process after the heat treatment may 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 generated due to the non-zero concentration metal oxide (s) varying 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 not 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 not zero, and from about 0 t to about 0.35 t, from about 0 t to about 0.4 t, from about 0 t to about 0.45 t, It varies along the thickness range of about 0.48 占.. Metal oxides can be described as causing stress 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 thickness segment 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 non-zero and which change along a portion of the thickness can be described as causing stress in glass-based products.

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 surface and the second surface, and increases from the point to the second surface.

The concentration of the metal oxide may include one or more metal oxides (e.g., a combination of Na ₂ O and K ₂ O). In some embodiments, if two metal oxides are utilized and the radius of the ions is different, the concentration of ions with a larger radius will exceed the concentration of ions with a smaller radius than at shallow depth, At deep depth, the concentration of ions with smaller radii exceeds the concentration of ions with larger radii. For example, when single Na- and K-containing baths are used in an ion exchange process, the concentration of K + ions in the glass-based product exceeds the concentration of Na + ions at a shallower depth, while the concentration of Na + It exceeds the concentration of K + ions at deeper depths. This is due, in part, to the size of the ions. In such glass-based products, the zone at or near the surface contains a larger CS due to a larger amount of larger ions (i.e., 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 (i.e., a spike in the stress profile at the surface).

The concentration gradient or change of the one or more metal oxides is produced by chemically enhancing the glass-based substrate, as already described herein, wherein the plurality of first metal ions in the glass-based substrate comprises a plurality of second metal ions . The first ion may be an ion of lithium, sodium, potassium, and rubidium. The second metal ion may be one of sodium, potassium, rubidium, and cesium, provided that the second alkali metal ion has an ion radius exceeding the ion radius of the first alkali metal ion. The second metal ion is present in the glass-based substrate as an oxide thereof (e.g., 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 the metal oxide is at least about 0.5 mol% in the CT layer 327. In some embodiments, the concentration of the metal oxide may be greater than about 0.5 mol% (e.g., greater than about 1 mol%) along the overall thickness of the glass-based article, and the first surface 302 and / And is substantially constant at a point between the first surface 302 and the second surface 304. At this point, the concentration of the 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 the particular metal oxide extends along a substantial portion or total thickness t of 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 the specific metal oxide in the glass-based product may range from about 1 mol% to about 20 mol%.

In one or more embodiments, the free-based product includes a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is in the range of about 0 &lt; RTI ID = 0.0 &gt; mol% to about 15 mol% and the second metal oxide concentration is from about 0 mol% to about 10 mol% from a second thickness range of from about 0 micrometers to about 25 micrometers (or from about 0 micrometers to about 12 micrometers) Range; However, the concentration of one or both of the first metal oxide and the second metal oxide is 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 comprises Na ₂ O, but the second metal oxide may comprise K ₂ O.

The concentration of the metal oxide may be determined from the reference amount of the metal oxide in the glass-based product before it is changed to include the concentration gradient of such metal oxide.

In some embodiments, the stress profile may 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, the heat treatment can result in a reduction in the slope of the stress profile at or near the surface. In some embodiments, if a steep or larger slope is desired at the surface, the ion-exchange process after heat treatment may be utilized to provide a "spike" or to increase the slope of the stress profile at or near the surface .

In at least one embodiment, the stress profile 312 is generated due to a non-zero concentration of the 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 not 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 not zero, and from about 0 t to about 0.35 t, from about 0 t to about 0.4 t, from about 0 t to about 0.45 t, It varies with the thickness range of about 0.48 占.. Metal oxides can be described as causing stress 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 thickness segment 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 which vary along a portion of the thickness can be described as causing stress in glass-based products.

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 surface and the second surface, and increases from the point to the second surface.

The concentration of the metal oxide may comprise one or more metal oxides (e.g., a combination of Na ₂ O and K ₂ O). In some embodiments, when two metal oxides are utilized and the radii of the ions are different, the concentration of ions with a larger radius exceeds the concentration of ions with a smaller radius at shallow depth, while at a deeper depth , The concentration of ions with a smaller radius exceeds the concentration of ions with a larger radius. For example, when single Na- and K-containing baths are used in an ion exchange process, the concentration of K + ions in the glass-based product exceeds the concentration of Na + ions in shallower depths, whereas the concentration of Na + It exceeds the concentration of K + ions at deeper depths. This is due, in part, to the size of the ions. In such glass-based products, the zone at or near the surface contains a larger CS due to a larger amount of larger ions (i.e., 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 (i.e., a spike in the stress profile at the surface).

The concentration gradient or change of the one or more metal oxides is produced by chemically enhancing the glass-based substrate, as already described herein, wherein the plurality of first metal ions in the glass- Exchange. The first ion may be an ion of lithium, sodium, potassium, and rubidium. The second metal ion may be one of sodium, potassium, rubidium, and cesium, provided that the second alkali metal ion has an ion radius exceeding the ion radius of the first alkali metal ion. The second metal ion is present in the glass-based substrate as an oxide thereof (e.g., 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 the metal oxide is greater than about 0.5 mol% in the CT layer 327. In some embodiments, the concentration of the metal oxide may be at least about 0.5 mol% (e.g., at least about 1 mol%), and the first surface 302 and / or at least about 0.5 mol%, depending on the overall thickness of the glass- And is substantially constant at a point between the first surface 302 and the second surface 304. At this point, the concentration of the metal oxide is minimum according to the total thickness t; However, the concentration is not zero at that point. In other words, the non-zero concentration of the particular metal oxide extends along a substantial portion of the total thickness t or 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 the particular metal oxide in the glass-based product may range from about 1 mol% to about 20 mol%.

In one or more embodiments, the free-based product comprises a first metal oxide concentration and a second metal oxide concentration, wherein the first metal oxide concentration is in the range of from about 0 t to about 0.5 t, % To about 15 mol%, and the second metal oxide concentration ranges from a second thickness range of from about 0 micrometers to about 25 micrometers (or from about 0 micrometers to about 12 micrometers), from about 0 mol% to about 10 mol% 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 substantial portion of the glass-based product. The glass-based product may include an optional third metal oxide concentration. While the first metal oxide that may contain Na ₂ O, and 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 product before it is changed to include the concentration gradient of such metal oxide.

The glass articles described herein may exhibit tensile energy stored in the range of 15 J / m &lt; 2 &gt; or more (e.g., about 15 J / m 2 to about 50 J / m 2). For example, in some embodiments, the stored tensile energy may range from about 20 J / m2 to about 150 J / m2. In some instances, the stored tensile energy is from about 25 J / m2 to about 150 J / m2, from about 30 J / m2 to about 150 J / m2, from about 35 J / m2 to about 150 J / About 150 J / m 2, about 45 J / m 2 to about 150 J / m 2, about 50 J / m 2 to about 150 J / From about 25 J / m 2 to about 130 J / m 2, from about 25 J / m 2 to about 120 J / m 2, from about 65 J / From about 30 J / m 2 to about 130 J / m 2, from about 40 J / m 2 to about 120 J / m 2, from about 25 J / , Or from about 40 J / m 2 to about 100 J / m 2. The thermally and chemically reinforced glass-based articles of one or more embodiments are stored at a temperature above about 40 J / m 2, above about 45 J / m 2, above about 50 J / m 2, about 60 J / m 2, or about 70 J / Tensile &lt; / RTI &gt; energy.

The stored tensile energy is calculated using the following equation:

&Quot; (2) &quot;

The stored tensile energy (J / m 2) = [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) can be found in Suresh T. Gulati, Frangibility of Tempered Soda-Lime Glass Sheet, GLASS PROCESSING DAYS, The Fifth International Conference on Architectural and Automotive Glass, pp. 1997, as equation (4).

Some embodiments of the glass product exhibit excellent mechanical performance, as evidenced by device drop testing or component level testing, as compared to known tempered glass products. In one or more embodiments, the glass article exhibits improved surface strength when applied 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 surface strength measurement for testing flat glass specimens, and ASTM C1499-09 (2013), entitled " Standard Test Method for Monotonic Equivalent Flexural Strength of Advanced Ceramics at Ambient Temperature " - serves as the basis for the on-ring worn ROR test methodology. The content of ASTM C1499-09 is incorporated herein by reference in its entirety. In one embodiment, the glass specimens are obtained from Annex A2 of ASTM C158-02 (2012), entitled " Standard Test Methods for Strength of Glass by Flexure (Flexion of Glasses by Flexure) On-ring test with 90 grit silicon carbide (SiC) particles that are transferred to the glass sample using the method and apparatus described herein. The contents of ASTM C158-02 and in particular Annex 2 are incorporated herein by reference in their entirety.

Before the ring-on-ring test, the surface of the glass article was abraded as described in ASTM C158-02, Annex 2, and the surface defect state of the sample was normalized and measured using the apparatus shown in Figure A2.1 of ASTM C158-02 / Or adjust. The abrasive is typically sandblasted onto the surface 110 of the glass article with a load or pressure of at least 15 psi using an air pressure of 44 psi (304 kPa). In some embodiments, the abrasive may be sandblasted onto the surface 110 with a load of 20 psi, 25 psi, or even 45 psi. After air flow is established, 5 cm3 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, a glass article having at least one abraded surface 112 as shown in Fig. 5 may have a shaft bending strength or breakage load (i. E. Is placed between two concentric rings of different sizes to determine the maximum stress that can be sustained if applied to bending between two concentric rings. In the worn ring-on-ring structure 100, the worn glass product 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 product by 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 and 120 should be concentrically aligned within 0.5% of the support ring diameter D2. The load cell used for 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 DEG C and a relative humidity of 40 +/- 10%.

