Precursor glasses with improved mechanical properties and glass ceramics formed therefrom

Abstract

A glass ceramic includes greater than or equal to 55 wt% to less than or equal to 75 wt% SiO2; al2O3 greater than or equal to 2 wt% to less than or equal to 10 wt%; greater than or equal to 8 wt% to less than or equal to 15 wt% Li2O; p2O5 greater than or equal to 2 wt% to less than or equal to 4 wt%; caO greater than or equal to 0.05 wt% and less than or equal to 4.0 wt%; greater than or equal to 5 wt% to less than or equal to 15 wt% of ZrO2; and a phase assembly comprising a crystalline phase and a glass phase wherein: the ratio of Li2O to Al2O3 is greater than 2 and less than or equal to 4; and the ratio of Li2O to ZrO2 is greater than or equal to 1.2 and less than or equal to 1.7.

Description

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 541,577, filed September 29, 2023, pursuant to 35 USC § 119, the contents of which are based and are incorporated herein by reference in their entirety. Technical Field

[0002] This specification generally relates to precursor glass and glass ceramics formed from said precursor glass, and more specifically, to glass ceramics having improved mechanical properties. Background Technology

[0003] There is a need for high-strength glass-based products that can be used in conjunction with, for example, portable electronic devices. Several materials are currently used on the market, such as glass, zirconium oxide, plastics, metals, and glass ceramics.

[0004] Glass-ceramics have certain advantages compared to other materials. However, it can be difficult to form glass-ceramics with the properties required for high-strength portable devices.

[0005] Therefore, there is a need for glass-ceramics with improved properties and methods for manufacturing such glass-ceramics. Summary of the Invention

[0006] According to the first aspect A1, a glass-ceramic comprises: greater than or equal to 55 wt% to less than or equal to 75 wt% SiO2; greater than or equal to 2 wt% to less than or equal to 10 wt% Al2O3; greater than or equal to 8 wt% to less than or equal to 15 wt% Li2O; greater than or equal to 2 wt% to less than or equal to 4 wt% P2O5; greater than or equal to 0.05 wt% and less than or equal to 4.0 wt% CaO; greater than or equal to 5 wt% to less than or equal to 15 wt% ZrO2; and a phase assembly comprising at least one crystalline phase and a residual amorphous glass phase, wherein: the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 4; and the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.2 and less than or equal to 1.7.

[0007] The second aspect A2 comprises the glass-ceramic according to aspect A1, wherein the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 3.5.

[0008] The third aspect A3 comprises a glass-ceramic according to any one of the preceding aspects, wherein the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.35 and less than or equal to 1.7.

[0009] The fourth aspect A4 comprises a glass-ceramic according to any one of the preceding aspects, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0 and less than or equal to 1.

[0010] The fifth aspect A5 comprises a glass-ceramic according to any one of the preceding aspects, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0.35 and less than or equal to 0.65.

[0011] The sixth aspect A6 comprises a glass ceramic according to any one of the preceding aspects, which further comprises greater than 0 wt% and less than or equal to 2 wt% Na2O.

[0012] The seventh aspect A7 comprises a glass-ceramic according to any one of the preceding aspects, which further comprises more than 0.1 wt% and less than or equal to 1 wt% K2O.

[0013] The eighth aspect A8 comprises a glass-ceramic according to any one of the preceding aspects, which further comprises more than or equal to 0.1 wt% to less than or equal to 1.0 wt% HfO2.

[0014] The ninth aspect A9 comprises a glass-ceramic according to any one of the preceding aspects, which contains more than or equal to 10 wt% to less than or equal to 14 wt% Li2O.

[0015] The tenth aspect A10 comprises a glass-ceramic according to any one of the preceding aspects, which contains more than or equal to 6 wt% to less than or equal to 10 wt% ZrO2.

[0016] The eleventh aspect A11 comprises a glass-ceramic according to any one of the preceding aspects, which contains more than or equal to 3 wt% to less than or equal to 8 wt% Al2O3.

[0017] The twelfth aspect A12 comprises a glass-ceramic according to any one of the preceding aspects, which contains more than or equal to 0.10 wt% to less than or equal to 1.00 wt% CaO.

[0018] The thirteenth aspect A13 comprises a glass-ceramic according to any one of the preceding aspects, wherein the phase combination comprises: a lithium disilicate crystalline phase; a lithium feldspar crystalline phase; and the residual amorphous glass phase.

[0019] The fourteenth aspect A14 comprises a glass-ceramic according to any one of the preceding aspects, which contains more than or equal to 15 wt% to less than or equal to 35 wt% of the residual amorphous glass phase.

[0020] The fifteenth aspect A15 comprises a glass-ceramic according to any one of the preceding aspects, which comprises more than or equal to 20 wt% to less than or equal to 45 wt% of the said lepidolite crystalline phase.

[0021] The sixteenth aspect A16 comprises a glass-ceramic according to any one of the preceding aspects, which comprises more than or equal to 35 wt% to less than or equal to 50 wt% of the lithium disilicate crystalline phase.

[0022] The seventeenth aspect A17 comprises a glass-ceramic according to any one of the preceding aspects, further comprising: a compressive stress layer extending from the surface of the glass-ceramic to a certain compression depth; and a central tension, wherein the central tension is greater than 170 MPa.

[0023] The eighteenth aspect A18 comprises a glass-ceramic according to any one of the preceding aspects, wherein the surface compressive stress of the compressive stress layer is greater than or equal to 200 MPa and less than or equal to 550 MPa.

[0024] Nineteenth aspect A19 comprises a glass-ceramic according to any one of the preceding aspects, wherein the glass-ceramic is ion-exchange strengthened.

[0025] The twentieth aspect A20 comprises a glass-ceramic according to any one of the preceding aspects, wherein the glass-ceramic has a thickness t, and the compression depth is greater than or equal to 0.09*t and less than or equal to 0.30*t.

[0026] The twenty-first aspect A21 comprises a glass-ceramic according to any one of the preceding aspects, wherein, with an article thickness of 0.5 mm, the glass-ceramic has a transmittance of greater than 90% for light wavelengths in the range of greater than or equal to 400 nm to less than or equal to 800 nm.

[0027] The twenty-second aspect A22 comprises a glass-ceramic according to any one of the preceding aspects, wherein the glass-ceramic has a fracture toughness greater than or equal to 1.0 MPa·m prior to strengthening by ion exchange. 1 / 2 And less than or equal to 2.0 MPa·m 1 / 2 .

[0028] The twenty-third aspect A23 comprises a glass-ceramic according to any one of the preceding aspects, wherein the elastic modulus of the glass-ceramic is greater than or equal to 90 GPa and less than or equal to 130 GPa.

[0029] The twenty-fourth aspect A24 includes an electronic device comprising a cover plate substrate comprising glass-ceramic according to any one of the preceding aspects.

[0030] A25 aspect comprises a glass-ceramic comprising: a lithium disilicate crystalline phase; a lithium feldspar crystalline phase; and a residual amorphous glass phase, wherein: the ratio of Li2O (wt%) to Al2O3 (wt%) in the glass-ceramic is greater than 2 and less than or equal to 4; and the ratio of Li2O (wt%) to ZrO2 (wt%) in the glass-ceramic is greater than or equal to 1.2 and less than or equal to 1.7.

[0031] The twenty-sixth aspect A26 comprises the glass-ceramic according to aspect A25, which contains greater than or equal to 15 wt% to less than or equal to 35 wt% of the residual amorphous glass phase.

[0032] The twenty-seventh aspect A27 includes a glass-ceramic according to any one of aspects A25 to A26, comprising more than or equal to 20 wt% to less than or equal to 45 wt% of the said lepidolite crystalline phase.

[0033] The twenty-eighth aspect A28 includes a glass-ceramic according to any one of aspects A25 to A27, comprising more than or equal to 35 wt% to less than or equal to 50 wt% of the lithium disilicate crystalline phase.

[0034] The twenty-ninth aspect A29 includes a glass-ceramic according to any one of aspects A25 to A28, further comprising: a compressive stress layer extending from the surface of the glass-ceramic to a certain compression depth; and a central tension, wherein the central tension is greater than 170 MPa.

[0035] Thirty aspect A30 includes a glass-ceramic according to any one of aspects A25 to A29, wherein the surface compressive stress of the compressive stress layer is greater than or equal to 200 MPa and less than or equal to 550 MPa.

[0036] The thirty-first aspect A31 includes a glass-ceramic according to any one of aspects A25 to A30, wherein the glass-ceramic is ion-exchange strengthened.

[0037] The thirty-second aspect A32 includes a glass-ceramic according to any one of aspects A25 to A31, wherein the glass-ceramic has a thickness t and the compression depth is greater than or equal to 0.09*t and less than or equal to 0.30*t.

[0038] The thirty-third aspect A33 includes a glass-ceramic according to any one of aspects A25 to A32, wherein, with an article thickness of 0.5 mm, the glass-ceramic has a transmittance of greater than 90% for light wavelengths in the range of greater than or equal to 400 nm to less than or equal to 800 nm.

[0039] The thirty-fourth aspect A34 includes an electronic device comprising a cover plate substrate comprising a glass-ceramic according to any one of aspects A25 to A33.

[0040] The thirty-fifth aspect A35 includes a glass-ceramic according to any one of aspects A25 to A34, wherein the glass-ceramic has a fracture toughness greater than or equal to 1.0 MPa·m prior to strengthening by ion exchange. 1 / 2 And less than or equal to 2.0 MPa·m 1 / 2 .

[0041] The thirty-sixth aspect A36 includes a glass-ceramic according to any one of aspects A25 to A35, wherein the elastic modulus of the glass-ceramic is greater than or equal to 90 GPa and less than or equal to 130 GPa.

[0042] A37 aspect includes a precursor glass comprising: greater than or equal to 55 wt% to less than or equal to 75 wt% SiO2; greater than or equal to 2 wt% to less than or equal to 10 wt% Al2O3; greater than or equal to 8 wt% to less than or equal to 15 wt% Li2O; greater than or equal to 2 wt% to less than or equal to 4 wt% P2O5; greater than or equal to 0.05 wt% and less than or equal to 4.0 wt% CaO; and greater than or equal to 5 wt% to less than or equal to 15 wt% ZrO2; wherein the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 4; and the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.2 and less than or equal to 1.7.

[0043] The thirty-eighth aspect A38 includes the precursor glass according to aspect A37, wherein the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 3.5.

[0044] The thirty-ninth aspect A39 includes a precursor glass according to any one of aspects A37 to A38, wherein the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.35 and less than or equal to 1.7.

[0045] Fortieth aspect A40 includes a precursor glass according to any one of aspects A37 to A39, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0 and less than or equal to 1.

[0046] Forty-one aspect A41 includes a precursor glass according to any one of aspects A37 to A40, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0.35 and less than or equal to 0.65.

[0047] Aspect 42 includes a precursor glass according to any one of aspects A37 to A41, which further contains greater than 0 wt% and less than or equal to 2 wt% Na2O.

[0048] Aspect 43 includes a precursor glass according to any one of aspects A37 to A42, which further comprises more than 0.1 wt% and less than or equal to 1 wt% K2O.

[0049] Aspect 44 includes a precursor glass according to any one of aspects A37 to A43, which further comprises more than or equal to 0.1 wt% to less than or equal to 1.0 wt% HfO2.

[0050] Aspect 45 includes a precursor glass according to any one of aspects A37 to A44, which contains more than or equal to 10 wt% to less than or equal to 14 wt% Li2O.

[0051] Aspect 46 includes a precursor glass according to any one of aspects A37 to A45, comprising more than or equal to 6 wt% to less than or equal to 10 wt% ZrO2.

[0052] Aspect 47 includes a precursor glass according to any one of aspects A37 to A46, which contains more than or equal to 3 wt% to less than or equal to 8 wt% Al2O3.

[0053] Aspect 48 includes a precursor glass according to any one of aspects A37 to A47, comprising more than or equal to 0.10 wt% to less than or equal to 1.00 wt% CaO.

[0054] Aspect 49 includes a precursor glass according to any one of aspects A37 to A48, wherein the liquidus viscosity of the precursor glass is greater than or equal to 0.5 kP and less than or equal to 3.5 kP.

[0055] Further features and advantages of the glass ceramic and the precursor glass used to form the glass ceramic will be set forth in the following detailed description, and will be apparent in part from the description or recognized by those skilled in the art through practice of the embodiments described herein (including the following detailed description, claims and drawings).

[0056] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated in and form a part of this specification. The drawings illustrate the various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. Attached Figure Description

[0057] Figure 1 It is a flowchart depicting a method according to embodiments disclosed and described herein;

[0058] Figure 2 A cross-section of a glass-ceramic product that has been chemically strengthened by ion exchange treatment is schematically depicted.

[0059] Figure 3 The drop test equipment is depicted schematically.

[0060] Figure 4 The illustration depicts the use of... Figure 3 Drop testing equipment;

[0061] Figure 5 The illustration depicts the use of... Figure 3 Drop testing equipment;

[0062] Figure 6A A top view of an electronic device comprising a glass-ceramic article according to embodiments disclosed and described herein is schematically depicted;

[0063] Figure 6B A perspective view of an electronic device comprising a glass-ceramic article according to embodiments disclosed and described herein is schematically depicted.

[0064] Figure 7 The maximum central tension (y-axis) of glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein is depicted graphically as a function of ion exchange time (x-axis).

[0065] Figure 8 The maximum central tension (y-axis) of glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein is graphically depicted as a function of ZrO2 concentration (x-axis).

[0066] Figure 9 The fracture stress (y-axis) of glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein after a four-point bending test is graphically depicted.

[0067] Figure 10The fracture stress (y-axis) of glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein after a four-point bending test is graphically depicted.

[0068] Figure 11 The maximum drop height (y-axis) of the glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein is graphically depicted from the drop test equipment.