For a fixture design, the radius r of the projecting 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 and 120 are typically made of hardened steel having a hardness HRc > 40. ROR fixtures are commercially available.

The intended breakage mechanism for the ROR test is to observe the fracture of the glass article 110 originating from the surface 130a within the loading ring 130. [ The fracture occurring outside this region, i.e. between the loading ring 130 and the support ring 120, is omitted from the data analysis. However, due to the thinness and high strength of the glass product 110, large deflections exceeding ½ of the sample thickness h are occasionally observed. Thus, it is common to observe a high percentage of fractures originating from below the loading ring 130. Stresses can not be accurately calculated without knowledge of the origins of failure in each specimen and the knowledge of stress development both inside and below the ring (collected via strain gage analysis). Therefore, the AROR test focuses on the peak load at failure as a measured response.

The strength of the glass product depends on the presence of surface flaws. However, as the strength of the glass is in fact based on statistics, the likelihood of scratches of a given size present can not 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 is determined by an AROR test using a load of 25 psi or even 45 psi to wear the surface, with a dynamic of at least 20 kgf and a maximum of about 45 kgf exhibiting axial bending strength or failure load . In another embodiment, the surface strength is at least 25 kgf, and in yet another embodiment, at least 30 kgf.

In some embodiments, the tempered glass article may exhibit improved drop performance. As used herein, dropping performance is evaluated by assembling a glass product to a mobile phone device. In some cases, multiple glass products can be assembled on the same mobile phone device, and can be tested equally. The hand-held device with the glass product is then dropped onto an abrasive paper (which may contain Al ₂ O ₃ particles or other abrasive) for a continuous drop starting at a height of 50 cm. As each sample withstands falling from the height, the mobile phone device with the sample drops again at the elevation height until the glass product breaks, at which point the breakage height of the sample is recorded as the maximum breakage height.

In some embodiments, the glass article exhibits a maximum breakage height of at least about 100 cm, with a thickness of about 1 mm. In some embodiments, the glass article has a maximum breakdown 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 . One or more embodiments of the glass article exhibits a diced fracture pattern after breaking at the break height. The diced fracture pattern includes indicating the aspect ratio described herein.

In one or more embodiments, the glass product herein is such that when the glass product is bonded directly to the substrate (i.e., the display unit), after the glass product is broken, at least 50% of the cracks are sub- Lt; RTI ID = 0.0 &gt; partially &lt; / RTI &gt; extended through the thickness and blocked below the surface). For example, in some instances, the crack may be partially extended through the thickness (t) of the glass article, for example, from 0.05 t to 0.95 t. The percentage of cracks in the partially extended glass product 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 described in terms of performance in a sandpaper reverse osmosis (IBoS) test. The IBoS test is a dynamic component-level test that mimics the principal mechanism for failure due to damage introduction plus bending that typically occurs in glass-based products used in mobile or portable electronic devices, as schematically shown in FIG. In the field, damage introduction (Fig. 7a) occurs at the upper surface of the glass-based product. 7 (b) or fracture occurs from the bending of the upper surface of the glass-based article or from the internal portion of the glass-based article 7 (c). The IBoS test is designed to apply bending under dynamic loading and to simultaneously introduce damage to the glass surface. In some cases, glass-based products exhibit improved drop performance when the same glass-based product does not include compressive stress, including compressive stresses.

The IBoS test apparatus is schematically shown in Fig. The apparatus 500 includes a test bed 510 and a ball 530. Ball 530 is a solid or solid ball, such as, for example, a stainless steel ball, or the like. In one embodiment, the ball 530 is 4.2 grams of stainless steel ball having a diameter of 10 mm. The ball 530 drops directly from the predetermined height h onto the glass-based product sample 518. The test bed 510 includes a solid foundation 512 comprising a hard, rigid material such as granite or the like. The sheet 514 having the abrasive disposed on the surface is placed on the upper surface of the solid base 512 with the surface having the abrasive facing upward. In some embodiments, the sheet 514 is a 30 grit surface, and in other embodiments, a sandpaper having a 180 grit surface. The glass-based product sample 518 is held in place on the sheet 514 by the sample holder 515 such that there is an air gap 516 between the glass-based product sample 518 and the sheet 514. The air gap 516 between the sheet 514 and the glass-based product sample 518 causes the glass-based product sample 518 to bend over the abrasive surface of the sheet 514 upon impact by the ball 530 Lt; / RTI &gt; In one embodiment, the glass-based product sample 518 is clamped across all of the corners to maintain the bend included only at the point of impact of the ball and to ensure repeatability. In some embodiments, the sample holder 514 and the test bed 510 are tailored to accommodate a sample thickness of about 2 mm or less. The air gap 516 ranges from about 50 microns to about 100 microns. The air gap 516 is tailored for adjustment for the difference in stiffness (Young's modulus, Emod) of the material, but also includes the Young's modulus and thickness of the sample. The adhesive tape 520 may be used to cover the upper surface of the glass-based product sample to collect debris in the event of breakage of the glass-based product sample 518 upon impact of the ball 530.

Various materials can be used as polishing surfaces. In one particular embodiment, the abrasive surface is any abrasive material known to those skilled in the art having sandpaper, such as silicon carbide or alumina sandpaper, engineered sandpaper, or similar hardness and / or sharpness. In some embodiments, sandpaper with 30 grit may be used because it has a more uniform surface topography than concrete or asphalt, and particle size and sharpness that produce 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. The glass-based product sample (518 in FIG. 6) is placed on the test bed 510, which has already been described, and the air gap 516 is formed between the sheet 514 having the polishing surface and the glass- And is fixed to the sample holder 515 so as to be formed between the product samples 518. The method 600 assumes that the sheet 514 having the polishing surface has already been placed on the test bed 510. However, in some embodiments, the method may include placing the sheet 514 in the test bed 510 with the surface with the abrasive facing up. In some embodiments (step 610a), the adhesive tape 520 is applied to the upper surface of the glass-based product sample 518 prior to securing the glass-based product sample 518 to the sample holder 510.

At step 620, the ball 530 is attached to the top surface (or top surface) at the approximate center of the top surface (i.e., within 1 mm, or within 3 mm, or within 5 mm, or within 10 mm of the center) 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, After impact in step 620, the degree of damage to the glass-based product sample 518 is determined (step 630). As mentioned above, the term "fracture " means that the crack propagates across the entire thickness and / or the entire surface of the substrate when the substrate is dropped or impacted by the object.

In method 600, sheet 514 with a polishing surface is replaced after each fall to avoid the "aging" effect observed in repeated use of other types of drop test surfaces (e.g., concrete or asphalt) .

The various predetermined drop height (h) and increment are typically used in method 600. The test can utilize, for example, a minimum drop height for starting (e.g., 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 aborted (step 631) when the glass-based product sample 518 is broken or broken. Alternatively, if the drop height h reaches a maximum drop height (e.g., about 100 cm) without breaking, the drop test of the method 600 may also be suspended, or until step 620 occurs It 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 applied to multiple tests at each height.

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

When applied to an inverse ball (IBoS) test for the sandpaper described above, embodiments of the glass-based articles described herein have a survival rate of at least about 60% when the ball is dropped from a height of 100 cm onto a glass surface . For example, a glass-based article can have five identical (or substantially identical) samples (i.e., approximately the same composition, as described herein, and, if enhanced, approximately the same compressive stress and compressive depth, ) Have been described as having a 60% survival rate when falling from a given height, if the IBOS drop test survives without breaking when dropped from the stated height (100 cm here). In another embodiment, the survival rate in a 100 cm IBoS test of an enhanced glass-based article is at least 70%, in other embodiments at least about 80%, and in other embodiments at least about 90%. In another embodiment, the survival rate of the reinforced free-based product dropped from a height of 100 cm in the IBoS test is at least about 60%, in other embodiments 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 survival rate of the reinforced free-based product dropped at a height of 150 cm in the IBoS test is at least about 60%, in other embodiments at least about 70%, in another embodiment at least about 80% And in other embodiments, at least about 90%.

A sample of a larger number (e.g., 10, 20, 30, etc.) is used to determine the survival rate of the free-based product when dropped from a predetermined height using the IBoS test method and apparatus described above At least five identical (or substantially identical) (i. E., Approximately the same composition, and, if enhanced, approximately the same compressive stress and compressive or &lt;Lt; / RTI &gt; depth) is tested. Each sample may be dropped once at a predetermined height (e.g., 100 cm or 150 cm), or alternatively, dropped at a higher height progressively until a predetermined height is reached without breaking, Visually (i. E., Visually) examining the evidence (total thickness of the sample and / or crack formation and propagation across the entire surface). The sample is considered "alive" in the drop test if there is no observed break after falling from a predetermined height, and "survived" (or "survived &quot; if the break is observed if the sample falls from a height below a predetermined height, Not "). The survival rate is determined by the percentage of sample population surviving the drop test. For example, if seven of the 10 groups are falling from a predetermined height and not broken, the survival rate of the glass will be 70%.