[0069] Figure 12 The maximum drop height (y-axis) of the glass ceramics and comparative glass ceramics according to the embodiments disclosed and described herein is graphically depicted from the drop test apparatus; and

[0070] Figure 13 The transmittance (y-axis) of the glass ceramic according to the embodiments disclosed and described herein is graphically depicted as a function of wavelength (x-axis). Detailed Implementation

[0071] Reference will now be made in detail to embodiments of the precursor glass and the glass-ceramic formed from the precursor glass, examples of which are illustrated in the accompanying drawings. Where possible, the same reference numerals will be used to refer to the same or similar parts throughout the drawings. According to embodiments, a glass-ceramic typically comprises 55 wt% to 75 wt% SiO2; 2 wt% to 10 wt% Al2O3; 8 wt% to 15 wt% Li2O; 2 wt% to 4 wt% P2O5; 0.05 wt% to 4.0 wt% CaO; 5 wt% to 15 wt% ZrO2; and a phase assembly comprising at least one crystalline phase and a residual amorphous glass phase, wherein: the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 4; and the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.2 and less than or equal to 1.7. Various embodiments of precursor glasses and glass-ceramics formed from said precursor glasses will be described herein with specific reference to the accompanying drawings.

[0072] As used herein, the term “glass-ceramic” refers to a solid prepared by controlled crystallization of a precursor glass and having one or more crystalline phases and a residual amorphous glass phase.

[0073] The liquidus temperature of a precursor glass is the temperature at which no crystalline phase can coexist in equilibrium with the precursor glass (unit: °C). The liquidus temperature is measured according to ASTM C829-81 (2022).

[0074] The liquidus viscosity (in poise) of a precursor glass is the viscosity of the precursor glass at its liquidus temperature. Liquidus viscosity is determined according to ASTM C965-23 (2023).

[0075] As used herein, “compression depth” or “DOC” refers to the depth of the compressive stress (CS) layer, and is the depth within a glass-ceramic article where the stress changes from compressive stress to tensile stress and the stress value is zero. According to convention commonly used in the art, compressive stress is expressed as negative (< 0) stress, and tensile stress as positive (> 0) stress. However, throughout this specification, and unless otherwise stated, CS is expressed as a positive or absolute value, i.e., as described herein. .

[0076] The CS, DOC, and maximum central tension (CT) values ​​were measured using a hybrid method that combines measurements using evanescent prism coupled spectroscopy (EPCS) and light scattering polarization measurement (LSP) as disclosed in U.S. Patent Application Publication No. 2020 / 0300615, which is incorporated herein by reference in its entirety.

[0077] Fracture toughness (K) 1C This indicates the fracture toughness of the precursor glass or glass-ceramic. Fracture toughness is measured on non-chemically strengthened precursor glass or glass-ceramic articles, such as measuring KL before ion exchange (IOX) treatment. 1C The value represents the characteristics of the article prior to IOX treatment. The fracture toughness testing method described herein is not suitable for glass already exposed to IOX treatment. However, as described herein, fracture toughness measurements performed on the same article (e.g., precursor glass or glass-ceramic substrate) prior to IOX treatment are correlated with fracture toughness after IOX treatment and are therefore used as is. The value used to measure K... 1C The chevron-notched short bar (CNSB) method is disclosed in Reddy, KPR et al., “Fracture Toughness Measurement of Glass and Ceramic Materials Using Chevron-Notched Specimens”, Journal of the American Ceramic Society, 71 [6], C-310-C-313 (1988), the difference being Y* mIt was calculated using Equation 5 from Bubsey, RT et al., "Closed-Form Expressions for Crack-Mouth Displacement and Stress Intensity Factors for Chevron-Notched Short Bar and Short Rod Specimens Based on Experimental Compliance Measurements," NASA Technical Memorandum 83796, pp. 1-30 (October 1992). The measurement of K is described in the following literature. 1C The double-torsion method and fixture for determining fracture toughness and slow crack growth of materials: Shyam, A. and Lara-Curzio, E., “The double-torsion testing technique for determination of fracturetoughness and slow crack growth of materials: A review”, J. Mater. Sci., 41, pp. 4093-4104, (2006). The double-torsion measurement method yields K... 1C The values ​​are typically slightly higher than those obtained using the CNSB method. Unless otherwise stated, all fracture toughness values ​​are measured using the CNSB method.

[0078] Young's modulus, shear modulus, and Poisson's ratio were measured using a general type of resonant ultrasonic spectroscopy technique as described in ASTM E2001-13 (2018).

[0079] Unless otherwise stated, the haze of glass-ceramic products is measured on a 0.6 mm thick glass-ceramic plate using a haze meter (such as BYK Gardner Haze-GardI) in accordance with ASTM D1003-21 (2021) or ASTM D1044-19 (2019).

[0080] Optical transmittance (also referred to herein as “transmittance”) was measured in the range of 250–1000 nm on optically polished samples with planar parallel surfaces using a Perkin Elmer Lambda 950 spectrophotometer at 2 nm data intervals. The transmittance was measured on the glass-ceramic articles themselves without any coatings or other applications.

[0081] The powdered samples were subjected to X-ray diffraction (XRD) using a Bruker D4 Endeavor equipped with Cu radiation and a LynxEye detector. The phase assemblies were determined using the Rietveld method and Bruker's Topas software package.

[0082] As described in the following literature, particularly the equation (4) of the publication, the stored strain energy of glass-ceramic articles is calculated: Gulati, Suresh T., “Frangibility of Tempered Soda-Lime Glass Sheet”, Glass Processing Days, 13-15 September 1997, pp. 72-76 (ISBN 952-90-8959-7).

[0083] The density was measured according to ASTM C693-93 (2019) as measured.

[0084] Hardness was measured using a MITUTOYO HM114 hardness tester with a Knoop indenter having an indentation load of 200 grams (dwell time of 15 seconds). The indentation diagonal was measured using a calibrated optical microscope. The value is the average of five indentation measurements for each sample. The test was performed on optically polished samples with flat, parallel surfaces.

[0085] As used herein, the term "softening point" refers to a glass composition with a viscosity of 1 × 10⁻⁶. 7.6 Temperature at poise. Softening point was determined using the parallel plate viscosity method according to ASTM C1351M-96 (2012).

[0086] As used in this article, the term "annealing point" refers to the point at which the viscosity of the precursor glass or glass-ceramic is 1 × 10⁻⁶. 13 The annealing temperature was determined using the beam bending viscosity method of ASTM C598-93 (2013).

[0087] As used in this article, the terms "strain point" and "T" are used interchangeably. 应变"This refers to the viscosity of the precursor glass or glass-ceramic being 3 × 10⁻⁶. 14 The temperature at which the strain point was measured was determined using the beam bending viscosity method according to ASTM C598-93 (2013).

[0088] The linear coefficient of thermal expansion (CTE) of glass ceramics in the temperature range of 0°C to 300°C is expressed as the average CTE in the range of ppm / °C (× 10-6 / °C) and determined using a pusher dilatometer according to ASTM E228-11 (2016).

[0089] The thermal diffusivity of the glass-ceramic was determined according to ASTM E1461-13 (2022).

[0090] The thermal conductivity of the glass-ceramic was determined according to ASTM E1461-13 (2022).

[0091] The heat capacity of glass ceramics, expressed in J / g*K, is determined according to ASTM E1269-11 (2018).

[0092] When the terms "free from" and "substantially free from" are used to describe the concentration and / or absence of a specific component in a precursor glass or glass-ceramic, the terms mean that the component was not intentionally added to the precursor glass or glass-ceramic. However, the precursor glass or glass-ceramic may contain trace amounts of the component as contaminants or residues, in amounts less than 0.01 wt%.

[0093] A range herein may be expressed as "less than or equal to" a specific value, and / or to "less than or equal to" another specific value. Another embodiment, when expressing this range, includes from one specific value and / or to another specific value. Similarly, when a value is expressed as an approximation using the antecedent "less than or equal to," it will be understood that the specific value forms another embodiment. It should be further understood that the endpoints of each range are valid both in relation to and independent of the other endpoint. Unless otherwise expressly stated, any range as used herein includes all ranges and subranges, and any values ​​in between.

[0094] As used herein, directional terms (e.g., up, down, right, left, front, back, top, bottom) are used only with reference to the accompanying drawings and are not intended to imply absolute orientation.

[0095] Unless otherwise expressly stated, it is never intended to interpret any method set forth herein as requiring its steps to be performed in a particular order, nor is it intended to require any particular orientation of any device. Therefore, it is never intended to infer any order or orientation in any respect where a method claim does not actually describe the order in which its steps are followed, or where any device claim does not actually describe the order or orientation of individual components, or where the claims or description do not otherwise specifically specify that the steps are limited to a particular order, or where a particular order or orientation of the components of the device is not described. This applies to any possible non-expressive basis for interpretation, including: logical questions relating to the arrangement of steps, the flow of operations, the order of components, or the orientation of components; simple meanings derived from grammatical organization or punctuation; and the number or type of embodiments described in the description.

[0096] As used herein, unless the context explicitly indicates otherwise, the singular forms “a / an” and “the” include plural indicators. Thus, for example, unless the context explicitly indicates otherwise, a reference to “a” component includes aspects having two or more such components.

[0097] Glass-ceramics possess properties that make them suitable for use as cover substrates and / or housings in mobile electronic devices. For example, without being bound by theory, glass-ceramics with high fracture toughness and / or Young's modulus can provide resistance to crack penetration and exhibit good drop performance. Their resistance to crack penetration and drop performance can be further improved when such glass-ceramics are chemically strengthened, for example, by ion exchange. High fracture toughness and / or Young's modulus also increase the amount of stored tensile energy and the maximum central tension that can be imparted to glass-ceramics through chemical tempering (e.g., by ion exchange strengthening). Furthermore, the optical properties of glass-ceramics, such as transparency and haze, can be customized by adjusting the heating / ceramization schedule used to convert the precursor glass into glass-ceramics.

[0098] Because thinner glass and glass-ceramics are needed to meet the requirements of evolving electronic devices (such as increasingly smaller and thinner electronic devices), it is desirable to improve the strength of thin precursor glass and glass-ceramics formed from said precursor glass by increasing the level of stress (both compressive and tensile stress) established in the glass-ceramic (e.g., through chemical tempering).

[0099] However, known glass-ceramic compositions have reached a plateau in the stress values ​​that can be established within the glass-ceramic. This includes both the magnitude of compressive stress (CS) obtainable at the glass-ceramic surface and the magnitude of central tension (CT) in the thickness of the glass-ceramic, the latter primarily contributing to the fragmentation behavior (also known as brittleness) of the glass-ceramic. In other words, existing glass-ceramics may not be able to achieve the desired fragmentation behavior because the material may not be able to obtain the necessary amount of central tension through, for example, chemical tempering.

[0100] The compositions of the precursor glass and glass-ceramics disclosed herein allow the glass-ceramics to exhibit sufficiently high central tensile strength (e.g., greater than or equal to 150 MPa to less than 230 MPa, as in a 0.6 mm thick substrate) after chemical tempering without exhibiting a highly fragmented fracture pattern. Without wishing to be bound by theory, it is considered that the relatively high central tensile strength in the glass-ceramics described herein allows for the generation of greater compressive stress at a deeper depth from the surface of the glass-ceramics, thereby improving the mechanical properties of the glass-ceramics, including but not limited to drop height and fracture strength.

[0101] According to the embodiments disclosed and described herein, one aspect that contributes to improving the stress level in glass-ceramics is the increase in the amount of Li₂O in the precursor glass. Lithium is the smallest alkali metal ion, and relatively high compressive stress and central tension values ​​can be obtained when lithium is replaced by sodium or potassium ions in the glass network during ion exchange strengthening. However, including too much lithium in the precursor glass can make the glass difficult to form, thus making it difficult to obtain the thin glass-ceramic articles required for handheld electronic devices such as mobile phones and tablets. Therefore, the compressive stress and central tension in the resulting glass-ceramic cannot be increased simply by increasing the amount of lithium in the precursor glass. As a result, the precursor glass cannot be easily and economically formed into thin sheets.

[0102] However, it has been found that the combination of a relatively large amount of zirconium oxide (ZrO2) in the precursor glass and a slightly larger amount of lithium in the precursor glass can generate higher compressive stress and central tension in the glass-ceramic after chemical tempering without unduly affecting the melting behavior of the precursor glass. Without being bound by any particular theory, it is believed that zirconium oxide helps to partition lithium in the residual amorphous glass phase of the glass-ceramic when it is formed by heat treatment, which will be described in further detail herein. Therefore, more lithium is present in the residual amorphous glass phase and readily exchanges with sodium and potassium during the chemical tempering process. Thus, while zirconium oxide is conventionally included in precursor glass and glass-ceramic compositions to prevent crystallization in the precursor glass prior to ceramization, the relatively large amount of zirconium oxide included in the embodiments disclosed and described herein goes beyond what is conventionally thought to improve crystallization of the precursor glass and has been found to improve the ion exchange properties of the glass-ceramic.

[0103] It has now been further determined that the central tension established in glass-ceramics can be maximized by balancing the amounts of Li₂O and ZrO₂ in the precursor glass and the resulting glass-ceramic. Specifically, it has been found that the central tension of the glass-ceramic strengthened by ion exchange can be maximized when the ratio of Li₂O (wt%) to ZrO₂ (wt%) in the precursor glass and the resulting glass-ceramic (i.e., Li₂O:ZrO₂) is greater than or equal to 1.2 to less than or equal to 1.7. In this regard, without wishing to be bound by any particular theory, it is considered that compositions including the Li₂O to ZrO₂ ratio within this range can maximize the amount of Li₂O in the residual amorphous glass phase of the glass-ceramic, which in turn allows for more ion exchange between the smaller lithium ions in the residual amorphous glass phase and the larger sodium and / or potassium ions in the ion exchange bath, thereby resulting in a greater central tension in the glass-ceramic.

[0104] Furthermore, it has now been determined that the amount of residual amorphous glass phase in the resulting glass-ceramic can be increased by balancing the amounts of Li₂O and Al₂O₃ in the precursor glass and the resulting glass-ceramic. Specifically, it has been found that when the ratio of Li₂O (wt%) to Al₂O₃ (wt%) in the precursor glass and the resulting glass-ceramic (i.e., Li₂O:Al₂O₃) is greater than or equal to 2 to less than or equal to 4, the amount of residual amorphous glass phase in the glass-ceramic increases, thereby allowing for a further increase in the central strain established in the glass-ceramic after chemical tempering. In this regard, without wishing to be bound by any particular theory, it is considered that increasing the amount of residual amorphous glass phase in the glass-ceramic, while also maximizing the amount of lithium in the residual amorphous glass phase (e.g., by balancing the amounts of Li₂O and ZrO₂ in the precursor glass and the resulting glass-ceramic), can further increase the amount of ion exchange that occurs between the smaller lithium ions in the residual amorphous glass phase and the larger sodium and / or potassium ions in the ion exchange bath, thereby further increasing the central strain in the glass-ceramic. In other words, increasing the amount of residual amorphous glass phase and the amount of lithium in the residual amorphous glass phase in glass ceramics can increase the amount of ion exchange between lithium ions and sodium and / or potassium ions, thereby increasing the amount of central tension that can be established in glass ceramics.