In one or more embodiments, the glass product exhibits a lower retardation rate (i.e., the glass product breaks, rapidly, or even immediately breaks at break). In some embodiments, this breaking rate can be attributed to deep DOC and high levels of CT. Specifically, the glass product is less likely to spontaneously break down after the damage has occurred to the glass product that induces breakage or breakage. In one or more embodiments, when the glass product is broken, the glass product can be obtained from Z. Tang, et al. Automated Apparatus for Measuring the Frangibility and Fragmentation of Strengthened Glass. The fracture is broken into a plurality of pieces within 2 seconds or within 1 second after the impact measured by "Vulnerability Test ", as described in Experimental Mechanics (2014) 54: 903-912. The vulnerability test was conducted on a 40 g weight (available from Fisher Scientific Industries under the trade designation TOSCO® and manufacturer identification # 13-378, 60 degree cone-spherical tip, available from Fisher Scientific Industries), a stylus with a tungsten carbide tip, The height of the stylus falls. In some embodiments, the primary fracture (or the first visible fracture that produces two debris) occurs immediately or within 0 or 0.1 seconds after the impact that causes fracture of the glass product. In one or more embodiments, the probability of a primary break occurring within the time period described herein, as measured by a vulnerability test, is greater than or equal to about 90%. In some embodiments, the secondary break (s) occur within 5 seconds (e.g., less than 4 seconds, less than 3 seconds, less than 2 seconds, or less than about 1 second). As used herein, "secondary fracture" means fracture occurring after primary fracture. In one or more embodiments, the probability of secondary break (s) occurring within the time period described herein, as measured by the vulnerability test, is greater than or equal to about 90%.

In one or more embodiments, at break, the glass product emits less and less debris that is a potential concern to the user than is presently seen by known glassware used in current portable electronic devices. As used herein, the term " released "or" released "means a debris moving from its original location or placement in a glass product after it has been broken. In some embodiments, about 10% or less (e.g., about 8% or less, about 6% or less, or about 5% or less) of the plurality of debris is released after the glass product is broken and a plurality of debris is formed. In some embodiments, after the glass product is broken and a plurality of fragments are formed, at least about 50% of the released portions of the plurality of fragments have a maximum dimension of less than 0.5 mm. In some embodiments, the number or amount of debris emitted may be characterized by a weight associated with the glass product before and after the fracture. For example, the difference between the weight of the glass product and the weight of the non-emissive portion of the debris (before breaking, including the total weight of the released portion of the plurality of debris and the non-emitted portion of the debris) , And may be less than about 1% of the impact weight. In some instances, the difference between the weight of the glass article and the weight of the non-emissive portion of the debris (before breaking, including the total weight of the released portion of the plurality of debris and the non-emitted portion of the debris) , Less than about 0.0005 g (e.g., less than 0.0004 g, less than 0.0003 g, less than 0.0002 g, or less than 0.0001 g).

In one or more embodiments, the glass article exhibits dicing of the height in a more uniform pattern across the surface and its volume. In some embodiments, dicing and uniformity of such a height occurs when the glass product has a non-uniform thickness (i.e., is formed to have a three-dimensional or a two-dimensional shape). Without being bound by theory, it is believed that by reinforcing the thinnest portion of the glass product to a sufficient degree, as defined by current industry standards, that some portions of the glass product exhibit fragility but the other portions are not vulnerable .

In at least one embodiment, the glass article (directly bonded to the substrate, i.e. display unit) exhibits haze after fracture due to the high density fracture pattern. Readability depends on the viewing angle and thickness of the glass-based article. At a viewing angle of 90 degrees to the major surface of the glass product, or at normal incidence, the broken glass product exhibits a low haze such that the underlying image or text is visible to the naked eye. At a viewing angle of less than 70 degrees (or at an angle of more than 30 degrees from normal incidence) to the major surface of the glass article, the broken glass article represents a haze that prevents the underlying image or text from being visible to the naked eye. It is to be understood that such haze is present when fragments of the glass product are still gathered together or when less than 10% of the debris is released from the glass product. While not wishing to be bound by theory, it is believed that glass articles after rupture 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 the glass product even after the glass product is broken, or when the touch and the touch are minimized or reduced to the user.

In one or more embodiments, the glass articles described herein can be combined with a sealing layer. The sealing layer is a material which, when broken, can contain debris of the glass product. For example, the sealing layer may comprise a polymer material. In one or more embodiments, the sealing layer may comprise an adhesive (such as a pressure-sensitive adhesive). In at least one embodiment, the sealing layer can 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 comprise a filled epoxy, unfilled epoxy, filled urethane or unfilled urethane.

Examples of filled epoxy are 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- % Silica nanoparticles), 3 wt% Coatosil MP-200 epoxy functional silane (adhesion promoter), 2.5 wt% Cyracril UVI-6976 (a cationic photoinitiator comprising triarylsulfonium hexafluoroantimonate salt in propylene carbonate) ), 0.25 wt% Tinuvine 292 amine stabilizer (bis (1,2,2,6,6-pentamethyl-4-piperidyl) -secarate and 1- (methyl) -8- , 6,6-pentamethyl-4-piperidinyl) -secarate).

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

In some embodiments, low modulus urethane acrylates can be used in the sealing layer. In some embodiments, the material may comprise 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 4 wt% Irgacure 2022 (photoinitiator, acylphosphine oxide / alpha hydroxy ketone), 3 wt% adhesion promoter (Example 1), 10 wt% Sartomer SR339 2 (phenoxyethyl acrylate) For example, Silquest A-189, gamma-mercaptopropyltrimethoxysilane). To form the filled urethane, 4 wt% silica powder (such as Hi Sil 233) may be added.

In one or more embodiments, the glass article may be combined with a sealing layer bonded thereto or not. In some embodiments, the glass article may be adhered and disposed on the sealing layer. The glass article may 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 (e.g., 12, 14 in FIG. 1A) of the glass article. 9A, the sealing layer 20 is not disposed at any portion of the minor surfaces 16, 18; However, the sealing layer 20 may extend at least partially along one or both of the minor surfaces 16, 18 from the main surface 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 alternative embodiments, the sealing layer formed on the major surface may be different from the sealing layer formed on any portion of the minor surface. Figure 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 16,18. 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 include a stress profile, including spikes, as described herein, such that the surface CS is in the range of about 400 MPa to about 1200 MPa, and (as shown in FIG. 9B (As well) includes a sealing material 20 on one major surface 14 and a second sealing material 22 on the 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 is in the range of about 150 MPa to about 500 MPa, and the surface (14) Only the sealing material 20 is present. The glass articles described herein can be incorporated into a variety of products and products, such as consumer electronics or devices (e.g., portable electronic devices and cover glasses for touch-enabled displays). The glass products may also be used in displays (or display products) (e.g. billboards, point of sale systems, computers, navigation systems and the like), architectural products (walls, fixtures, (Eg, washing machines, dryers, dishwashers, refrigerators and the like), packaging (for example, automobiles, automobiles, For example, pharmaceutical packaging or containers), or any product that requires some rupture resistance.

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

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

In one or more embodiments, the glass articles described herein may be used for packaging. For example, the packaging may include glassware in the form of bottles, vials or containers that contain liquid, solid or gaseous material. In at least one embodiment, the glass article is a vial containing a chemical such as a pharmaceutical substance. In at least one embodiment, the packaging includes a housing including an opening, an outer surface, and an inner surface defining the enclosure. The housing may be formed from the glass article described herein. The glass article comprises a sealing layer. In some embodiments, the enclosure is filled with a chemical or pharmaceutical material. 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 include an amorphous substrate, a crystalline substrate, or a combination thereof (e.g., a glass-ceramic substrate). The glass product may comprise an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate glass or an alkali aluminoborosilicate glass. In one or more embodiments, the glass substrate substrate (before being chemically tempered 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, Wherein the composition comprises a composition comprising B ₂ O ₃ in the range of from about 0 to about 10, R ₂ O in the range of from about 0 to about 20, and RO in the range of from about 0 to about 15, in mole percent, . In some instances, the composition may include one or both of ZrO ₂ in the range of about 0 mol% to about 5 mol% and P ₂ O ₅ in the range of about 0 to about 15 mol%. The TiO ₂ may be present from about 0 mol% to about 2 mol%.

In some embodiments, the glass composition comprises SiO ₂ in mol%, from about 45 to about 80, from about 45 to about 75, from about 45 to about 70, from about 45 to about 65, from about 45 to about 60, from about 45 to about 60, About 65 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 comprises Al ₂ O ₃ in mol%, from about 5 to about 28, from about 5 to about 26, from about 5 to about 25, from about 5 to about 24, from about 5 to about 22, From about 5 to about 20, from about 6 to about 30, from about 8 to about 30, from about 10 to about 30, from about 12 to about 30, from about 14 to about 30, from about 16 to about 30, from about 18 to about 30, To about &lt; RTI ID = 0.0 &gt; 28. &Lt; / RTI &gt;

In one or more embodiments, the glass composition comprises B ₂ O ₃ in mol%, from about 0 to about 8, from about 0 to about 6, from about 0 to about 4, from about 0.1 to about 8, from about 0.1 to about 6, From about 0.1 to about 4, from about 1 to about 10, from about 2 to about 10, from about 4 to about 10, from about 2 to about 8, from about 0.1 to about 5, or from about 1 to about 3. In some instances, the glass composition may be substantially free of B ₂ O ₃ . As used herein, the phrase "substantially free " with respect to the components of the composition may be present as impurities in an amount less than about 0.001 mol%, although the components are not actively or intentionally added to the composition during initial batching. .

In some embodiments, the glass composition may include one or more alkaline earth metal oxides, such as MgO, CaO, and ZnO. In some embodiments, the total amount of the at least one alkaline earth metal oxide may be a non-zero amount up to about 15 mol%. In at least one particular embodiment, the total amount of any one of the alkaline earth metal oxides may be 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% mol%, up to about 2 mol%, or up to about 1.5 mol%. In some embodiments, the total amount of the at least one alkaline earth metal oxide is in the range of about 0.1 to about 10, about 0.1 to about 8, about 0.1 to about 6, about 0.1 to about 5, about 1 to about 10, about 2 to about 10, Can range from about 2.5 to 8. The amount of MgO may range from about 0 mol% to about 5 mol% (e.g., from about 2 mol% to about 4 mol%). The amount of ZnO may range from about 0 to about 2 mol%. The amount of CaO may be from about 0 mol% to about 2 mol%. In one or more embodiments, the glass composition may comprise MgO, and may be substantially free of CaO and ZnO. In one variation, the glass composition may comprise either CaO or ZnO, and substantially none of MgO, CaO and ZnO. In at least one particular embodiment, the glass composition may comprise only two of the alkaline earth metal oxides of MgO, CaO and ZnO, and may be substantially free of the third earth metal oxide.

The total amount of alkali metal oxide R ₂ O in the glass composition is in the range of 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, From about 5 to about 20, from about 6 to about 20, from about 7 to about 20, from about 8 to about 20, from about 9 to about 20, from about 10 to about 20, from about 10 to about 12, from about 5 to about 10, from about 5 to about 8, from about 5 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 Na ₂ O in an amount 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% 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 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 controlled to a certain amount or ratio to balance formability and ion exchange potential. For example, as the amount of Li ₂ O increases, the liquidus viscosity may be reduced, thus hindering the use of some molding methods; However, such glass compositions are ion-exchanged to deeper DOC levels, as described herein. The amount of Na ₂ O can change the liquidus viscosity but can inhibit ion exchange at 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 alternative 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% , 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 comprises Li ₂ O in an amount 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% In an amount of 8 mol%. In one or more alternative embodiments, the glass composition may be substantially free of Li ₂ O, as defined herein.

In one or more embodiments, the glass composition may comprise Fe ₂ O ₃ . In such embodiments, the Fe ₂ O ₃ may comprise 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 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol%, and all ranges and sub-ranges therebetween. In one or more alternative 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 comprise ZrO ₂ . In such embodiments, the ZrO ₂ may comprise 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 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol%, and all ranges and sub-ranges therebetween. In one or more alternative embodiments, the glass composition may be substantially free of ZrO ₂ , as defined herein.

In one or more embodiments, the glass composition comprises P ₂ O ₅ in an amount ranging 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% , 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% . In some instances, the glass composition may be substantially free of P ₂ O ₅ .

In one or more embodiments, the glass composition may comprise TiO _2. In such embodiments, the 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 at least one alternative embodiment, the glass composition, as defined herein, can be substantially free are TiO _2. In some embodiments, the TiO ₂ is present in an amount ranging from about 0.1 mol% to about 6 mol%, or from about 0.1 mol% to about 4 mol%. In some embodiments, the glass may be substantially no TiO _2.

In some embodiments, the glass composition may comprise 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 from 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 include a difference between the total amount of R _x O (mol%) and the amount of Al ₂ O ₃ in the range of from about 0 to about 3. The glass composition of one or more embodiments may exhibit a ratio of the amount of MgO (mol%) to the total amount of RO (mol%) in the range of from about 0 to about 2.

In some embodiments, the composition used for the glass substrate, the 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 And may be co-opted with at least one fining agent. The glass composition according to one or more embodiments further comprises SnO ₂ in the range of from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 2, from about 0.1 to about 1, or from about 1 to about 2 . The glass compositions disclosed herein may be substantially free of As ₂ O ₃ and / or Sb ₂ O ₃ .

In one or more embodiments, the composition specifically includes 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 from 0.05 mol% to about 0.2 mol% SnO ₂ .

In at least one embodiment, the composition comprises from 67 mol% to about 74 mol% SiO ₂ ; From about 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 at least one embodiment, 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 from 0.05 mol% to about 0.2 mol% SnO ₂ .

In at least one embodiment, the composition comprises from 52 mol% to about 63 mol% SiO ₂ ; From about 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% P ₂ O ₅ , Na ₂ O and optionally Li ₂ O, wherein Li ₂ O (mol%) / Na ₂ O (mol% &Lt; 1. Additionally, these compositions may be substantially free of B ₂ O ₃ and K ₂ O. In some embodiments, the composition may include ZnO, MgO, and SnO _2.

In some embodiments, the composition comprises: from about 58 mol% to about 65 mol% SiO ₂ ; From about 11 mol% to about 19 mol% Al ₂ O ₃ ; From 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 from 0 mol% to about 6 mol% ZnO. In some embodiments, the composition comprises about 63 mol% to about 65 mol% SiO ₂ ; From about 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 from 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, where R ₂ O = Li ₂ O + Na ₂ O. In some embodiments, 65 mol% <SiO ₂ (mol%) + P ₂ O ₅ (mol%) <67 mol%. In certain _{embodiments, R 2 O (mol%)} + R'O (mol%) - Al 2 O 3 (mol%) + P 2 O 5 (mol%)> -3 mol% , wherein 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 the glass product before being chemically strengthened, as described herein, are shown in Table 1.

Representative compositions 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

Other representative compositions of glass-based products before being chemically reinforced, as described herein, are shown in Table 1A. Table 1B lists the selected physical properties determined for the embodiments listed in Table 1A. The physical properties listed in Table 1B are: density; Cold and hot CTE; Strain point, annealing point and softening point; 10 ¹¹ Poise, 35 kP, 200 kP, liquidus, and zircon decomposition temperatures; Zircon decomposition and liquid phase viscosity; Poa Songbee; Young; 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 lower and / or a Young's modulus of at least 70 GPa, and in some embodiments, a Young's modulus of up to 80 GPa.

[Table 1A]

Representative compositions before chemical strengthening.

[Table 1B]

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

When the glass article comprises glass-ceramics, the crystalline phase may comprise? -Spodulmene, 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 forms or sculpted substrates. In some cases, the glass product may have a 3D or 2.5D form. The glass article may 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, the refractive index value is 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 at least one 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 area of the glass article. The length, width and thickness dimensions of the glass product may also vary depending on the application or use of the product.

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

Float-forming glass articles can be characterized by a smooth surface, and a uniform thickness is created by flowing molten glass onto a layer of molten metal, typically tin. In the representative process, the molten glass injected onto the surface of the molten tin layer forms a floating glass ribbon. As the glass ribbon flows along the tin bath, the temperature gradually decreases until the glass ribbon solidifies into a solid glass product that can be lifted from the tin onto the roller. As soon as the glass product is taken out of the bath, the glass product can be further cooled and annealed to reduce internal stress. When the glass product is a glass ceramic, the glass product formed from the float process can be applied to a ceramicization process in which one or more crystalline phases are generated.

The down-drawing process produces a glass article having a uniform thickness that has a relatively intact surface. Since the average flexural strength of the glass product is controlled by the amount and size of the surface flaws, the original surface with minimal contact has a higher initial strength. If such a high strength glass product is then further strengthened (e.g., chemically), the resulting strength may be higher than the strength of the glass product having a lapped and polished surface. Down-drawn glass articles can be drawn to a thickness of less than about 2 mm. In addition, the down-pulled glass product has a very flat, smooth surface that can be used for its final application without costly grinding and polishing. If the glass product is a glass ceramic, the glass product formed from the down-drawing process may be applied to a ceramicization 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 channels have weirs on top of each other along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the weir. Due to gravity, the molten glass flows under the outer surface of the drawing tank with two flowing glass films. These outer surfaces of the draw tank extend downward and inward so that they engage at the edge under the draw tank. The two flowing glass films combine at this edge to fuse and form a single flowing glass product. The fusion drawing method offers the advantage that no part of the outer surface of the resultant glass product comes into contact with any part of the device because the two overflowing glass films fuse together in the channel. Thus, the surface properties of the fusion drawn glass product are not affected by such contact. When the glass product is a glass ceramic, the glass product formed from the fusion process may be applied to a ceramification process in which one or more crystalline phases are generated.