[0105] Furthermore, according to the embodiments disclosed and described herein, the precursor glass and glass-ceramic also include a relatively large amount of calcium oxide (CaO). Without being bound by any particular theory, it is believed that the additional calcium oxide increases the density of the glass-ceramic and thus slows down ion diffusion into the glass-ceramic during chemical strengthening. This slowdown in diffusion slows down the ion exchange process, but the glass-ceramic exhibits greater compressive stress and central tension compared to the lower-density precursor glass and glass-ceramic. Additionally, zirconium oxide is also believed to contribute to increasing the density of the glass-ceramic.

[0106] In various embodiments, the composition of the precursor glass is selected such that the resulting glass-ceramic has a phase assembly comprising a lithium feldspar crystalline phase and a lithium silicate crystalline phase, particularly a lithium disilicate crystalline phase, wherein the weight percentage of the lithium feldspar crystalline phase and the lithium disilicate crystalline phase is higher than the weight percentage of other crystalline phases present in the glass-ceramic article. The phase assembly also includes a residual amorphous glass phase.

[0107] The crystalline phase of petalite (LiAlSi4O) 10 Lithium nitride (LN) is a monoclinic crystal with a three-dimensional framework structure consisting of layered Si₂O₅ layers connected by folded Li and Al tetrahedra. Li is tetrahedral coordinated with oxygen. The mineral lithite is the lithium source and is used as a low-thermal-expansion phase to improve the thermal shock resistance of glass ceramics or ceramic parts.

[0108] In the glass-ceramic embodiments described herein, the weight percentage of the lithium feldspar crystalline phase in the glass-ceramic can be within the following ranges: greater than or equal to 20 wt% to less than or equal to 70 wt%, greater than or equal to 20 wt% to less than or equal to 65 wt%, greater than or equal to 20 wt% to less than or equal to 60 wt%, greater than or equal to 20 wt% to less than or equal to 55 wt%, greater than or equal to 20 wt% to less than or equal to 50 wt%, greater than or equal to 20 wt% to less than or equal to 45 wt%, greater than or equal to 20 wt% to less than or equal to 40 wt%, greater than or equal to 20 wt% to less than or equal to 35 wt%, greater than or equal to 20 wt% to less than or equal to 30 wt%, greater than or equal to 20 wt% to less than or equal to 25 wt%, greater than or equal to 25 wt% to less than or equal to 70 wt%, greater than or equal to 25 wt% to less than or equal to 65 wt%, greater than or equal to 25 wt% to less than or equal to 60 wt%. wt%, greater than or equal to 25 wt% to less than or equal to 55 wt%, greater than or equal to 25 wt% to less than or equal to 50 wt%, greater than or equal to 25 wt% to less than or equal to 45 wt%, greater than or equal to 25 wt% to less than or equal to 40 wt%, greater than or equal to 25 wt% to less than or equal to 35 wt%, greater than or equal to 25 wt% to less than or equal to 30 wt%, greater than or equal to 30 wt% to less than or equal to 70 wt%, greater than or equal to 30 wt% to less than or equal to 65 wt%, greater than or equal to 30 wt% to less than or equal to 60 wt%, greater than or equal to 30 wt% to less than or equal to 55 wt%, greater than or equal to 30 wt% to less than or equal to 50 wt%, greater than or equal to 30 wt% to less than or equal to 45 wt%, greater than or equal to 30 wt% to less than or equal to 40 wt%, greater than or equal to 30 wt% to less than or equal to 35 wt%, greater than or equal to 35 wt%. wt% to less than or equal to 70 wt%, greater than or equal to 35 wt% to less than or equal to 65 wt%, greater than or equal to 35 wt% to less than or equal to 60 wt%, greater than or equal to 35 wt% to less than or equal to 55 wt%, greater than or equal to 35 wt% to less than or equal to 50 wt%, greater than or equal to 35 wt% to less than or equal to 45 wt%, greater than or equal to 35 wt% to less than or equal to 40 wt%, greater than or equal to 40 wt% to less than or equal to 70 wt%, greater than or equal to 40 wt% to less than or equal to 65 wt%, greater than or equal to 40 wt% to less than or equal to 60 wt%, greater than or equal to 40 wt% to less than or equal to 55 wt%, greater than or equal to 40 wt% to less than or equal to 50 wt%, greater than or equal to 40 wt% to less than or equal to 45wt%, greater than or equal to 45 wt% to less than or equal to 70 wt%, greater than or equal to 45 wt% to less than or equal to 65 wt%, greater than or equal to 45 wt% to less than or equal to 60 wt%, greater than or equal to 45 wt% to less than or equal to 55 wt%, greater than or equal to 45 wt% to less than or equal to 50 wt%, greater than or equal to 50 wt% to less than or equal to 70 wt%, greater than or equal to 50 wt% to less than or equal to 65 wt%, greater than or equal to 50 wt% to less than or equal to 60 wt%, greater than or equal to 55 wt% to less than or equal to 70 wt%, greater than or equal to 55 wt% to less than or equal to 65 wt%, greater than or equal to 55 wt% to less than or equal to 60 wt%, greater than or equal to 60 wt% to less than or equal to 70 wt%, greater than or equal to 60 wt% to less than or equal to 65 wt%, or even greater than or equal to 65 wt%. wt% to less than or equal to 70 wt%. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range. In embodiments, the glass ceramic may comprise about 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67wt%, 68 wt%, 69 wt% or 70 wt% of lepidolite crystalline phase.

[0109] Lithium disilicate (Li₂Si₂O₅) is an orthorhombic crystal based on a corrugated plate of {Si₂O₅} tetrahedral arrays. The crystals are typically plate-like or lath-like in shape, with prominent cleavage planes. Lithium disilicate-based glass ceramics offer highly desirable mechanical properties, including high crystalline strength and fracture toughness, due to their unoriented, interlocking crystal microstructure—a crystal structure that forces cracks to propagate through tortuous paths around these crystals within the material.

[0110] In the embodiments, the weight percentage of the lithium disilicate crystalline phase (also referred to herein as "L2S") in the glass-ceramic can be within the following ranges: greater than or equal to 20 wt% to less than or equal to 60 wt%, greater than or equal to 20 wt% to less than or equal to 55 wt%, greater than or equal to 20 wt% to less than or equal to 50 wt%, greater than or equal to 20 wt% to less than or equal to 45 wt%, greater than or equal to 20 wt% to less than or equal to 40 wt%, greater than or equal to 20 wt% to less than or equal to 35 wt%, greater than or equal to 20 wt% to less than or equal to 30 wt%, greater than or equal to 20 wt% to less than or equal to 25 wt%, greater than or equal to 25 wt% to less than or equal to 60 wt%, greater than or equal to 25 wt% to less than or equal to 55 wt%, greater than or equal to 25 wt% to less than or equal to 50 wt%, greater than or equal to 25 wt% to less than or equal to 45 wt%, greater than or equal to 25 wt% to less than or equal to 40 wt%. wt%, greater than or equal to 25 wt% to less than or equal to 35 wt%, greater than or equal to 25 wt% to less than or equal to 30 wt%, greater than or equal to 30 wt% to less than or equal to 60 wt%, greater than or equal to 30 wt% to less than or equal to 55 wt%, greater than or equal to 30 wt% to less than or equal to 50 wt%, greater than or equal to 30 wt% to less than or equal to 45 wt%, greater than or equal to 30 wt% to less than or equal to 40 wt%, greater than or equal to 30 wt% to less than or equal to 35 wt%, greater than or equal to 35 wt% to less than or equal to 60 wt%, greater than or equal to 35 wt% to less than or equal to 55 wt%, greater than or equal to 35 wt% to less than or equal to 50 wt%, greater than or equal to 35 wt% to less than or equal to 45 wt%, greater than or equal to 35 wt% to less than or equal to 40 wt%, greater than or equal to 40 wt% to less than or equal to 60 wt%, greater than or equal to 40 wt%. wt% to less than or equal to 55 wt%, greater than or equal to 40 wt% to less than or equal to 50 wt%, greater than or equal to 40 wt% to less than or equal to 45 wt%, greater than or equal to 45 wt% to less than or equal to 60 wt%, greater than or equal to 45 wt% to less than or equal to 55 wt%, greater than or equal to 45 wt% to less than or equal to 50 wt%, greater than or equal to 50 wt% to less than or equal to 60 wt%, greater than or equal to 50 wt% to less than or equal to 55 wt%, or greater than or equal to 55 wt% to less than or equal to 60 wt%. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.In embodiments, the glass-ceramic may contain about 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, or 60 wt% of lithium disilicate crystalline phase.

[0111] In the embodiments, the content of residual amorphous glass phase in the glass-ceramic is greater than or equal to 13 wt% and less than or equal to 35 wt%, greater than or equal to 14 wt% and less than or equal to 35 wt%, greater than or equal to 15 wt% and less than or equal to 35 wt%, greater than or equal to 16 wt% and less than or equal to 35 wt%, greater than or equal to 17 wt% and less than or equal to 35 wt%, greater than or equal to 18 wt% and less than or equal to 35 wt%, greater than or equal to 19 wt% and less than or equal to 35 wt%, greater than or equal to 20 wt% and less than or equal to 35 wt%, greater than or equal to 21 wt% and less than or equal to 35 wt%, greater than or equal to 22 wt% and less than or equal to 35 wt%, greater than or equal to 23 wt% and less than or equal to 35 wt%, greater than or equal to 24 wt% and less than or equal to 35 wt%, greater than or equal to 25 wt% and less than or equal to 35 wt%, greater than or equal to 26 wt%. wt% and less than or equal to 35 wt%, greater than or equal to 27 wt% and less than or equal to 35 wt%, greater than or equal to 28 wt% and less than or equal to 35 wt%, greater than or equal to 29 wt% and less than or equal to 35 wt%, greater than or equal to 30 wt% and less than or equal to 35 wt%, greater than or equal to 31 wt% and less than or equal to 35 wt%, greater than or equal to 20 wt% and less than or equal to 35 wt%, greater than or equal to 20 wt% and less than or equal to 34 wt%, greater than or equal to 20 wt% and less than or equal to 33 wt%, greater than or equal to 20 wt% and less than or equal to 32 wt%, greater than or equal to 21 wt% and less than or equal to 35 wt%, greater than or equal to 21 wt% and less than or equal to 34 wt%, greater than or equal to 21 wt% and less than or equal to 33 wt%, greater than or equal to 21 wt% and less than or equal to 32 wt%, greater than or equal to 22 wt% and less than or equal to 35 wt%. wt%, greater than or equal to 22 wt% and less than or equal to 34 wt%, greater than or equal to 22 wt% and less than or equal to 33 wt%, greater than or equal to 22 wt% and less than or equal to 32 wt%, greater than or equal to 23 wt% and less than or equal to 35 wt%, greater than or equal to 23 wt% and less than or equal to 34 wt%, greater than or equal to 23 wt% and less than or equal to 33 wt%, greater than or equal to 23 wt% and less than or equal to 32 wt%, greater than or equal to 24 wt% and less than or equal to 35 wt%, greater than or equal to 24 wt% and less than or equal to 34 wt%, greater than or equal to 24 wt% and less than or equal to 33 wt%, greater than or equal to 24 wt% and less than or equal to 32 wt%, greater than or equal to 25 wt% and less than or equal to 35 wt%, greater than or equal to 25 wt% and less than or equal to 34 wt%.The content of residual amorphous glass may be 35 wt%, greater than or equal to 25 wt% and less than or equal to 33 wt%, or even greater than or equal to 25 wt% and less than or equal to 32 wt%. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range. In embodiments, the residual amorphous glass content may be 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 29 wt%, 28 wt%, 27 wt%, 26 wt%, 25 wt%, 24 wt%, 23 wt%, 22 wt%, 21 wt%, 20 wt%, 19 wt%, 18 wt%, 17 wt%, 16 wt%, 15 wt%, 14 wt%, or 13 wt%.

[0112] The precursor glasses and glass-ceramics described herein are generally described as lithium aluminum silicate precursor glasses and glass-ceramics containing SiO2, Al2O3, P2O5, ZrO2, CaO, and Li2O. In addition to SiO2, Al2O3, and Li2O, the precursor glasses and glass-ceramics described herein may also contain alkali oxides such as Na2O, K2O, Rb2O, or Cs2O, and one or more other components as described herein. As described herein, the main crystalline phases of the phase assemblages of the glass-ceramics include lithium feldspar and lithium disilicate. In embodiments, the glass-ceramics may contain less than 7 wt%, such as less than 6 wt%, less than 5 wt%, less than 4 wt%, or even less than 3 wt% of other crystalline phases (such as, but not limited to, lithium silicate (Li2SiO3), lithium aluminum silicate (Li...). x Al x Si 3-x The combination of zirconia (ZrO2), cristobalite (SiO2), quartz (SiO2), zircon (ZrO2), zircon (ZrO2), spodumene (LiAlSi2O6), and lithium phosphate (Li3PO4) provides a glass-ceramic with low haze (high clarity) and improved mechanical properties.

[0113] SiO2 (an oxide involved in glass formation) can be used to stabilize the network structure of precursor glasses and glass-ceramics. The concentration of SiO2 should be high enough to form a crystalline phase of lepidolite when the precursor glass is heat-treated to convert it into a glass-ceramic. The amount of SiO2 can be limited to control the melting temperature of the glass, as the melting temperature of pure SiO2 or high-SiO2 glasses is undesirably high. In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 55 wt% and less than or equal to 80 wt% SiO2, greater than or equal to 55 wt% and less than or equal to 75 wt% SiO2, greater than or equal to 55 wt% and less than or equal to 73 wt% SiO2, greater than or equal to 55 wt% and less than or equal to 72 wt% SiO2, greater than or equal to 60 wt% and less than or equal to 80 wt% SiO2, greater than or equal to 60 wt% and less than or equal to 75 wt% SiO2, greater than or equal to 60 wt% and less than or equal to 73 wt% SiO2, greater than or equal to 60 wt% and less than or equal to 72 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 80 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 75 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 73 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 73 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 80 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 75 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 73 wt% SiO2, greater than or equal to 65 wt% and less than or equal to 75 ... The ranges are defined as follows: wt% and less than or equal to 72 wt% SiO2, greater than or equal to 68 wt% and less than or equal to 80 wt% SiO2, greater than or equal to 68 wt% and less than or equal to 75 wt% SiO2, greater than or equal to 68 wt% and less than or equal to 73 wt% SiO2, or even greater than or equal to 68 wt% and less than or equal to 72 wt% SiO2. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0114] Al₂O₃ also provides stability to the network and offers improved mechanical properties and chemical durability. However, if the amount of Al₂O₃ is too high, the fraction of lithium disilicate crystals may decrease, potentially to the point where interlocking structures cannot be formed. The amount of Al₂O₃ can be customized to control the viscosity of the precursor glass during melting and forming. Furthermore, if the amount of Al₂O₃ is too high, the viscosity of the melt will generally also increase. In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 2 wt% and less than or equal to 15 wt% Al2O3, greater than or equal to 3 wt% and less than or equal to 15 wt% Al2O3, greater than or equal to 4 wt% and less than or equal to 15 wt% Al2O3, greater than or equal to 5 wt% and less than or equal to 15 wt% Al2O3, 2 wt% and less than or equal to 12 wt% Al2O3, greater than or equal to 4 wt% and less than or equal to 12 wt% Al2O3, greater than or equal to 5 wt% and less than or equal to 12 wt% Al2O3, 2 wt% and less than or equal to 10 wt% Al2O3, greater than or equal to 3 wt% and less than or equal to 10 wt% Al2O3, greater than or equal to 4 wt% and less than or equal to 10 wt% Al2O3, greater than or equal to 5 ...10 wt% and less than or equal to 10 wt% Al2O3, greater than or equal to 5 wt% and less than or equal to 10 wt% Al2O3, greater than or equal to 10 wt% and less than or equal to 10 The ranges are defined as follows: wt% and less than or equal to 10 wt% Al2O3, 2 wt% and less than or equal to 8 wt% Al2O3, greater than or equal to 3 wt% and less than or equal to 8 wt% Al2O3, greater than or equal to 4 wt% and less than or equal to 8 wt% Al2O3, greater than or equal to 5 wt% and less than or equal to 8 wt% Al2O3, 2 wt% and less than or equal to 6 wt% Al2O3, greater than or equal to 3 wt% and less than or equal to 6 wt% Al2O3, or even greater than or equal to 4 wt% and less than or equal to 6 wt% Al2O3. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0115] In the precursor glasses and glass-ceramics described herein, Li₂O facilitates the formation of both the lithiofeldspar and lithium disilicate crystalline phases. In fact, to obtain lithiofeldspar and lithium disilicate as the dominant crystalline phases, the composition needs to contain at least about 7 wt% Li₂O. Furthermore, it has been found that once Li₂O approaches about 17 wt%, the viscosity of the precursor glass may decrease to an undesirable level.Therefore, in the embodiments, the precursor glass and glass-ceramic may contain greater than or equal to 7 wt% and less than or equal to 17 wt% Li2O, 8 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 10 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 11 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 12 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 14 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 16 wt% and less than or equal to 17 wt% Li2O, greater than or equal to 7 wt% and less than or equal to 16 wt% Li2O, greater than or equal to 8 wt% and less than or equal to 16 wt% Li2O, greater than or equal to 10 wt% and less than or equal to 16 wt% Li2O, greater than or equal to 11 wt% and less than or equal to 16 wt% Li2O, greater than or equal to 12 wt% and less than or equal to 17 ...6 wt% Li2O, greater than or equal to 12 wt% and less than or equal to Li₂O wt% and less than or equal to 16 wt%, Li₂O wt% and greater than or equal to 14 wt% and less than or equal to 16 wt%, Li₂O wt% and greater than or equal to 7 wt% and less than or equal to 15 wt%, Li₂O wt% and greater than or equal to 8 wt% and less than or equal to 15 wt%, Li₂O wt% and greater than or equal to 10 wt% and less than or equal to 15 wt%, Li₂O wt% and greater than or equal to 11 wt% and less than or equal to 15 wt%, Li₂O wt% and greater than or equal to 12 wt% and less than or equal to 15 wt%, Li₂O wt% and greater than or equal to 14 wt%, Li₂O wt% and greater than or equal to 10 wt% and less than or equal to 14 wt%, Li₂O wt% and greater than or equal to 11 wt% and less than or equal to 14 wt%. Li₂O, greater than or equal to 12 wt% and less than or equal to 14 wt% Li₂O, greater than or equal to 7 wt% and less than or equal to 13 wt% Li₂O, greater than or equal to 8 wt% and less than or equal to 13 wt% Li₂O, greater than or equal to 10 wt% and less than or equal to 13 wt% Li₂O, greater than or equal to 11 wt% and less than or equal to 13 wt% Li₂O, greater than or equal to 12 wt% and less than or equal to 13 wt% Li₂O, greater than or equal to 7 wt% and less than or equal to 12 wt% Li₂O, greater than or equal to 8 wt% and less than or equal to 12 wt% Li₂O, or even greater than or equal to 10 wt% and less than or equal to 12 wt% Li₂O. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0116] As described herein, it has been found that when the ratio of Li2O (wt%) to Al2O3 (wt%) in the current driving glass and the resulting glass ceramic (i.e., Li2O:Al2O3) is greater than or equal to 2.0 to less than or equal to 4.0, the amount of residual amorphous glass phase in the glass ceramic increases, thereby allowing for a further increase in the central tension established in the glass ceramic after chemical tempering. In the embodiments, the ratio of Li2O to Al2O3 is greater than or equal to 2.0 and less than or equal to 3.8, greater than or equal to 2.0 and less than or equal to 3.6, greater than or equal to 2.0 and less than or equal to 3.4, greater than or equal to 2.0 and less than or equal to 3.2, greater than or equal to 2.0 and less than or equal to 3.0, greater than or equal to 2.0 and less than or equal to 2.8, greater than or equal to 2.0 and less than or equal to 2.6, greater than or equal to 2.0 and less than or equal to 2.5, greater than or equal to 2.0 and less than or equal to 2.4, greater than or equal to 2.0 and less than or equal to 2.3, greater than or equal to 2.1 and less than or equal to 4.0, greater than or equal to 2.1 and less than or equal to 3.8, greater than or equal to 2.1 and less than or equal to 3.6, greater than or equal to 2.1 and less than or equal to 3.4, greater than or equal to 2.1 and less than or equal to 3.2, and greater than or equal to 3.2. The range is equal to or greater than 2.1 and less than or equal to 3.0, greater than or equal to 2.1 and less than or equal to 2.8, greater than or equal to 2.1 and less than or equal to 2.6, greater than or equal to 2.1 and less than or equal to 2.5, greater than or equal to 2.1 and less than or equal to 2.4, greater than or equal to 2.1 and less than or equal to 2.3, greater than or equal to 2.2 and less than or equal to 4.0, greater than or equal to 2.2 and less than or equal to 3.8, greater than or equal to 2.2 and less than or equal to 3.6, greater than or equal to 2.2 and less than or equal to 3.4, greater than or equal to 2.2 and less than or equal to 3.2, greater than or equal to 2.2 and less than or equal to 3.0, greater than or equal to 2.2 and less than or equal to 2.8, greater than or equal to 2.2 and less than or equal to 2.6, greater than or equal to 2.2 and less than or equal to 2.5, or even greater than or equal to 2.2 and less than or equal to 2.4. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0117] As described herein, alkali metal oxides Li₂O are commonly used to form various glass ceramics. However, other alkali metal oxides tend to reduce glass ceramic formation, instead forming aluminosilicate residual amorphous glass within the glass ceramic. It has been found that exceeding about 5 wt% Na₂O or K₂O, or combinations thereof, results in an excessive amount of amorphous residual glass, which can lead to deformation during crystallization and undesirable microstructures from a mechanical property perspective. The composition of the amorphous residual glass can be tailored to control viscosity during crystallization, thereby minimizing deformation or undesirable thermal expansion, or controlling microstructure properties. Therefore, precursor glasses can typically contain relatively small amounts of non-lithium alkali metal oxides. For example, in embodiments, the precursor glass or glass ceramic may contain greater than or equal to 0 wt% to less than or equal to 5.5 wt% R₂O, where R is one or more of the alkali cations Na and K. In embodiments, the precursor glass or glass ceramic composition may contain greater than or equal to 1 wt% to less than or equal to 3 wt% R₂O, where R is one or more of the alkali cations Na and K. In embodiments, the precursor glass or glass-ceramic composition may contain greater than or equal to 0.1 wt% to less than or equal to 0.5 wt% R₂O, greater than or equal to 0.1 wt% to less than or equal to 0.3 wt% R₂O, or even greater than or equal to 0.1 wt% to less than or equal to 0.25 wt% R₂O, wherein R is one or more of the basic cations Na and K. It should be understood that, in embodiments, the precursor glass and glass-ceramic do not contain R₂O. In embodiments, the precursor glass and glass-ceramic are substantially free of R₂O.