The slot drawing process is distinguished from the fusion drawing method. In the slot drawing process, the molten raw glass is provided in the drawing tank. The bottom of the draw tank has an open slot with a nozzle extending the length of the slot. The molten glass flows through the slots / nozzles and is drawn downward into the continuous glass product and into the annealing area. If the glass product is a glass ceramic, the glass product formed from the slot-drawing process can be applied to a ceramicization process in which one or more crystalline phases are generated.

In some embodiments, the glass article is disclosed in U.S. Patent No. 8,713,972 entitled "Precision Glass Roll Forming Process and Apparatus", U.S. Patent No. 9,003,835 entitled "Precision Roll Forming of Textured Sheet Glass" U.S. Patent Publication No. 20150027169 entitled " Methods And Apparatus For Forming A Glass Ribbon ", and U.S. Patent Publication No. 20050099618 entitled " Apparatus and Method for Forming Glass Glass Articles & May be formed using a rolling process, the entire contents of which are incorporated herein by reference. More particularly, the glass article comprises a supply of a vertical stream of molten glass, a supply of molten glass or glass-ceramics having a pair of forming rolls maintained at a surface temperature of at least about 500 ° C or at least about 600 ° C Forming a formed glass ribbon having a thickness formed by forming a stream, forming a glass ribbon having a pair of sizing rolls held at a surface temperature of about 400 DEG C or less, To produce a sagged glass ribbon having a desired thickness and a desired thickness uniformity. The apparatus used to form the glass ribbon comprises: a glass injection device for supplying a fed stream of molten glass; A pair of forming rolls maintained at a surface temperature of at least about 500 DEG C to form a formed glass ribbon having a thickness formed by receiving a fed stream of molten glass and thinning the fed stream of molten glass between the forming rolls A shaping roll spaced closely adjacent to each other defining a glass forming gap between shaping rolls having a vertically positioned glass forming gap below a glass injection apparatus for the glass forming apparatus; And a pair of sieving rolls maintained at a surface temperature of 400 DEG C or lower, wherein the sieving rolls comprise a glass ribbon formed to produce a sagged glass ribbon having a desired thickness and a desired thickness uniformity Are spaced apart from each other by defining a glass siding gap between the sieving rolls having a glass siding gap vertically positioned below the forming roll to receive and thin the formed glass ribbon.

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 drawing methods. For example, thin rolls can be utilized to form glass articles when the glass exhibits a liquidus viscosity of less than 100 kP.

The glass product may be acid-polished or otherwise treated to remove or reduce the effects of surface flaws.

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

In some embodiments, the method may include chemically enriching or ion-exchanging the glass substrate in one or more steps using a continuous immersion step in one or more bathtubs. For example, two or more baths can be used continuously. The composition of one or more baths may comprise a single metal (e.g., Ag +, Na +, K +, Rb +, or Cs +) or a combination of metals in the same bath. When one or more baths are utilized, the baths may have the same or different compositions and / or temperatures. The immersion time in each such bath can be varied to provide the same or a desired stress profile.

In one or more embodiments, the second bath or subsequent bath can 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 chemical depth of the DOC and / or layer. In such embodiments, the second or subsequent bath may comprise a single metal (e.g., 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 produce a larger surface CS. In some embodiments, the immersion time of the glass material in the second or subsequent bath may also be adjusted to produce a larger surface CS without affecting the chemical depth of the DOC and / or layer. For example, the immersion time in the second or subsequent bath may be less than 10 hours (e.g., less than about 8 hours, less than about 5 hours, less than about 4 hours, less than about 2 hours, less than about 1 hour, about 30 minutes About 15 minutes or less, or about 10 minutes or less).

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

Example

Various embodiments will be made more apparent by the following examples.

Example 1

Example 1A-1B and comparative examples is a glass article according to 1C-1G, 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 RTI ID = 0.0 &gt; ₅ &lt; / RTI &gt; nominal glass composition. The glass substrate has a thickness of 0.4 mm and a length and width dimension of 50 mm. The glass substrate is chemically strengthened by an ion exchange process comprising immersing 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 with 90 grit SiC particles at a pressure of 5 psi, 15 psi, or 25 psi, as also shown in Table 2, and the major surfaces of each sample were polished and the AROR It applies to the test. Table 2 shows the breakage load or average axial flexural strength of glass products.

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

The fracture loads or average axial flexural strengths of the examples after abrasion at 15 psi and 25 psi are plotted in FIG. As shown in FIG. 11, Examples 1A and 1B show the maximum average dynamic flexural strength after worn at 25 psi. Thus, the AROR performance of Examples 1A and 1B show that these glass products exhibit a highly diced fracture pattern, which, in particular, shows an improved retention strength 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 reinforcing the glass substrate. The glass substrates used in Examples 2A-2C and Comparative Examples 2E-2F were a mixture of 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 in Example 1.

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

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

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

Example 3

Glass products according to Examples 3A-3K and Comparative Examples 3L-3X are made by providing a glass substrate and strengthening the glass substrate. The substrate used in Examples 3A-3D had the same composition as in Example 1 and the substrates used in Comparative Examples 3L-3X were 69 mol% SiO ₂ , 10.3 mol% Al ₂ O ₃ , 15.2 mol% Na ₂ O, it has a nominal glass composition of 5.4 mol% MgO, and 0.2 mol% SnO _2.

The glass substrate has a thickness of 0.4 mm and a length and width dimension 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. Comparative Example 3L-3X was ion-exchanged and the resulting glass product exhibited a surface CS of 912 MPa and a DOC of 37 탆, as measured by FSM.

The resulting glass article is then subjected to a tungsten carbide conical spherical scribe for one shot from a falling distance (as shown in Tables 4 and 5) to one major surface of each product, Is applied to the fracture by the step of evaluating the breakage or breakage pattern in terms of how much debris results and the vulnerability of the glass product, whether it is broken immediately or not at all.

Breakage characteristics and fracture mechanics of Examples 3A-3K. room. Hit number Number of shards (#) Break (Y / N) Falling distance (inches) Time for 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

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

* DNB = not broken

As shown in Table 4-5, as compared to the chemically reinforced glass products (i.e., Examples 3A-3K) under the conditions of dicing / fragmentation of heights occurring at breakage, conditions near the frangibility limit It is clear that the chemically reinforced glass product (i.e., Comparative Example 3L-3X) is much more likely to experience delayed failure. Specifically, more than 80% of Comparative Example 3L-3X was broken in a delayed manner, whereas in Table 4 the sample was not broken or destroyed immediately. In addition, Comparative Example 3L-3X exhibits fewer, larger, and larger debris fragments than Examples 3A-4K, which are broken by dicing of height and exhibiting debris with a low aspect ratio.

Example 4

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

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

Figure 14 shows the results of the steps of providing the same substrate as in 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 , Measured by Roussev I with IWKB analysis, which represents the stress profile.

Example 5

A glass article according to Examples 5A-5D (Comparative Examples B and C) is made by providing a glass substrate having the same nominal composition as Examples 2A-2C and reinforcing 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 Melting bath composition Melting bath temperature (캜) Immersion time (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

Example 5A and Comparative Example 5B were bonded to a transparent substrate using a pressure sensitive adhesive supplied by 3M under the trade name 468MP, which was applied in the same manner and with the same thickness. Example 5A and Comparative Example 5B were broken, and the resulting fractured glass product was evaluated. Figs. 15A and 15B show a fractured image of Example 5A and Comparative Example 5B, respectively. As shown in FIG. 15A, Example 5A exhibits a higher dicing behavior and results in debris having an aspect ratio of less than about 2. As shown in FIG. 15B, Comparative Example 5B results in debris having a higher aspect ratio.

Comparative Example 5C and Example 5D are not constrained by the adhesive, and are broken. The resulting fractured glass product is evaluated. Figs. 15C and 15D show fractured images of Comparative Examples 5C and 5D, respectively. As shown in Fig. 15C, Comparative Example 5C shows larger debris. As shown in FIG. 15D, Example 5D results in debris showing dicing. Sub-fragments (not shown) are believed not to extend through the thickness of the glass article.

Example 6

The glass product according to Example 6 is made by providing the glass substrate having the same nominal composition as Examples 3A-3K and reinforced in the same manner. Example 6 is evaluated for haze or readability after rupture at different viewing angles. After rupture, Example 6 shows a high degree of dicing, but still exhibits excellent readability in a 90 [deg.] Viewing angle relative to the surface plane or major surface of the glass article. The readability drops as the viewing angle decreases, as illustrated in the images of Figures 16A-16D. Figure 16a shows that the text placed after Example 6 is still visible and readable at a viewing angle of 90 degrees relative to the surface plane or major surface of the glass article. Figure 16B shows that it is somewhat visible and readable at a viewing angle of about 67.5 degrees. 16C-16D, the text is not clear or readable at a viewing angle of 45 degrees and 22.5 degrees relative to the surface plane or major surface of the glass article. Thus, Embodiment 6 can function as a personal protection screen when only the viewer is used in the display to clearly read or view the display, but other viewers beside the viewer can not clearly read the display .

Example 7

The glass product according to Examples 7A-7C is made by providing a glass substrate having a 2.5-dimensional shape, but each having a different thickness (i.e., Example 7A has a thickness of 1 mm, Example 7B has a thickness of 0.8 mm Thickness, and Example 7C has 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 is the same as in Examples 2A-2C. The storage tensile energy of each substrate is calculated according to a function of ion exchange time using a molten bath having a temperature of 430 캜. The storage tensile energy is calculated using the total amount of stress over the CT region (327 in Figure 4) as measured by SCALP. The calculated storage tensile energy is plotted as a function of ion exchange time in FIG. For illustrative purposes, the dotted line at the storage tensile energy value of 10 J / m &lt; 2 &gt; is drawn to show an approximate threshold for vulnerability. The highlighted zone represents the ion-exchange conditions for a single part having a thickness range of 0.5-1.0 mm, which represents the behavior described herein. Specifically, this range allows for optimal mechanical performance and similar degree of dicing across the area of the part when the part is broken.

When the known vulnerability limits are used to determine the ion exchange parameters for various thicknesses, at time A, which is the ion exchange time at which the storage tensile energy reaches less than 10 J / m &lt; 2 &gt;, the glass substrate, It is not easy, and a glass substrate having 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 fragile, and a glass substrate having a thickness of 1 mm to 0.8 mm is considered fragile. Thus, when using the current definition of vulnerability, Figure 17 shows that a relatively thick portion in a given bath at a given temperature, or a relatively thick portion in a given bath temperature, rather than a thinner portion of intentionally non- Lt; RTI ID = 0.0 &gt; ion-exchange &lt; / RTI &gt; time for regions of non-uniform thickness. In order to provide a substantially-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 achieve fragmentation or dicing It may be desirable to install a higher storage tension energy that will be selected to limit the degree of storage tension.

Figure 18 shows that the installed tensile energy, shown at 11, is represented by the center tension (CT), which is used as the more common descriptor of tensile energy in the central region of the ion- The sample shown in Fig. 17 is shown.

Example 8

Example 8 includes a glass product made by the steps of providing a glass substrate having the same nominal composition as in Example 1 and reinforcing the glass substrate. The glass substrate has a thickness of 0.4 mm and is chemically reinforced by a two-step ion exchange process wherein the glass substrate is first subjected to a first step 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 product 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, as measured by Roussev I applied to IWKB analysis. FIG. 19 shows the compressive stress (expressed as a negative value) and the tensile stress (expressed as a positive value) as a function of depth in micrometers.

Viewpoints (1) of the present disclosure include a first surface and a second surface opposing the first surface, the thickness defining a thickness t of about 1.1 mm or less; And a compressive stress layer extending from the first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; Here, after the glass product is broken according to the vulnerability test, the glass product includes a plurality of fragments, wherein at least 90% of the plurality of fragments have an aspect ratio of about 5 or less.

The perspective (2) of the present disclosure is that, in the tempered glass article of the perspective (1), the glass article is measured by the vulnerability test and is broken into a plurality of fragments in one second or less.

Viewpoint (3) of the present disclosure is that, in tempered glass articles of perspective (1) or perspective (2), at least 80% of the plurality of fragments have a maximum dimension of 3 · t or less.

Viewpoint (4) of the present disclosure is that, in a tempered glass article according to any one of aspects (1) to (3), at least 50% of the plurality of fragments comprises an aspect ratio of 2 or less.

Viewpoint (5) of the present disclosure is that, in a tempered glass article according to any one of aspects (1) to (4), at least 50% of the plurality of fragments comprise a volume of less than or equal to about 10..

A perspective (6) of the present disclosure relates to a tempered glass article according to any one of aspects (1) to (5), wherein the plurality of fragments comprise a released part of the debris, , And 10% or less of the plurality of fragments.

A perspective (7) of the present disclosure relates to a tempered glass article according to any of aspects (1) to (6), wherein the glass article comprises a first weight before breaking, Wherein the non-ejected portion of the debris has a second weight, and a difference between the first and second weights is greater than a first weight of the first weight %to be.

The viewpoint (8) of the present disclosure is measured by the vulnerability 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 one second or less 99% or more.

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

A perspective (10) of the present disclosure relates to a tempered glass article according to any of aspects (1) to (9), wherein the glass article comprises a surface compressive stress and a center tensile, Is in the range of about 0.1 to about 1.

Viewpoint 11 of the present disclosure is that in a tempered glass article of perspective 10 the center tension is 100 MPa / (t / 1 mm) or more (in MPa units), where t is mm.

View 12 of the present disclosure is the tempered glass article of any one of viewpoints 10 to 11 wherein the center tension is 50 MPa or more.

View 13 of the present disclosure is the tempered glass article of any one of viewpoints 10 to 12 wherein the surface compressive stress is at least 150 MPa.

View 14 of the present disclosure is the tempered glass article of any one of viewpoints 10 to 13 wherein the surface compressive stress is at least 400 MPa.

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

A perspective (16) of the present disclosure relates to a tempered glass article according to any of aspects (1) to (15), wherein the glass article comprises an alkali aluminosilicate glass, Or an alkali aluminoborosilicate glass.

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

Viewpoints 18 of this 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 compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; Here, the glass product exhibits a breakdown load of at least about 10 kgf after being polished with 90-grit SiC particles for 5 seconds at a pressure of 25 psi.

View 19 of the present disclosure, in a tempered glass article of perspective 18, the glass article comprises a stored tensile energy of 20 J / m &lt; 2 &gt;

A perspective 20 of the present disclosure relates to a tempered glass article according to any of aspects 18 or 19 wherein the glass article comprises a surface compressive stress and a center tensile force, The ratio of the tension is in the range of about 0.1 to about 1.

The perspective 21 of the present disclosure is that in the tempered glass article of perspective 20, the center tension CT is at least 50 MPa.

View 22 of the present disclosure, in tempered glass article of perspective 20 or view 21, the surface compressive stress is at least 150 MPa.

View 23 of the present disclosure is the tempered glass article of any one of viewpoints 20 to 22 wherein the surface compressive stress is at least 400 MPa.

View 24 of this disclosure is that, in a tempered glass article from any one of viewpoints 20 to 23, the DOC comprises at least about 0.2 t.

Viewpoint 25 is characterized in that in a tempered glass article according to any of aspects 18 to 24, said glass article is selected from the group consisting of alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminosporosilicate glass or alkali aluminosilicate glass, Novolacsilate glass.

View 26 of this disclosure is that, in a tempered glass article from any one of viewpoints 20 to 25, the glass article is attached to the substrate.

View (27) of the present disclosure relates to a tempered glass substrate; A sealing layer; And a support, wherein the tempered glass substrate defines a first surface and a second surface opposing the first surface, the first surface defining a thickness t of about 1.1 mm or less, (DOC) of greater than about 0.11 占 으로부터, and a center tension (CT) of at least 50 MPa, wherein the device is a tablet, a transparent display, a mobile phone, a video player, A terminal device, an electronic-reader, a laptop computer, or a non-transparent display.

Viewpoint 28 is characterized in that in the apparatus of point 27, after the glass product is broken according to the vulnerability test, the glass product comprises a plurality of fragments having an aspect ratio of about 5 or less.

Viewpoint 29 is an apparatus in view 27 or view 28 wherein the glass product is measured by a vulnerability test and is broken into a plurality of fragments in 1 second or less.

Viewpoint 30 is such that in an apparatus of perspective 28 or view 29, at least 80% of the plurality of fragments have a maximum dimension of 5 · t or less.

In viewpoint (31), in any one of the viewpoints (28) to (30), at least 50% of the plurality of fragments each include an aspect ratio of 2 or less.

Viewpoint 32 is any one of view 28 to view 31 wherein at least 50% of the plurality of fragments comprise a volume of about 10 ㎣ or less.

Viewpoint 33 is any of the viewpoints 28 to 32 wherein the plurality of debris comprises a released portion of the debris wherein the released portion of the debris comprises the plurality of It contains less than 10% of the debris.

Viewpoint 34 is characterized in that in any one of view 28 to view 33 the glass product comprises a first weight before fracture and wherein said plurality of fragments comprises a portion of the debris and / The non-ejected portion of the debris has a second weight, and the difference between the first weight and the second weight is 1% of the first weight.

The viewpoint 35 is measured by the vulnerability test in any one of the viewpoints 28 to 34. The probability that the glass product will be broken into a plurality of fragments in 1 second or less is 99% .

Viewpoint 36 is any of the viewpoints 28 to 35 wherein the glass product comprises a stored tensile energy of greater than or equal to 20 J / m 2.

The viewpoint (37) is characterized in that, in the viewpoint (27) to the viewpoint (36), the glass product includes a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress Range from about 0.1 to about 1.

Viewpoint 38 is the apparatus of point 37, wherein the surface compressive stress is at least 150 MPa.

In viewpoint 39, in any one of viewpoints 27 to 38, the DOC includes about 0.2 t or more.

Viewpoint 40 is any of the viewpoints 27 to 39 wherein the glass article is selected from the group consisting of an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminosporosilicate glass, Silicate glass.

In viewpoint (41), in any one of the viewpoints (27) to (40), the glass product is disposed on the sealing layer.

Viewpoint 42 includes a first surface and a second surface opposing the first surface, defining a thickness t of about 1.1 mm or less; And a compressive stress layer extending from the first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; Here, after the glass article is laminated to the sealing layer and broken according to the vulnerability test, the glass article comprises a rupture, wherein at least 5% of the rupture extends only partially through the thickness.