[0118] In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.5 wt% Na2O, greater than or equal to 0 wt% and less than or equal to 2 wt% Na2O, greater than or equal to 0 wt% and less than or equal to 1 wt% Na2O, or even greater than or equal to 0 wt% and less than or equal to 0.5 wt% Na2O. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0119] In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 3 wt% K2O, greater than or equal to 0 wt% and less than or equal to 2 wt% K2O, greater than or equal to 0 wt% and less than or equal to 1 wt% K2O, greater than or equal to 0.05 wt% and less than or equal to 1 wt% K2O, or even greater than or equal to 0.1 wt% and less than or equal to 1 wt% K2O. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0120] Precursor glasses and glass-ceramics include P2O5. P2O5 can act as a nucleating agent to produce a large number of nucleations. If the concentration of P2O5 is too low, the precursor glass will indeed crystallize, but only at higher temperatures (due to lower viscosity) and from the surface inward, resulting in brittle and often deformable crystals. However, if the concentration of P2O5 is too high, it can be difficult to control crystallization during cooling during the formation of the glass sheet. Examples of precursor glasses and glass-ceramics contain greater than or equal to 0.1 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 0.5 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 1.0 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 1.5 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 2.0 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 2.25 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 2.5 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 3.0 wt% and less than or equal to 5.0 wt% P2O5, greater than or equal to 0.1 wt% and less than or equal to 4.5 wt% P2O5, and greater than or equal to 0.5 wt% and less than or equal to 4.5 wt% P2O5. P2O5, greater than or equal to 1.0 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 1.5 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 2.0 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 2.25 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 2.5 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 3.0 wt% and less than or equal to 4.5 wt%; P2O5, greater than or equal to 0.1 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 0.5 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 1.0 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 1.5 wt% and less than or equal to 4.0 wt% P2O5, greater than or equal to 2.0 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 2.25 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 2.5 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 3.0 wt% and less than or equal to 4.0 wt%; P2O5, greater than or equal to 0.1 wt% and less than or equal to 3.5 wt%; P2O5, greater than or equal to 0.5 wt% and less than or equal to 3.5 wt%; P2O5, greater than or equal to 1.0 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 1.5 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 2.0 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 2.25 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 2.5 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 3.0 wt% and less than or equal to 3.5 wt% P2O5, greater than or equal to 0.1 wt% and less than or equal to 3.0 wt% P2O5, greater than or equal to 0.5 wt% and less than or equal to 3.0 wt% P2O5, greater than or equal to 1.0 wt% and less than or equal to 3.0 wt% P2O5, greater than or equal to 1.5 wt% and less than or equal to 3.0 wt% P2O5, greater than or equal to 2.0 wt% and less than or equal to 3.0 wt% P2O5. wt% P2O5, greater than or equal to 2.25 wt% and less than or equal to 3.0 wt%; P2O5, greater than or equal to 2.5 wt% and less than or equal to 3.0 wt%; P2O5, greater than or equal to 0.1 wt% and less than or equal to 2.5 wt%; P2O5, greater than or equal to 0.5 wt% and less than or equal to 2.5 wt%; P2O5, greater than or equal to 1.0 wt% and less than or equal to 2.5 wt%; P2O5, greater than or equal to 1.5 wt% and less than or equal to 2.5 wt%; P2O5, greater than or equal to 2.0 wt% and less than or equal to 2.5 wt%; P2O5, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt%; P2O5, greater than or equal to 0.5 wt% and less than or equal to 2.0 wt%; P2O5, greater than or equal to 1.0 wt% and less than or equal to 2.0 wt% P2O5, greater than or equal to 1.5 wt% and less than or equal to 2.0 wt%; greater than or equal to 0.1 wt% and less than or equal to 1.5 wt%; greater than or equal to 0.5 wt% and less than or equal to 1.5 wt%; greater than or equal to 1.0 wt% and less than or equal to 1.5 wt%; greater than or equal to 0.1 wt% and less than or equal to 1.0 wt%; greater than or equal to 0.5 wt% and less than or equal to 1.0 wt%; or greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% P2O5. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0121] In addition to the other effects of ZrO2 described in this paper, ZrO2 is generally found to improve the stability of Li2O—Al2O3—SiO2—P2O5 glasses by significantly reducing glass crystallization during forming and lowering the liquidus temperature. At concentrations exceeding 8 wt%, ZrSiO4 can form a primary liquidus phase at high temperatures, thereby significantly reducing the liquidus viscosity. When the glass contains more than 2 wt% ZrO2, a transparent precursor glass can be formed. The addition of ZrO2 can also help reduce the particle size of lithopelite, thus contributing to the formation of transparent glass-ceramics.In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 4 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 5 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 6 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 7 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 8 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 10 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 12 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 14 wt% and less than or equal to 15 wt% ZrO2, greater than or equal to 4 wt% and less than or equal to 14 wt% ZrO2, greater than or equal to 5 wt% and less than or equal to 14 wt% ZrO2, greater than or equal to 6 wt% and less than or equal to 14 wt% ZrO2, greater than or equal to 7 wt% ZrO2, and less than or equal to 7 wt% ZrO2. ZrO2 wt% and less than or equal to 14 wt%, ZrO2 wt% and greater than or equal to 8 wt% and less than or equal to 14 wt%, ZrO2 wt% and greater than or equal to 10 wt% and less than or equal to 14 wt%, ZrO2 wt% and greater than or equal to 12 wt%, ZrO2 wt% and greater than or equal to 4 wt% and less than or equal to 14 wt%, ZrO2 wt% and greater than or equal to 4 wt% and less than or equal to 14 wt%, ZrO2 wt% and greater than or equal to 4 wt% and less than or equal to 12 wt%, ZrO2 wt% and greater than or equal to 5 wt% and less than or equal to 10 wt%. ZrO2, greater than or equal to 6 wt% and less than or equal to 10 wt% ZrO2, greater than or equal to 7 wt% and less than or equal to 10 wt% ZrO2, greater than or equal to 8 wt% and less than or equal to 10 wt% ZrO2, greater than or equal to 4 wt% and less than or equal to 9 wt% ZrO2, greater than or equal to 6 wt% and less than or equal to 9 wt% ZrO2, or greater than or equal to 7 wt% and less than or equal to 9 wt% ZrO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0122] As described herein, it has been found that when the ratio of Li₂O (wt%) to ZrO₂ (wt%) in the precursor glass and the resulting glass-ceramic (i.e., Li₂O:ZrO₂) is greater than or equal to 1.20 and less than or equal to 1.70, the central tension of the glass-ceramic strengthened by ion exchange can be maximized. In the embodiments, the ratios of Li₂O to ZrO₂ in the precursor glass and glass-ceramic are greater than or equal to 1.30 and less than or equal to 1.70, greater than or equal to 1.35 and less than or equal to 1.70, greater than or equal to 1.40 and less than or equal to 1.70, greater than or equal to 1.45 and less than or equal to 1.70, greater than or equal to 1.50 and less than or equal to 1.70, greater than or equal to 1.55 and less than or equal to 1.70, greater than or equal to 1.60 and less than or equal to 1.70, and greater than or equal to 1.20 and less than or equal to 1. 65. Values ​​greater than or equal to 1.20 and less than or equal to 1.60, greater than or equal to 1.20 and less than or equal to 1.55, greater than or equal to 1.20 and less than or equal to 1.50, greater than or equal to 1.20 and less than or equal to 1.45, greater than or equal to 1.20 and less than or equal to 1.40, greater than or equal to 1.25 and less than or equal to 1.65, greater than or equal to 1.30 and less than or equal to 1.60, greater than or equal to 1.35 and less than or equal to 1.55, or even greater than or equal to 1.40 and less than or equal to 1.50. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0123] In embodiments, the ratio of Al2O3 (wt%) to ZrO2 (wt%) (i.e., Al2O3:ZrO2) can be greater than 0 and less than or equal to 1. Without being bound by theory, it is considered that an Al2O3 to ZrO2 ratio in the range of greater than 0 and less than or equal to 1 can reduce the liquidus viscosity of the precursor glass. In embodiments, the Al2O3 to ZrO2 ratio can be greater than or equal to 0.1 and less than or equal to 0.9, greater than or equal to 0.15 and less than or equal to 0.85, greater than or equal to 0.20 and less than or equal to 0.80, greater than or equal to 0.25 and less than or equal to 0.75, greater than or equal to 0.30 and less than or equal to 0.70, greater than or equal to 0.35 and less than or equal to 0.65, or even greater than or equal to 0.40 and less than or equal to 0.65. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0124] CaO can enter the petalite crystals in the form of a partial solid solution. In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0.05 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 1.0 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 1.5 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 2.0 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 2.5 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 3.0 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 3.5 wt% and less than or equal to 4.0 wt% CaO, greater than or equal to 0.1 ... wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 1.0 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 1.5 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 2.0 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 2.5 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 3.0 wt% and less than or equal to 3.5 wt% CaO, greater than or equal to 0.05 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 1.0 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 1.5 wt% CaO, and greater than or equal to 1.5 wt% CaO. wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 2.0 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 2.5 wt% and less than or equal to 3.0 wt% CaO, greater than or equal to 0.05 wt% and less than or equal to 2.5 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 2.5 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 2.5 wt% CaO, greater than or equal to 1.0 wt% and less than or equal to 2.5 wt% CaO, greater than or equal to 1.5 wt% and less than or equal to 2.5 wt% CaO, greater than or equal to 2.0 wt% and less than or equal to 2.0 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 2.0 wt% CaO, greater than or equal to 1.0 wt% and less than or equal to 2.0 wt% CaO, greater than or equal to 1.5 wt% and less than or equal to 2.0 wt% CaO, greater than or equal to 0.05 wt% and less than or equal to 1.5 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% CaO, greater than or equal to 0.05 wt% and less than or equal to 1.0 wt% CaO, greater than or equal to 0.5 wt% and less than or equal to 1.0 wt% CaO, greater than or equal to 0.05 wt% CaO, greater than or equal to 0.05 wt% CaO, less than or equal to 1.0 wt% CaO, greater than or equal to 0.05 wt% CaO, less than or equal to 1.0 wt% CaO, greater than or equal to 0.05 wt% CaO, less than or equal to 1.0 wt% CaO, less ... The concentrations are defined as follows: wt% and less than or equal to 0.5 wt% CaO, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% CaO, or greater than or equal to 0.05 wt% and less than or equal to 0.1 wt% CaO. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0125] In the embodiments, the precursor glass or glass-ceramic may further comprise MgO. Without being bound by theory, it is considered that the addition of MgO may enter the residual amorphous glass phase or the lithium feldspar crystalline phase. It is believed that the addition of MgO into the residual amorphous glass phase can reduce the diffusion rate of alkali ions in the glass, as in ion exchange processes. Therefore, the MgO content in the embodiments described herein is limited to 2.0 wt% to avoid any detrimental effects on ion exchange performance. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% to less than or equal to 2.0 wt% MgO, greater than or equal to 0 wt% to less than or equal to 1.5 wt% MgO, greater than or equal to 0 wt% to less than or equal to 1.0 wt% MgO, greater than or equal to 0 wt% to less than or equal to 0.5 wt% MgO, greater than or equal to 0.1 wt% to less than or equal to 2.0 wt% MgO, greater than or equal to 0.1 wt% to less than or equal to 1.5 wt% MgO, greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% MgO, or even greater than or equal to 0.1 wt% to less than or equal to 0.5 wt% MgO. In embodiments, the precursor glass and glass-ceramic do not contain MgO. In embodiments, the precursor glass and glass-ceramic are substantially free of MgO. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0126] In embodiments, the precursor glass or glass-ceramic may further include SrO. It is not desirable to be bound by theory, but it is thought that SrO (when present) may increase the amount of residual glass in the resulting glass-ceramic. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% SrO, greater than or equal to 0 wt% and less than or equal to 1.5 wt% SrO, greater than or equal to 0 wt% and less than or equal to 1.0 wt% SrO, greater than or equal to 0 wt% and less than or equal to 0.5 wt% SrO, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% SrO, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% SrO, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% SrO, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% SrO. In embodiments, the precursor glass and glass-ceramic do not include SrO. In the embodiments, the precursor glass and glass-ceramic are substantially free of SrO. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0127] In embodiments, the precursor glass or glass-ceramic may further include BaO. It is not desirable to be bound by theory, but it is thought that BaO (when present) may increase the amount of residual glass in the resulting glass-ceramic. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% BaO, greater than or equal to 0 wt% and less than or equal to 1.5 wt% BaO, greater than or equal to 0 wt% and less than or equal to 1.0 wt% BaO, greater than or equal to 0 wt% and less than or equal to 0.5 wt% BaO, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% BaO, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% BaO, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% BaO, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% BaO. In embodiments, the precursor glass and glass-ceramic do not include BaO. In embodiments, the precursor glass and glass-ceramic are substantially free of BaO. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0128] In some embodiments, the precursor glass or glass ceramic may further include ZnO. In the embodiments, the precursor glass and glass-ceramic comprise ≥0 wt% and ≤4.0 wt% ZnO, ≥0 wt% and ≤3.0 wt% ZnO, ≥0 wt% and ≤2.5 wt% ZnO, ≥0 wt% and ≤2.0 wt% ZnO, ≥0 wt% and ≤1.5 wt% ZnO, ≥0 wt% and ≤1.0 wt% ZnO, ≥0 wt% and ≤0.5 wt% ZnO, ≥0.1 wt% and ≤4.0 wt% ZnO, ≥0.1 to ≤3 wt% ZnO, ≥0.1 wt% and ≤2.5 wt% ZnO, and ≥0.1 wt% and ≤2.0 wt% ZnO. ZnO, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% ZnO, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% ZnO, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% ZnO. In embodiments, the precursor glass and glass ceramic do not include ZnO. In embodiments, the precursor glass and glass ceramic are substantially free of ZnO. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0129] In embodiments, the precursor glass or glass-ceramic may further comprise B2O3. It is thought that, without being bound by theory, the addition of B2O3 may partition into the amorphous residual glass. It is also thought that the addition of B2O3 may reduce the viscosity of the precursor glass at the ceramization temperature. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% B2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% B2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% B2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% B2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% B2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% B2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% B2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% B2O3. In embodiments, the precursor glass and glass-ceramic do not contain B2O3. In embodiments, the precursor glass and glass-ceramic are substantially free of B2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0130] Fe2O3 can lower the melting point of precursor glasses and glass-ceramics. However, adding too much Fe2O3 can alter the color of precursor glasses and glass-ceramics. In embodiments, the precursor glasses and glass-ceramics do not contain Fe2O3. In embodiments, the precursor glasses and glass-ceramics are substantially free of Fe2O3. In embodiments, the precursor glasses and glass-ceramics contain greater than 0.0 wt% and less than or equal to 1.0 wt% Fe2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Fe2O3, greater than 0.0 wt% and less than or equal to 0.3 wt% Fe2O3, greater than or equal to 0.0 wt% and less than or equal to 0.2 wt% Fe2O3, or greater than 0.0 wt% and less than or equal to 0.1 wt% Fe2O3. It should be understood that the above scope includes all subscopes within the explicitly disclosed scope.

[0131] In the embodiments, the precursor glass or glass-ceramic may further include HfO2. Without being bound by theory, it is considered that the addition of HfO2 can at least partially replace ZrO2 in the composition. In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 3.0 wt% HfO2, greater than or equal to 0 wt% and less than or equal to 2.5 wt% HfO2, greater than or equal to 0 wt% and less than or equal to 2.0 wt% HfO2, greater than or equal to 0 wt% and less than or equal to 1.5 wt% HfO2, greater than or equal to 0 wt% and less than or equal to 1.0 wt% HfO2, greater than or equal to 0 wt% and less than or equal to 0.5 wt% HfO2, greater than or equal to 0.1 to less than or equal to 3 wt% HfO2, greater than or equal to 0.1 wt% and less than or equal to 2.5 wt% HfO2, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% HfO2, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% HfO2, and greater than or equal to 0.1 wt% HfO2. The content of HfO2 is wt% and less than or equal to 1.0 wt% or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% wt%. In embodiments, the precursor glass and glass-ceramic do not contain HfO2. In embodiments, the precursor glass and glass-ceramic are substantially free of HfO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0132] In embodiments, the precursor glass or glass-ceramic may further include Y₂O₃. It is assumed that adding Y₂O₃ can increase the refractive index of the precursor glass and the resulting glass-ceramic, without being bound by theory. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Y₂O₃, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Y₂O₃, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Y₂O₃, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Y₂O₃, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Y₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Y₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Y₂O₃, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Y₂O₃. In this embodiment, the precursor glass and glass-ceramic do not contain Y2O3. In this embodiment, the precursor glass and glass-ceramic are substantially free of Y2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0133] In the embodiments, the precursor glass or glass-ceramic may further include La2O3. Without being bound by theory, it is believed that the addition of La2O3 can increase the refractive index of the precursor glass and the resulting glass-ceramic. It is also believed that the addition of La2O3 can alter the liquidus temperature of the precursor glass. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% La2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% La2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% La2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% La2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% La2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% La2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% La2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% La2O3. In embodiments, the precursor glass and glass-ceramic do not contain La2O3. In embodiments, the precursor glass and glass-ceramic are substantially free of La2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0134] In embodiments, the precursor glass or glass-ceramic may further include CeO2. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% CeO2, greater than or equal to 0 wt% and less than or equal to 1.5 wt% CeO2, greater than or equal to 0 wt% and less than or equal to 1.0 wt% CeO2, greater than or equal to 0 wt% and less than or equal to 0.5 wt% CeO2, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% CeO2, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% CeO2, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% CeO2, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% CeO2. In embodiments, the precursor glass and glass-ceramic do not include CeO2. In embodiments, the precursor glass and glass-ceramic are substantially free of CeO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0135] In embodiments, the precursor glass or glass-ceramic may further include Eu2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Eu2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Eu2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Eu2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Eu2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Eu2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Eu2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Eu2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Eu2O3. In embodiments, the precursor glass and glass-ceramic do not include Eu2O3. In embodiments, the precursor glass and glass-ceramic are substantially free of Eu2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0136] In embodiments, the precursor glass or glass-ceramic may further comprise Dy2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Dy2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Dy2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Dy2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Dy2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Dy2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Dy2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Dy2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Dy2O3. In embodiments, the precursor glass and glass-ceramic do not contain Dy2O3. In the embodiments, the precursor glass and glass-ceramic are substantially free of Dy2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0137] In embodiments, the precursor glass or glass-ceramic may further include Tb4O7. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Tb4O7, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Tb4O7, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Tb4O7, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Tb4O7, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Tb4O7, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Tb4O7, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Tb4O7, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Tb4O7. In embodiments, the precursor glass and glass-ceramic do not contain Tb4O7. In the embodiments, the precursor glass and glass-ceramic are substantially free of Tb4O7. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0138] In embodiments, the precursor glass or glass-ceramic may further include Yb₂O₃. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Yb₂O₃, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Yb₂O₃, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Yb₂O₃, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Yb₂O₃, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Yb₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Yb₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Yb₂O₃, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Yb₂O₃. In embodiments, the precursor glass and glass-ceramic do not contain Yb₂O₃. In the embodiments, the precursor glass and glass-ceramic are substantially free of Yb2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0139] In embodiments, the precursor glass or glass-ceramic may further comprise Gd₂O₃. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Gd₂O₃, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Gd₂O₃, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Gd₂O₃, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Gd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Gd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Gd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Gd₂O₃, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Gd₂O₃. In embodiments, the precursor glass and glass-ceramic do not contain Gd₂O₃. In the embodiments, the precursor glass and glass-ceramic are substantially free of Gd2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0140] In embodiments, the precursor glass or glass-ceramic may further include Tm2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Tm2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Tm2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Tm2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Tm2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Tm2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Tm2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Tm2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Tm2O3. In embodiments, the precursor glass and glass-ceramic do not contain Tm2O3. In the embodiments, the precursor glass and glass-ceramic are substantially free of Tm2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0141] In embodiments, the precursor glass or glass-ceramic may further include Lu2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Lu2O3, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Lu2O3, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Lu2O3, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Lu2O3, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Lu2O3, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Lu2O3, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Lu2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Lu2O3. In embodiments, the precursor glass and glass-ceramic do not include Lu2O3. In embodiments, the precursor glass and glass-ceramic are substantially free of Lu2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0142] In embodiments, the precursor glass or glass-ceramic may further include Nd₂O₃. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Nd₂O₃, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Nd₂O₃, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Nd₂O₃, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Nd₂O₃, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Nd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Nd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Nd₂O₃, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Nd₂O₃, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Nd₂O₃. In the embodiments, the precursor glass and glass-ceramic do not contain Nd₂O₃. In the embodiments, the precursor glass and glass-ceramic are substantially free of Nd₂O₃. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0143] In embodiments, the precursor glass or glass-ceramic may further include Pr2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Pr2O3, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Pr2O3, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Pr2O3, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Pr2O3, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Pr2O3, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Pr2O3, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Pr2O3, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Pr2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Pr2O3. In some embodiments, the precursor glass and glass-ceramic do not contain Pr2O3. In others, the precursor glass and glass-ceramic are substantially free of Pr2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0144] In embodiments, the precursor glass or glass-ceramic may further include Er2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Er2O3, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Er2O3, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Er2O3, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Er2O3, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Er2O3, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Er2O3, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Er2O3, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Er2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Er2O3. In this embodiment, the precursor glass and glass-ceramic do not contain Er2O3. In this embodiment, the precursor glass and glass-ceramic are substantially free of Er2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0145] In embodiments, the precursor glass or glass-ceramic may further include Sm2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Sm2O3, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Sm2O3, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Sm2O3, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Sm2O3, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Sm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Sm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Sm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Sm2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Sm2O3. In this embodiment, the precursor glass and glass-ceramic do not contain Sm2O3. In this embodiment, the precursor glass and glass-ceramic are substantially free of Sm2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0146] In embodiments, the precursor glass or glass-ceramic may further include Ho2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Ho2O3, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Ho2O3, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Ho2O3, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Ho2O3, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Ho2O3, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Ho2O3, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Ho2O3, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Ho2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Ho2O3. In this embodiment, the precursor glass and glass-ceramic do not contain Ho2O3. In this embodiment, the precursor glass and glass-ceramic are substantially free of Ho2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0147] In embodiments, the precursor glass or glass-ceramic may further include Pm2O3. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 0.5 wt% Pm2O3, greater than or equal to 0 wt% and less than or equal to 0.4 wt% Pm2O3, greater than or equal to 0 wt% and less than or equal to 0.3 wt% Pm2O3, greater than or equal to 0 wt% and less than or equal to 0.2 wt% Pm2O3, greater than or equal to 0 wt% and less than or equal to 0.1 wt% Pm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Pm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.4 wt% Pm2O3, greater than or equal to 0.1 wt% and less than or equal to 0.3 wt% Pm2O3, or even greater than or equal to 0.1 wt% and less than or equal to 0.2 wt% Pm2O3. In this embodiment, the precursor glass and glass-ceramic do not contain Pm2O3. In this embodiment, the precursor glass and glass-ceramic are substantially free of Pm2O3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0148] In embodiments, the precursor glass or glass-ceramic may further include Ta2O5. Without being bound by theory, it is believed that adding Ta2O5 can increase the refractive index of the precursor glass and the resulting glass-ceramic. It is also believed that adding Ta2O5 can increase the elastic modulus of the precursor glass and the resulting glass-ceramic. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% Ta₂O₅, greater than or equal to 0 wt% and less than or equal to 1.5 wt% Ta₂O₅, greater than or equal to 0 wt% and less than or equal to 1.0 wt% Ta₂O₅, greater than or equal to 0 wt% and less than or equal to 0.5 wt% Ta₂O₅, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% Ta₂O₅, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% Ta₂O₅, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% Ta₂O₅, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% Ta₂O₅. In embodiments, the precursor glass and glass-ceramic do not contain Ta₂O₅. In embodiments, the precursor glass and glass-ceramic are substantially free of Ta₂O₅. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0149] In the embodiments, the precursor glass or glass-ceramic may further include GeO2. It is assumed, without being bound by theory, that the addition of GeO2 can increase the refractive index of the precursor glass and the resulting glass-ceramic. In the embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 5.0 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 4.5 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 4.0 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 3.5 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 3.0 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 2.5 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 2.0 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 1.5 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 1.0 wt% GeO2, greater than or equal to 0 wt% and less than or equal to 0.5 wt% GeO2, and greater than or equal to 0.1 wt% and less than or equal to 5.0 wt% GeO2. GeO2, greater than or equal to 0.1 wt% and less than or equal to 4.5 wt%; greater than or equal to 0.1 wt% and less than or equal to 4.0 wt%; greater than or equal to 0.1 wt% and less than or equal to 3.5 wt%; greater than or equal to 0.1 wt% and less than or equal to 3.0 wt%; greater than or equal to 0.1 wt% and less than or equal to 2.5 wt%; greater than or equal to 0.1 wt% and less than or equal to 2.0 wt%; greater than or equal to 0.1 wt% and less than or equal to 1.5 wt%; greater than or equal to 0.1 wt% and less than or equal to 1.0 wt%; or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% GeO2. In embodiments, the precursor glass and glass-ceramic do not contain GeO2. In embodiments, the precursor glass and glass-ceramic are substantially free of GeO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0150] In embodiments, the precursor glass or glass-ceramic may further comprise TiO2. In embodiments, the precursor glass and glass-ceramic contain greater than or equal to 0 wt% and less than or equal to 2.0 wt% TiO2, greater than or equal to 0 wt% and less than or equal to 1.5 wt% TiO2, greater than or equal to 0 wt% and less than or equal to 1.0 wt% TiO2, greater than or equal to 0 wt% and less than or equal to 0.5 wt% TiO2, greater than or equal to 0.1 wt% and less than or equal to 2.0 wt% TiO2, greater than or equal to 0.1 wt% and less than or equal to 1.5 wt% TiO2, greater than or equal to 0.1 wt% and less than or equal to 1.0 wt% TiO2, or even greater than or equal to 0.1 wt% and less than or equal to 0.5 wt% TiO2. In embodiments, the precursor glass and glass-ceramic do not contain TiO2. In embodiments, the precursor glass and glass-ceramic are substantially free of TiO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0151] In embodiments, the precursor glass or glass-ceramic may further comprise a chemical clarifying agent. Such clarifying agents include, but are not limited to, SnO2, As2O3, Sb2O3, SO3, F, Cl, and Br. In some embodiments, the concentration of the chemical clarifying agent is maintained at levels of 3 wt%, 2 wt%, 1 wt%, or 0.5 wt%, >0 wt%. In an embodiment, the chemical clarifying agent is SnO2, and the precursor glass or glass-ceramic contains greater than or equal to 0 to less than or equal to 3 wt% SnO2. In the embodiments, the precursor glass or glass-ceramic contains greater than or equal to 0 wt% and less than or equal to 2.5 wt% SnO2, greater than or equal to 0 wt% and less than or equal to 2.0 wt% SnO2, greater than or equal to 0 wt% and less than or equal to 1.5 wt% SnO2, greater than or equal to 0 wt% and less than or equal to 1.0 wt% SnO2, greater than or equal to 0 wt% and less than or equal to 0.5 wt% SnO2, greater than 0.01 wt% to less than or equal to 3 wt% SnO2, greater than 0.01 wt% and less than or equal to 2.5 wt% SnO2, greater than 0.01 wt% and less than or equal to 2.0 wt% SnO2, greater than 0.01 wt% and less than or equal to 1.5 wt% SnO2, greater than 0.01 wt% and less than or equal to 1.0 wt% SnO2, or even greater than 0.01 wt% and less than or equal to 0.5 wt% SnO2. SnO2. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope. In embodiments, chemical clarifying agents may also include CeO2, Fe2O3, and other transition metal oxides, such as MnO2. These oxides may introduce undesirable color into the precursor glass or glass ceramic via visible absorption of their final valence state in the glass, and therefore, when present, their concentrations are typically maintained at levels of 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, or > 0 wt%. In embodiments, the precursor glass or glass ceramic does not include chemical clarifying agents.

[0152] In some embodiments, the precursor glass or glass-ceramic may be substantially free of Sb₂O₃, As₂O₃, or combinations thereof. For example, the precursor glass or glass-ceramic may contain 0.05 wt% or less of Sb₂O₃ or As₂O₃, or combinations thereof; the precursor glass or glass-ceramic may contain 0 wt% of Sb₂O₃ or As₂O₃, or combinations thereof; or the precursor glass or glass-ceramic may, for example, be free of any intentionally added Sb₂O₃, As₂O₃, or combinations thereof.

[0153] In embodiments, glass having the composition described herein can initially be formed by mixing ingredients from component sources (i.e., SiO2 source, Al2O3 source, etc.), heating the ingredients to form molten glass, and then shaping or forming the molten glass into a glass article using conventional forming processes (such as slot drawing, float glass, rolling, fusion molding, etc.). In this case, the glass or glass article may be referred to as "precursor glass," which refers to glass or glass article prior to ceramization to transform the glass into glass ceramics to form glass ceramic articles.

[0154] The method for manufacturing glass-ceramics according to an embodiment includes heat-treating a precursor glass at two preselected temperatures for one or more preselected times to induce glass homogenization and crystallization (i.e., nucleation and growth) of one or more crystalline phases (e.g., having one or more compositions, amounts, morphologies, sizes, or size distributions). These two temperatures may be referred to as the nucleation temperature and the growth temperature, respectively.

[0155] Now for reference Figure 1 This document typically describes an embodiment of a method 1000 for manufacturing glass-ceramics. Initially, at step 1001, a precursor glass is heated in an oven to a nucleation temperature greater than or equal to 550°C and less than or equal to 650°C. It should be understood that the nucleation temperature corresponds to the temperature of the oven in which the precursor glass is heated, and that the temperature of the precursor glass can be within + / - 5°C of the nucleation temperature when the oven temperature is at the nucleation temperature. At step 1002, the precursor glass is held in the oven for a first duration within a temperature range greater than or equal to the nucleation temperature and less than or equal to 650°C to form a nucleated precursor glass. At step 1003, the nucleated precursor glass is heated to a growth temperature greater than or equal to 680°C and less than or equal to 800°C. At step 1004, the nucleated precursor glass is held for a second duration within a temperature range greater than or equal to the growth temperature and less than or equal to 800°C to form a glass-ceramic. In an embodiment, at step 1005, the glass-ceramic may be exposed to an ion exchange medium comprising molten potassium salt, molten sodium salt, or a combination thereof, with or without the addition of LiNO3 to the ion exchange bath to form a reinforced glass-ceramic. Each of these steps will be described in more detail below.