Viewpoint 43 is a tempered glass article of perspective 42 in which the glass article is measured by a vulnerability test and is broken into a plurality of fragments in less than one second.

Viewpoint 44 is a tempered glass article of perspective 42 or view 43 wherein the glass article comprises a stored tensile energy of at least 20 J / m 2.

Viewpoint 45 is characterized in that in a tempered glass article from any one of viewpoints 44 to 44, the glass article comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress Is in the range of about 0.1 to about 1.

Viewpoint 46 is a tempered glass article of perspective 45 wherein the center tension is 50 MPa or greater.

Viewpoint 47 is a tempered glass article of perspective 45 or view 46 wherein the surface compressive stress is at least 150 MPa.

Viewpoint 48 is the tempered glass article of any one of aspects 42 to 47 wherein the DOC comprises at least about 0.2 t.

Viewpoint 49 is a tempered glass article according to any of aspects 42 to 48 wherein the glass article comprises an alkali aluminosilicate glass, an alkali containing borosilicate glass or an alkali aluminoborosilicate glass .

Viewpoint 50 is that in a tempered glass article from any of view 42 to view 49, the glass article is disposed on the sealing layer. Viewpoint 51 includes a housing having a front surface; An electrical component at least partially provided within the housing and including at least a controller, a memory, and a display; And a cover glass disposed on the front of the housing and on the display, the cover glass comprising a tempered glass article, wherein the tempered glass article has a thickness (t) of less than about 1.1 mm, A second surface opposing the first surface and the first surface; A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; And a center tension (CT) of at least about 50 MPa.

Viewpoint 52 is a consumer electronics device in perspective 51 wherein after the glass product is broken according to the vulnerability test, the glass product comprises a plurality of fragments having an aspect ratio of about 5 or less.

Viewpoint 53 is the consumer electronics of perspective 52 where the glass product is measured by the vulnerability test and is broken into a plurality of fragments in less than one second.

Viewpoint 54 is such that in consumer electronics of perspective 52 or view 53, at least 80% of the plurality of fragments have a maximum dimension of 2 · t or less.

Viewpoint (55) is that, in any of consumer viewpoints (52) to (54), at least 50% of said plurality of fragments each comprise an aspect ratio of 2 or less.

Viewpoint (56) is that, in any of consumer viewpoints (52) to (55), at least 50% of the plurality of fragments comprise a volume of about 10 ㎣ or less.

Viewpoint 57 is a consumer electronic device according to any one of aspects 52 to 56 wherein the plurality of fragments comprise a discharged portion of the debris, But not more than 10% of a plurality of fragments.

Viewpoint 58 is a consumer electronic device according to any one of aspects 52 to 57 wherein the glass product comprises a first weight prior to rupture and wherein the plurality of ruptures comprise Wherein the non-ejected portion of the debris has a second weight, and wherein the difference between the first weight and the second weight is greater than a first weight of the first weight %to be.

Viewpoint 59 is measured by a vulnerability test in any consumer electronics device from perspective 53 to perspective 58 and the probability that the glass product will break into multiple fragments in less than one second is 99 %.

The perspective 60 is that, in a consumer electronic device according to any of aspects 51 to 59, the glass product comprises a stored tensile energy of 20 J / m 2 or more.

A perspective view (61) is a view of a consumer electronic device according to any of aspects (51) to (60), wherein the glass product comprises a surface compressive stress and a center tension, Is in the range of about 0.1 to about 1.

Viewpoint 62, in the consumer electronics of viewpoint 61, said surface compressive stress is greater than or equal to 150.

Viewpoint (63), in any of consumer viewpoints (51) to (62), the DOC includes about 0.2 t or more.

Viewpoint 64 is characterized in that in a consumer electronic device according to any of aspects 51 to 63, the glass article is selected from the group consisting of an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminosporosilicate, And a silicate glass.

Viewpoint 65 is that in a consumer electronic device according to any one of aspects 51 to 64, the glass article is disposed on a sealing layer.

Viewpoint 66 is a consumer electronic device according to any of aspects 51 to 65 wherein the consumer electronics product is a tablet, transparent display, cell phone, video player, information terminal device, electronic reader, , Or a non-transparent display.

Viewpoint 67 is a packaging product comprising a housing including an opening, an exterior surface, and an interior surface defining the enclosure, Wherein the housing comprises a tempered glass product, wherein the tempered glass product has 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 said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; And a center tension (CT) of 50 MPa or more.

Viewpoint 68 is characterized in that in the packaging product of aspect 67 the glass product comprises a plurality of debris having an aspect ratio of about 5 or less after the glass product is broken according to the vulnerability test, The product, as measured by the vulnerability test, is broken into a plurality of pieces at 1 second or less.

Viewpoint 69 is such that in a packaging product of view 68, at least 80% of the plurality of fragments have a maximum dimension of 2 · t or less.

Viewpoint 70 is the packaging product of aspect 68 or aspect 69 wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less.

In viewpoint (71), in any one of the packaging products of aspects (68) to (70), at least 50% of the plurality of fragments comprise a volume of less than or equal to about 10..

A perspective view (72) according to any one of aspects (68) to (71), wherein said plurality of debris comprises a discharged portion of debris, wherein said discharged portion of said debris Lt; / RTI &gt; of the debris of &lt; RTI ID =

A perspective view (73) according to any one of aspects (68) to (72), wherein the glass product comprises a first weight before breaking, and wherein the plurality of fragments Wherein the non-ejected portion of the debris has a second weight, and wherein the difference between the first weight and the second weight is less than 1% of the first weight, to be.

The perspective 74 is measured by a vulnerability test in any one of the packaging products from the perspective view 68 to the viewpoint 73. The probability that the glass product is broken into a plurality of fragments at a time of 1 second or less is 99% Or more.

Viewpoint (75) is the packaging product of any one of aspects (67) to (74), wherein the glass product comprises a stored tensile energy of greater than or equal to 20 J / m 2.

A perspective view (76) according to any one of aspects 67 to 75, wherein the glass article comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress, Range from about 0.1 to about 1.

In viewpoint (77), in the packaging product of aspect (76), the surface compressive stress is 150 or more.

In viewpoint 78, in any one of the perspective products 67 to 77, the DOC includes about 0.2 t or more.

A viewpoint (79) is that in any of the packaging products from any of aspects (67) to (78), the glass article is selected from the group consisting of an alkali aluminosilicate glass, an alkali containing borosilicate glass, an alkali aluminosporosilicate or an alkali aluminoboron Silicate glass.

The perspective view 80 is that, in any of the packaging products of aspects 67 to 72, the glass product is disposed on the sealing layer.

The perspective 82 further comprises a pharmaceutical substance in any one of the packaging products from aspects 67 to 80.

The perspective 83 further comprises a cap disposed in the opening in any one of the perspective view 67 to the perspective view 81 packaging product.

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

Claims (82)

A second surface confronting the first surface and a first surface defining a thickness t of about 1.1 mm or less;
A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏;
Here, after the glass product is broken according to the vulnerability test, the glass product includes a plurality of fragments, wherein at least 90% of the plurality of fragments have an aspect ratio of about 5 or less. The method according to claim 1,
Wherein the glass product is measured by a vulnerability test and is broken into a plurality of fragments in 1 second or less. The method according to claim 1 or 2,
Wherein at least 80% of the plurality of fragments have a maximum dimension of 3 · t or less. The method according to any one of the preceding claims,
Wherein at least 50% of the plurality of fragments comprises an aspect ratio of 2 or less. The method according to any one of the preceding claims,
Wherein at least 50% of the plurality of debris comprises a volume of less than or equal to about 10 microns. The method according to any one of the preceding claims,
Wherein the plurality of fragments comprises a released portion of the debris, wherein the released portion of the debris comprises no more than 10% of the plurality of debris. The method according to any one of the preceding claims,
Wherein the glass product comprises a first weight prior to fracture and wherein the plurality of fragments comprise a released portion of the debris and a non-emitted portion of the debris, wherein the non- And wherein the difference between the first weight and the second weight is 1% of the first weight. The method according to any one of the preceding claims,
Measured by vulnerability testing, the glass product has a 99% or greater probability of fracture by multiple debris in less than one second. The method according to any one of the preceding claims,
Said glass product comprising a stored tensile energy of at least 20 J / m &lt; 2 &gt;. The method according to any one of the preceding claims,
Wherein the glass article comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. &lt; Desc / Clms Page number 17 &gt; The method of claim 10,
Wherein the center tension is not less than 100 MPa / (t / 1 mm) (unit of MPa), wherein t is mm. The method of claim 10,
Wherein said center tension is at least 50 MPa. The method according to any one of claims 10-12,
Wherein the surface compressive stress is at least 150 MPa. The method according to any one of claims 10-13,
Wherein said surface compressive stress is at least 400 MPa. The method according to any one of claims 10-14,
Wherein the DOC comprises at least about 0.2 t. The method according to any one of the preceding claims,
Wherein the glass article comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate glass or an alkali aluminoborosilicate glass. The method according to any one of the preceding claims,
Wherein the glass article is disposed on the sealing layer. A second surface confronting the first surface and a first surface defining a thickness t of about 1.1 mm or less;
A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏;
Wherein the glass product exhibits a break load greater than about 10 kgf after being polished with 90-grit SiC particles for 5 seconds at a pressure of 25 psi. 19. The method of claim 18,
Wherein said glass product comprises a stored tensile energy of at least 20 J / m &lt; 2 &gt;. The method according to claim 18 or 19,
Wherein the glass product comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. The method of claim 20,
Wherein said center tension (CT) is at least 50 MPa. The method according to claim 20 or 21,
Wherein the surface compressive stress is at least 150 MPa. The method of any one of claims 20-22,
Wherein said surface compressive stress is at least 400 MPa. The method according to any one of claims 18-23,
Wherein the DOC comprises at least about 0.2 t. The method according to any one of claims 18-24,
Wherein the glass article comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate glass or an alkali aluminoborosilicate glass. The method according to any one of claims 18 to 25,
Wherein the glass article is attached to a substrate. Tempered glass substrate;
A sealing layer; And
An apparatus comprising a support,
Wherein the tempered glass substrate has 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 in depth (DOC), and a center tension (CT) of at least 50 MPa,
Wherein the device comprises a tablet, a transparent display, a cell phone, a video player, an information terminal device, an electronic reader, a laptop computer, or a non-transparent display. 28. The method of claim 27,
Wherein the glass product comprises a plurality of debris having an aspect ratio of about 5 or less after the glass product is broken according to the vulnerability test. 29. The method of claim 28,
Wherein the glass product is measured by a vulnerability test and is broken into a plurality of fragments in 1 second or less. 29. The method of claim 28 or 29,
Wherein at least 80% of the plurality of fragments have a maximum dimension of 5 · t or less. 28. The method of any one of claims 28-30,
Wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less. 28. The method of any one of claims 28-31,
Wherein at least 50% of the plurality of debris comprises a volume of less than or equal to about 10 pounds. 29. The method of any one of claims 28-32,
Wherein the plurality of debris comprises a discharged portion of the debris, wherein the discharged portion of the debris comprises less than or equal to 10% of the plurality of debris. 28. A method according to any one of claims 28-33,
Wherein the glass product comprises a first weight before fracture and wherein the plurality of fragments comprise a released portion of the debris and a non-emitted portion of the debris, wherein the non- And wherein the difference between the first weight and the second weight is 1% of the first weight. 28. The method of any one of claims 28-34,
Wherein the glass product has a probability of breaking up into a plurality of fragments of not less than 99% under 1 second or less as measured by a vulnerability test. 35. The method of any one of claims 27-35,
Wherein the glass product comprises a stored tensile energy of at least 20 J / m &lt; 2 &gt;. 35. The method of any one of claims 27-36,
Wherein the glass product comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. &lt; Desc / Clms Page number 17 &gt; 37. The method of claim 37,
Wherein the surface compressive stress is at least 150 MPa. 38. The method of any one of claims 27-38,
Wherein the DOC comprises at least about 0.2 t. 39. The method of any one of claims 27-39,
Wherein the glass article comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate glass or an alkali aluminoborosilicate glass. 40. The method of any one of claims 27-40,
Wherein the glass article is disposed on the sealing layer. A second surface confronting the first surface and a first surface defining a thickness t of about 1.1 mm or less;
A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏;
Wherein after the glass article is laminated to the sealing layer and broken according to the vulnerability test, the glass article comprises a rupture, wherein at least 5% of the rupture extends only partially through the thickness, Tempered glass products. 43. The method of claim 42,
Wherein the glass product is measured by a vulnerability test and is broken into a plurality of fragments in 1 second or less. 43. The method of claim 42 or 43,
Said glass product comprising a stored tensile energy of at least 20 J / m &lt; 2 &gt;. 42. The method of any one of claims 42-44,
Wherein the glass product comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. 46. The method of claim 45,
Wherein said center tension is at least 50 MPa. 45. The method of claim 45 or 46,
Wherein said surface compressive stress is at least 150 MPa. 42. A method according to any one of claims 42-47,
Wherein the DOC comprises at least about 0.2 t. 42. A compound according to any one of claims 42-48,
Wherein the glass article comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass or an alkali aluminoborosilicate glass. 42. The method of any one of claims 42-49,
Wherein the glass article is disposed on the sealing layer. A housing having a front surface;
An electrical component at least partially provided within the housing and including at least a controller, a memory, and a display; And
And a cover glass disposed on the front of the housing and over the display and including a tempered glass article,
Wherein the tempered glass article comprises:
A second surface confronting the first surface and a first surface defining a thickness t of about 1.1 mm or less;
A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; And
And a center tension (CT) of at least about 50 MPa. 54. The method of claim 51,
Wherein the glass product comprises a plurality of debris having an aspect ratio of about 5 or less after the glass product is broken according to the vulnerability test. 53. The method of claim 52,
Wherein the glass product is measured by a vulnerability test and is broken into a plurality of fragments in 1 second or less. 53. The method of claim 52 or 53,
Wherein at least 80% of the plurality of fragments have a maximum dimension of 2 · t or less. 52. The method of any one of claims 52-54,
Wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less. 55. The method of any one of claims 52-55,
Wherein at least 50% of the plurality of debris comprises a volume of less than about 10 microns. 52. The method of any one of claims 52-56,
Wherein the plurality of debris comprises a discharged portion of the debris, wherein the discharged portion of the debris comprises no more than 10% of the plurality of debris. 52. The method of any one of claims 52-57,
Wherein the glass product comprises a first weight before fracture and wherein the plurality of fragments comprise a released portion of the debris and a non-emitted portion of the debris, wherein the non- 2 weight, and wherein the difference between the first weight and the second weight is 1% of the first weight. 54. The method of any one of claims 53-58,
Measured by a vulnerability test, the probability that the glass product will break into multiple pieces below 1 second or less is 99% or more. 51. The method of any one of claims 51-59,
Said glass product comprising a stored tensile energy of at least 20 J / m &lt; 2 &gt;. 60. The method of any one of claims 51-60,
Wherein the glass product comprises a surface compressive stress and a center tension wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. 62. The method of claim 61,
Wherein the surface compressive stress is greater than or equal to 150. 62. The method of any one of claims 51-62,
Wherein the DOC comprises at least about 0.2 t. 62. The method of any one of claims 51-63,
The glass article comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate or an alkali aluminoborosilicate glass. 60. The method of any one of claims 51-64,
Wherein the glass article is disposed on the sealing layer. 60. The method of any one of claims 51-65,
The consumer electronics product includes 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. CLAIMS What is claimed is: 1. A packaging article comprising: a housing including an opening, an exterior surface and an interior surface defining the enclosure;
Wherein the housing comprises a tempered glass article,
Wherein the tempered glass article comprises:
A second surface confronting the first surface and a first surface defining a thickness t of about 1.1 mm or less;
A compressive stress layer extending from said first surface to a depth of compression (DOC) in excess of about 0.11 占 퐏; And
And a center tension (CT) of at least 50 MPa. 65. The method of claim 67,
After the glass article is broken according to the vulnerability test, the glass article comprises a plurality of fragments having an aspect ratio of about 5 or less, and
Here, the glass product is measured by a vulnerability test, and is broken into a plurality of fragments in 1 second or less. 69. The method of claim 68,
Wherein at least 80% of the plurality of fragments have a maximum dimension of 2 · t or less. 69. The method of claim 68 or 69,
Wherein at least 50% of the plurality of fragments each comprise an aspect ratio of 2 or less. 70. The method of any one of claims 68-70,
Wherein at least 50% of the plurality of debris comprises a volume of less than or equal to about 10 pounds. 69. The method of any one of claims 68-71,
Wherein the plurality of debris comprises a discharged portion of the debris, wherein the discharged portion of the debris comprises no more than 10% of the plurality of debris. 68. The method of any one of claims 68-72,
Wherein the glass product comprises a first weight before fracture and wherein the plurality of fragments comprise a released portion of the debris and a non-emitted portion of the debris, wherein the non- 2, and wherein the difference between the first weight and the second weight is 1% of the first weight. 68. The method of any one of claims 68-73,
Measured by a vulnerability test, the probability that the glass product breaks into a plurality of fragments in less than one second is greater than or equal to 99%. 67. The method of any one of claims 67-74,
Wherein the glass product comprises a stored tensile energy of at least 20 J / m &lt; 2 &gt;. 67. The method of any one of claims 67-75,
Wherein the glass product comprises a surface compressive stress and a center tension, wherein the ratio of the center tension to the surface compressive stress ranges from about 0.1 to about 1. 78. The method of claim 76,
Wherein the surface compressive stress is 150 or greater. 67. The method of any one of claims 67-77,
Wherein the DOC comprises about 0.2 t or more. 67. The method of any one of claims 67-78,
Wherein the glass product comprises an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosporosilicate or an alkali aluminoborosilicate glass. 67. The method of any one of claims 67-79,
Wherein the glass article is disposed on the sealing layer. 70. The method of any one of claims 67-80,
&Lt; / RTI &gt; further comprising a drug substance. 67. The method of any one of claims 67-81,
And a cap disposed in said opening.

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