[0156] In this embodiment, the nucleation stage occurs while the precursor glass is held at a predetermined nucleation temperature for a predetermined duration. In this embodiment, the nucleation temperatures are greater than or equal to 550°C and less than or equal to 650°C, greater than or equal to 560°C and less than or equal to 650°C, greater than or equal to 570°C and less than or equal to 650°C, greater than or equal to 580°C and less than or equal to 650°C, greater than or equal to 590°C and less than or equal to 650°C, greater than or equal to 600°C and less than or equal to 650°C, greater than or equal to 610°C and less than or equal to 650°C, greater than or equal to 620°C and less than or equal to 650°C, greater than or equal to 630°C and less than or equal to 650°C, greater than or equal to 640°C and less than or equal to 650°C, greater than or equal to 550°C and less than or equal to 640°C, greater than or equal to 560°C, and less than or equal to 560°C. 0℃ and less than or equal to 640℃, greater than or equal to 570℃ and less than or equal to 640℃, greater than or equal to 580℃ and less than or equal to 640℃, greater than or equal to 590℃ and less than or equal to 640℃, greater than or equal to 600℃ and less than or equal to 640℃, greater than or equal to 610℃ and less than or equal to 640℃, greater than or equal to 620℃ and less than or equal to 640℃, greater than or equal to 630℃ and less than or equal to 640℃, greater than or equal to 550℃ and less than or equal to 630℃, greater than or equal to 560℃ and less than or equal to 630℃, greater than or equal to 570℃ and less than or equal to 630℃, greater than or equal to 580℃ and less than or equal to 630℃, greater than or equal to 590℃ and less than or equal to 630℃, greater than or equal to 600℃ and less than or equal to 630℃, greater than or equal to 610℃ and less than or equal to 630℃, greater than or equal to 620℃ and less than or equal to 630℃, greater than or equal to 550℃ and less than or equal to 620℃, greater than or equal to 560℃ and less than or equal to 620℃, greater than or equal to 570℃ and less than or equal to 620℃, greater than or equal to 580℃ and less than or equal to 620℃, greater than or equal to 590℃ and less than or equal to 620℃, greater than or equal to 600℃ and less than or equal to 620℃, greater than or equal to 610℃ and less than or equal to 620℃, greater than or equal to 550℃ and less than or equal to 610℃, greater than The following temperatures are considered acceptable: 560℃ and less than or equal to 610℃; 570℃ and less than or equal to 610℃; 580℃ and less than or equal to 610℃; 590℃ and less than or equal to 610℃; 600℃ and less than or equal to 610℃; 550℃ and less than or equal to 600℃; 560℃ and less than or equal to 600℃; 570℃ and less than or equal to 600℃; 580℃ and less than or equal to 600℃; 590℃ and less than or equal to 600℃; 550℃ and less than or equal to 590℃; 560℃ and less than or equal to 590℃.The temperatures are greater than or equal to 570℃ and less than or equal to 590℃, greater than or equal to 580℃ and less than or equal to 590℃, greater than or equal to 550℃ and less than or equal to 580℃, greater than or equal to 560℃ and less than or equal to 580℃, greater than or equal to 570℃ and less than or equal to 580℃, greater than or equal to 550℃ and less than or equal to 570℃, greater than or equal to 560℃ and less than or equal to 570℃, or greater than or equal to 550℃ and less than or equal to 560℃. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0157] In an embodiment, the precursor glass is maintained at the nucleation temperature for the following durations: greater than or equal to 1 minute and less than or equal to 360 minutes, greater than or equal to 30 minutes and less than or equal to 360 minutes, greater than or equal to 60 minutes and less than or equal to 360 minutes, greater than or equal to 90 minutes and less than or equal to 360 minutes, greater than or equal to 120 minutes and less than or equal to 360 minutes, greater than or equal to 150 minutes and less than or equal to 360 minutes, greater than or equal to 180 minutes and less than or equal to 360 minutes, greater than or equal to 210 minutes and less than or equal to 360 minutes, greater than or equal to 240 minutes and less than or equal to 360 minutes, greater than or equal to 270 minutes and less than or equal to 360 minutes, greater than or equal to 30 minutes and less than or equal to 30 minutes. 0 minutes to less than or equal to 360 minutes, greater than or equal to 330 minutes to less than or equal to 360 minutes, greater than or equal to 1 minute to less than or equal to 330 minutes, greater than or equal to 30 minutes to less than or equal to 330 minutes, greater than or equal to 60 minutes to less than or equal to 330 minutes, greater than or equal to 90 minutes to less than or equal to 330 minutes, greater than or equal to 120 minutes to less than or equal to 330 minutes, greater than or equal to 150 minutes to less than or equal to 330 minutes, greater than or equal to 180 minutes to less than or equal to 330 minutes, greater than or equal to 210 minutes to less than or equal to 330 minutes, greater than or equal to 240 minutes to less than or equal to 330 minutes, greater than or equal to 270 minutes to less than or equal to 330 minutes 0 minutes, 300 minutes or more to 330 minutes or less, 1 minute or more to 300 minutes or less, 30 minutes or more to 300 minutes or less, 60 minutes or more to 300 minutes or less, 90 minutes or more to 300 minutes or less, 120 minutes or more to 300 minutes or less, 150 minutes or more to 300 minutes or less, 180 minutes or more to 300 minutes or less, 210 minutes or more to 300 minutes or less, 240 minutes or more to 300 minutes or less, 270 minutes or more to 300 minutes or less, 1 minute or more Clocks up to 270 minutes or less, 30 minutes or more, 60 minutes or more, 90 minutes or more, 120 minutes or more, 150 minutes or more, 180 minutes or more, 210 minutes or more, 240 minutes or more, 1 minute or more, 30 minutes or more, 60 minutes or more, and 240 minutes or more.90 minutes or more and 240 minutes or less; 120 minutes or more and 240 minutes or less; 150 minutes or more and 240 minutes or less; 180 minutes or more and 240 minutes or less; 210 minutes or more and 240 minutes or less; 1 minute or more and 210 minutes or less; 30 minutes or more and 210 minutes or less; 60 minutes or more and 210 minutes or less; large 90 minutes or less than or equal to 210 minutes, 120 minutes or more than or equal to 210 minutes, 150 minutes or more than or equal to 210 minutes, 180 minutes or more than or equal to 210 minutes, 1 minute or more than or equal to 180 minutes, 30 minutes or more than or equal to 180 minutes, 60 minutes or more than or equal to 180 minutes, 90 minutes or more than or equal to 180 minutes, or more than or equal to 90 minutes. 120 minutes to less than or equal to 180 minutes, greater than or equal to 150 minutes to less than or equal to 180 minutes, greater than or equal to 1 minute to less than or equal to 150 minutes, greater than or equal to 30 minutes to less than or equal to 150 minutes, greater than or equal to 60 minutes to less than or equal to 150 minutes, greater than or equal to 90 minutes to less than or equal to 150 minutes, greater than or equal to 120 minutes to less than or equal to 150 minutes, greater than or equal to 1 minute to less than or equal to 120 minutes, greater than or equal to 30 minutes The timeframes are defined as follows: 120 minutes or less; 60 minutes or more; 90 minutes or more; 1 minute or more; 30 minutes or more; 60 minutes or more; 1 minute or more; 30 minutes or more; or 1 minute or more. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range. After the nucleation stage, the precursor glass is referred to as the nucleated precursor glass.

[0158] The growth stage occurs while the precursor glass for nucleation is held at a predetermined growth temperature for a predetermined duration. In embodiments, the growth temperature is higher than the nucleation temperature. In embodiments, the growth temperatures are greater than or equal to 680°C and less than or equal to 800°C, greater than or equal to 690°C and less than or equal to 800°C, greater than or equal to 700°C and less than or equal to 800°C, greater than or equal to 710°C and less than or equal to 800°C, greater than or equal to 720°C and less than or equal to 800°C, greater than or equal to 730°C and less than or equal to 800°C, greater than or equal to 740°C and less than or equal to 800°C, greater than or equal to 750°C and less than or equal to 800°C, greater than or equal to 760°C and less than or equal to 800°C, greater than or equal to 770°C and less than or equal to 800°C, greater than or equal to 780°C and less than or equal to 800°C, greater than... The following temperatures are considered high: 790℃ and less than or equal to 800℃; 680℃ and less than or equal to 790℃; 690℃ and less than or equal to 790℃; 700℃ and less than or equal to 790℃; 710℃ and less than or equal to 790℃; 720℃ and less than or equal to 790℃; 730℃ and less than or equal to 790℃; 740℃ and less than or equal to 790℃; 750℃ and less than or equal to 790℃; 760℃ and less than or equal to 790℃; 770℃ and less than or equal to 790℃; and 780℃ and less than or equal to 790℃. 790℃, greater than or equal to 680℃ and less than or equal to 780℃, greater than or equal to 690℃ and less than or equal to 780℃, greater than or equal to 700℃ and less than or equal to 780℃, greater than or equal to 710℃ and less than or equal to 780℃, greater than or equal to 720℃ and less than or equal to 780℃, greater than or equal to 730℃ and less than or equal to 780℃, greater than or equal to 740℃ and less than or equal to 780℃, greater than or equal to 750℃ and less than or equal to 780℃, greater than or equal to 760℃ and less than or equal to 780℃, greater than or equal to 770℃ and less than or equal to 690℃, greater than or equal to 690℃ and less than or equal to 78 ... 0℃ and less than or equal to 770℃, greater than or equal to 700℃ and less than or equal to 770℃, greater than or equal to 710℃ and less than or equal to 770℃, greater than or equal to 720℃ and less than or equal to 770℃, greater than or equal to 730℃ and less than or equal to 770℃, greater than or equal to 740℃ and less than or equal to 770℃, greater than or equal to 750℃ and less than or equal to 770℃, greater than or equal to 760℃ and less than or equal to 770℃, greater than or equal to 680℃ and less than or equal to 760℃, greater than or equal to 690℃ and less than or equal to 760℃, greater than or equal to 700℃ and less than or equal to 760℃, greater than or equal to 710℃ and less than or equal to 760℃,720℃ or higher and 760℃ or lower; 730℃ or higher and 760℃ or lower; 740℃ or higher and 760℃ or lower; 750℃ or higher and 760℃ or lower; 680℃ or higher and 750℃ or lower; 690℃ or higher and 750℃ or lower; 700℃ or higher and 750℃ or lower; 710℃ or higher and 750℃ or lower 720℃ or higher and 750℃ or lower; 730℃ or higher and 750℃ or lower; 740℃ or higher and 750℃ or lower; 680℃ or higher and 740℃ or lower; 690℃ or higher and 740℃ or lower; 700℃ or higher and 740℃ or lower; 710℃ or higher and 740℃ or lower; 720℃ or higher and 740℃ or lower 730℃ or higher and 740℃ or lower; 680℃ or higher and 730℃ or lower; 690℃ or higher and 730℃ or lower; 700℃ or higher and 730℃ or lower; 710℃ or higher and 730℃ or lower; 720℃ or higher and 730℃ or lower; 680℃ or higher and 720℃ or higher; 690℃ or higher and 720℃ or lower The temperatures are defined as follows: greater than or equal to 700℃ and less than or equal to 720℃; greater than or equal to 710℃ and less than or equal to 720℃; greater than or equal to 680℃ and less than or equal to 710℃; greater than or equal to 690℃ and less than or equal to 710℃; greater than or equal to 700℃ and less than or equal to 710℃; greater than or equal to 680℃ and less than or equal to 700℃; greater than or equal to 690℃ and less than or equal to 700℃; or greater than or equal to 680℃ and less than or equal to 690℃. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0159] In the embodiments, the nucleation precursor glass is maintained at the growth temperature for the following durations: greater than or equal to 1 minute to less than or equal to 240 minutes, greater than or equal to 30 minutes to less than or equal to 240 minutes, greater than or equal to 60 minutes to less than or equal to 240 minutes, greater than or equal to 90 minutes to less than or equal to 240 minutes, greater than or equal to 120 minutes to less than or equal to 240 minutes, greater than or equal to 150 minutes to less than or equal to 240 minutes, greater than or equal to 180 minutes to less than or equal to 240 minutes, and greater than or equal to 210 minutes to less than or equal to 240 minutes. 40 minutes, greater than or equal to 1 minute and less than or equal to 210 minutes, greater than or equal to 30 minutes and less than or equal to 210 minutes, greater than or equal to 60 minutes and less than or equal to 210 minutes, greater than or equal to 90 minutes and less than or equal to 210 minutes, greater than or equal to 120 minutes and less than or equal to 210 minutes, greater than or equal to 150 minutes and less than or equal to 210 minutes, greater than or equal to 180 minutes and less than or equal to 210 minutes, greater than or equal to 1 minute and less than or equal to 180 minutes, greater than or equal to 30 minutes and less than or equal to 180 minutes, large The following are the time intervals for the following time intervals: 60 minutes or less than or equal to 180 minutes, 90 minutes or more than or equal to 180 minutes, 120 minutes or more than or equal to 180 minutes, 150 minutes or more than or equal to 180 minutes, 1 minute or more than or equal to 150 minutes, 30 minutes or more than or equal to 150 minutes, 60 minutes or more than or equal to 150 minutes, 90 minutes or more than or equal to 150 minutes, 120 minutes or more than or equal to 150 minutes, and so on. The timeframes are defined as follows: 1 minute to less than or equal to 120 minutes; greater than or equal to 30 minutes to less than or equal to 120 minutes; greater than or equal to 60 minutes to less than or equal to 120 minutes; greater than or equal to 90 minutes to less than or equal to 1 minute; greater than or equal to 30 minutes to less than or equal to 90 minutes; greater than or equal to 60 minutes to less than or equal to 90 minutes; greater than or equal to 1 minute to less than or equal to 60 minutes; greater than or equal to 30 minutes to less than or equal to 60 minutes; or greater than or equal to 1 minute to less than or equal to 30 minutes. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range. The growth stage transforms the nucleation precursor glass into a glass-ceramic material (i.e., glass ceramic or glass-ceramic articles).

[0160] If the precursor glass articles disclosed and described herein are maintained at the nucleation and growth temperatures for the durations disclosed and described herein, they will form a structure containing a residual amorphous glass phase and lithium feldspar (LiAlSi4O3). 10This invention relates to a glass-ceramic composite of a crystalline phase and a lithium disilicate (Li2Si2O5) crystalline phase. As described herein, this phase composite provides glass-ceramics with low haze (high clarity) and improved mechanical properties.

[0161] The nucleation temperature, growth temperature, and duration disclosed and described herein are considered to be the primary heat treatments that cause the desired phase assemblies in glass-ceramics. Additional heat treatments can be included before the nucleation stage, between the nucleation and growth stages, and after the growth stage without causing significant deviations in the phase assemblies of the glass-ceramic material. These additional heat treatments include isothermal holding, heating according to specific heating arrangements (including many different heating rates), and combinations thereof.

[0162] Therefore, in embodiments, one or more additional temperature holdings may exist between the nucleation temperature and the growth temperature. In embodiments, after holding the precursor glass at the nucleation temperature, the article may be heated to one or more intermediate temperatures (wherein the intermediate temperature is within the range between the nucleation temperature and the growth temperature), held at said one or more intermediate temperatures for a predetermined time (e.g., between 1 minute and 360 minutes, and all ranges and subranges therebetween), and then heated to the growth temperature.

[0163] In one embodiment, the nucleation phase includes an isothermal hold at a single nucleation temperature for a period of time. However, in other embodiments, the nucleation phase includes heating the precursor glass at one or more heating rates within the nucleation temperature range described herein (i.e., greater than or equal to 550°C to less than or equal to 650°C). Similarly, in one embodiment, the growth phase includes an isothermal hold at a single growth temperature for a period of time. However, in other embodiments, the growth phase includes heating or cooling the nucleated precursor glass at one or more heating rates within the growth temperature range described herein (i.e., greater than or equal to 680°C to less than or equal to 800°C).

[0164] According to embodiments, during the nucleation stage, between the nucleation stage and the growth stage, during the growth stage, and after the growth stage, the heating rates for heating from room temperature to the nucleation temperature are greater than or equal to 0.1°C / min and less than or equal to 50°C / min, greater than or equal to 5°C / min and less than or equal to 50°C / min, greater than or equal to 10°C / min and less than or equal to 50°C / min, greater than or equal to 15°C / min and less than or equal to 50°C / min, greater than or equal to 20°C / min and less than or equal to 50°C / min, greater than or equal to 25°C / min and less than or equal to 50°C / min, and greater than or equal to 30°C / min and less than or equal to 50°C / min. 50℃ / min, greater than or equal to 35℃ / min and less than or equal to 50℃ / min, greater than or equal to 40℃ / min and less than or equal to 50℃ / min, greater than or equal to 45℃ / min and less than or equal to 50℃ / min, greater than or equal to 0.1℃ / min and less than or equal to 45℃ / min, greater than or equal to 5℃ / min and less than or equal to 45℃ / min, greater than or equal to 10℃ / min and less than or equal to 45℃ / min, greater than or equal to 15℃ / min and less than or equal to 45℃ / min, greater than or equal to 20℃ / min and less than or equal to 45℃ / min, greater than or equal to 25℃ / min and less than or equal to 45℃ / min The following are temperature readings: ≥30℃ / min and ≤45℃ / min; ≥35℃ / min and ≤45℃ / min; ≥40℃ / min and ≤45℃ / min; ≥0.1℃ / min and ≤40℃ / min; ≥5℃ / min and ≤40℃ / min; ≥10℃ / min and ≤40℃ / min; ≥15℃ / min and ≤40℃ / min; ≥20℃ / min and ≤40℃ / min; ≥25℃ / min and ≤40℃ / min; ≥... Or equal to 30℃ / min and less than or equal to 40℃ / min, greater than or equal to 35℃ / min and less than or equal to 40℃ / min, greater than or equal to 0.1℃ / min and less than or equal to 35℃ / min, greater than or equal to 5℃ / min and less than or equal to 35℃ / min, greater than or equal to 10℃ / min and less than or equal to 35℃ / min, greater than or equal to 15℃ / min and less than or equal to 35℃ / min, greater than or equal to 20℃ / min and less than or equal to 35℃ / min, greater than or equal to 25℃ / min and less than or equal to 35℃ / min, greater than or equal to 30℃ / min and less than or equal to 35℃ / min, greater than or equal to 0.1℃ / min and less than or equal to 30℃ / min, greater than or equal to 5℃ / min and less than or equal to 30℃ / min, greater than or equal to 10℃ / min and less than or equal to 30℃ / min, greater than or equal to 15℃ / min and less than or equal to 30℃ / min, greater than or equal to 20℃ / min and less than or equal to 30℃ / min, greater than or equal to 25℃ / min and less than or equal to 30℃ / min, greater than or equal to 0.1℃ / min and less than or equal to 25℃ / min, greater than or equal to 5℃ / min and less than or equal to 25℃ / min, greater than or equal to 10℃ / min and less than or equal to 25℃ / min, greater than or equal to 15℃ / min and less than or equal to 25℃ / min, greater than or equal to 20℃ / min and less than or equal to 30℃ / min. The heating rates are 25°C / min, greater than or equal to 0.1°C / min and less than or equal to 20°C / min, greater than or equal to 5°C / min and less than or equal to 20°C / min, greater than or equal to 10°C / min and less than or equal to 20°C / min, greater than or equal to 15°C / min and less than or equal to 20°C / min, greater than or equal to 0.1°C / min and less than or equal to 15°C / min, greater than or equal to 5°C / min and less than or equal to 15°C / min, greater than or equal to 10°C / min and less than or equal to 15°C / min, greater than or equal to 0.1°C / min and less than or equal to 10°C / min, greater than or equal to 5°C / min and less than or equal to 10°C / min, or greater than or equal to 0.1°C / min and less than or equal to 5°C / min. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range. This heating rate allows for adequate nucleation and crystal growth without damaging the glass-ceramic product. If heating is completed too quickly, the material may be damaged. However, if heating is completed too slowly, normal nucleation and growth may not occur.

[0165] In this embodiment, the glass-ceramic is held at the growth temperature and then cooled. In this embodiment, the glass-ceramic may be cooled to room temperature at a constant cooling rate in a single stage, at different cooling rates in two stages, or at different cooling rates in three or more stages. In this embodiment, the glass-ceramic is cooled from the growth temperature at a controlled rate to minimize the temperature gradient on the article and to minimize residual stress on the article. Differences in temperature gradient and residual stress can cause the article to warp during cooling. Therefore, controlling cooling to control the temperature gradient and residual stress can also minimize the warping of the glass-ceramic.

[0166] After the precursor glass undergoes the aforementioned heat treatment, the resulting glass-ceramic has a phase composition, wherein lithium disilicate and petalite are the crystalline phases with the highest weight percentage. In the embodiments, the weight ratio of lithium disilicate to petalite in the glass-ceramic is greater than or equal to 0.8 and less than or equal to 2.5, greater than or equal to 0.85 and less than or equal to 2.5, greater than or equal to 0.9 and less than or equal to 2.5, greater than or equal to 0.8 and less than or equal to 2.4, greater than or equal to 0.85 and less than or equal to 2.4, greater than or equal to 0.9 and less than or equal to 2.4, greater than or equal to 0.7 and less than or equal to 2.3, greater than or equal to 0.8 and less than or equal to 2.3, greater than or equal to 0.9 and less than or equal to 2.3, and greater than or equal to 0. 7 and less than or equal to 2.2, greater than or equal to 0.8 and less than or equal to 2.2, greater than or equal to 0.9 and less than or equal to 2.2, greater than or equal to 0.7 and less than or equal to 2.1, greater than or equal to 0.8 and less than or equal to 2.1, greater than or equal to 0.9 and less than or equal to 2.1, greater than or equal to 0.7 and less than or equal to 2.0, greater than or equal to 0.8 and less than or equal to 2.0, greater than or equal to 0.9 and less than or equal to 2.0, greater than or equal to 0.7 and less than or equal to 1.9, greater than or equal to 0.8 and less than or equal to 1.9, greater than or equal to 0. 0.9 and less than or equal to 1.9, greater than or equal to 0.7 and less than or equal to 1.8, greater than or equal to 0.8 and less than or equal to 1.8, greater than or equal to 0.9 and less than or equal to 1.8, greater than or equal to 0.7 and less than or equal to 1.7, greater than or equal to 0.8 and less than or equal to 1.7, greater than or equal to 0.9 and less than or equal to 1.7, greater than or equal to 0.7 and less than or equal to 1.6, greater than or equal to 0.8 and less than or equal to 1.6, greater than or equal to 0.9 and less than or equal to 1.6, greater than or equal to 0.7 and less than or equal to 1.5, greater than or equal to 1.5, etc. The ranges are defined as follows: 0.8 and less than or equal to 1.5; greater than or equal to 0.9 and less than or equal to 1.5; greater than or equal to 0.7 and less than or equal to 1.4; greater than or equal to 0.8 and less than or equal to 1.4; greater than or equal to 0.9 and less than or equal to 1.4; greater than or equal to 0.7 and less than or equal to 1.3; greater than or equal to 0.8 and less than or equal to 1.3; greater than or equal to 0.9 and less than or equal to 1.3; greater than or equal to 0.7 and less than or equal to 1.2; greater than or equal to 0.8 and less than or equal to 1.2; or even greater than or equal to 0.9 and less than or equal to 1.2. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0167] The phase combination of the glass-ceramics described herein (i.e., the corresponding percentages of the crystalline phase and the residual glass phase) limits the refractive index mismatch between the crystalline and residual amorphous glass phases, thereby reducing light scattering and the resulting haze of the glass-ceramics, while improving the transmittance of the glass-ceramics.

[0168] The grain size of crystals in the crystalline phase is a factor affecting the transparency of glass-ceramics. In the embodiments, the longest grain size is in the following ranges: about 5 nm to about 150 nm, about 5 nm to about 125 nm, about 5 nm to about 100 nm, about 5 nm to about 75 nm, about 5 nm to about 50 nm, about 25 nm to about 150 nm, about 25 nm to about 125 nm, about 25 nm to about 100 nm, about 25 nm to about 75 nm, about 50 nm to about 150 nm, about 50 nm to about 125 nm, about 50 nm to about 100 nm, and all ranges and sub-ranges therebetween. In the embodiments, the longest grain size is less than 150 nm, less than 125 nm, less than 100 nm, less than 75 nm, less than 50 nm, or less than 25 nm. The longest grain size is measured using scanning electron microscopy (SEM) and image analysis.

[0169] In this embodiment, the glass-ceramic exhibits high transparency and low haze, making it suitable for use as cover glass for electronic devices, such as mobile electronic devices. In this embodiment, the glass-ceramic is transparent because its average light transmittance in the wavelength range of 450 nm to 800 nm is 85% or greater, 86% or greater, 87% or greater, 88% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, 93% or greater, or 94% or greater, as measured for a glass-ceramic article with a thickness of 1 mm.

[0170] In other embodiments, the glass-ceramic may be translucent in the wavelength range of 450 nm to 1000 nm. In embodiments, the average transmittance of the translucent glass-ceramic in the wavelength range of about 450 nm to about 800 nm may be from about 20% to less than about 85%, as measured for a glass-ceramic article with a thickness of 1 mm.

[0171] In the embodiments, the haze of the glass-ceramic article is less than or equal to 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, 0.14, 0.13, 0.12, 0.11, 0.10, 0.09, 0.08, 0.07, 0.06, or 0.05, as measured on a glass-ceramic article with a thickness of 0.6 mm.

[0172] In embodiments, glass-ceramics and glass-ceramic articles may be strengthened to create a compressive stress layer on one or more of their surfaces. Reference now is made to... Figure 2For example, an exemplary cross-sectional side view is depicted of a reinforced glass-ceramic article 100 having a first surface 102 spaced apart by a thickness (t) and an opposite second surface 104. In an embodiment, the reinforced glass-ceramic article 100 has undergone ion exchange and has a compressive stress (CS) layer 106 (or a first region) extending from the first surface 102 to the depth of compression (DOC). In an embodiment, as... Figure 2 As shown, the glass-ceramic article 100 also has a compressive stress (CS) layer 108 extending from the second surface 104 to the compression depth DOC'. A center tension region 110 with center tension (CT) is located between DOC and DOC'.

[0173] In embodiments, glass ceramics and glass ceramic articles can be chemically tempered (also known as chemically strengthened) using one or more ion exchange techniques. In these embodiments, ion exchange can be performed by subjecting one or more surfaces of such glass ceramics or glass ceramic articles to one or more ion exchange media (e.g., molten salt baths) having a specific composition and temperature for a specified period of time to apply a layer of compressive stress to one or more surfaces. In embodiments, the ion exchange media is a molten salt bath containing ions (e.g., alkali metal ions) larger than those present in the glass ceramics or glass ceramic articles, wherein the larger ions in the molten bath exchange with smaller ions in the glass ceramic articles to impart compressive stress to the glass ceramics or glass ceramic articles and thereby increase the strength of the glass ceramics or glass ceramic articles.

[0174] In this embodiment, a one-step ion exchange process can be used. In other embodiments, a multi-step ion exchange process (such as a two-step ion exchange process) can be used. In this embodiment, for both one-step and multi-step ion exchange processes, the ion exchange medium (e.g., a molten bath) may include potassium nitrate (KNO3) and sodium nitrate (NaNO3) as main components. In this embodiment, the ion exchange medium may also include lithium nitrate (LiNO3), sodium nitrite (NaNO2), and silicic acid.

[0175] In the embodiments, the ion exchange medium comprises 50 wt% and less than or equal to 70 wt% KNO3, 55 wt% and less than or equal to 70 wt% KNO3, 60 wt% and less than or equal to 70 wt% KNO3, 65 wt% and less than or equal to 70 wt% KNO3, 50 wt% and less than or equal to 65 wt% KNO3, 55 wt% and less than or equal to 65 wt% KNO3, 50 wt% and less than or equal to 60 wt% KNO3, 55 wt% and less than or equal to 60 wt% KNO3, or 50 wt% and less than or equal to 55 wt% KNO3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0176] In the embodiments, the ion exchange medium comprises greater than or equal to 30 wt% and less than or equal to 80 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 75 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 70 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 65 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 60 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 55 wt% NaNO3, greater than or equal to 30 wt% and less than or equal to 50 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 80 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 75 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 70 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 65 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 35 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 70 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 65 wt% NaNO3, greater than or equal to 35 wt% and less than or equal to 70 ... NaNO3 wt% and less than or equal to 60 wt%, NaNO3 wt% and less than or equal to 55 wt%, NaNO3 wt% and less than or equal to 50 wt%, NaNO3 wt% and less than or equal to 40 wt% and less than or equal to 80 wt%, NaNO3 wt% and less than or equal to 75 wt%, NaNO3 wt% and less than or equal to 70 wt%, NaNO3 wt% and less than or equal to 65 wt%, NaNO3 wt% and less than or equal to 60 wt%, NaNO3 wt% and less than or equal to 55 wt%, NaNO3 wt% and less than or equal to 50 wt%, NaNO3 wt% and less than or equal to 80 wt%, NaNO3 wt% and less than or equal to 75 wt%. NaNO3, greater than or equal to 45 wt% and less than or equal to 70 wt%; NaNO3, greater than or equal to 45 wt% and less than or equal to 65 wt%; NaNO3, greater than or equal to 45 wt% and less than or equal to 60 wt%; NaNO3, greater than or equal to 45 wt% and less than or equal to 55 wt%; NaNO3, greater than or equal to 45 wt% and less than or equal to 50 wt%; NaNO3, greater than or equal to 30 wt% and less than or equal to 45 wt%; NaNO3, greater than or equal to 35 wt% and less than or equal to 40 wt%; NaNO3, greater than or equal to 35 wt% and less than or equal to 40 wt%NaNO3 or greater than or equal to 30 wt% and less than or equal to 35 wt% NaNO3. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0177] In the embodiments, the ion exchange medium comprises greater than or equal to 0.05 wt% and less than or equal to 0.25 wt% LiNO3, greater than or equal to 0.08 wt% and less than or equal to 0.25 wt% LiNO3, greater than or equal to 0.10 wt% and less than or equal to 0.25 wt% LiNO3, greater than or equal to 0.15 wt% and less than or equal to 0.25 wt% LiNO3, greater than or equal to 0.20 wt% and less than or equal to 0.05 wt% LiNO3, greater than or equal to 0.05 wt% and less than or equal to 0.20 wt% LiNO3, greater than or equal to 0.10 wt% and less than or equal to 0.20 wt% LiNO3, greater than or equal to 0.15 wt% and less than or equal to 0.20 wt% LiNO3, and greater than or equal to 0.05 wt% LiNO3. The following concentrations are specified: wt% and less than or equal to 0.15 wt% LiNO3, greater than or equal to 0.08 wt% and less than or equal to 0.15 wt% LiNO3, greater than or equal to 0.10 wt% and less than or equal to 0.15 wt% LiNO3, greater than or equal to 0.12 wt% and less than or equal to 0.15 wt% LiNO3, greater than or equal to 0.05 wt% and less than or equal to 0.12 wt% LiNO3, greater than or equal to 0.08 wt% and less than or equal to 0.12 wt% LiNO3, greater than or equal to 0.10 wt% LiNO3, greater than or equal to 0.05 wt% and less than or equal to 0.08 wt% LiNO3. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0178] In the embodiments, the ion exchange medium comprises greater than or equal to 0.40 wt% and less than or equal to 0.60 wt% NaNO2, greater than or equal to 0.45 wt% and less than or equal to 0.60 wt% NaNO2, greater than or equal to 0.50 wt% and less than or equal to 0.60 wt% NaNO2, greater than or equal to 0.55 wt% and less than or equal to 0.40 wt% NaNO2, greater than or equal to 0.45 wt% and less than or equal to 0.55 wt% NaNO2, greater than or equal to 0.50 wt% and less than or equal to 0.50 wt% NaNO2, greater than or equal to 0.40 wt% and less than or equal to 0.50 wt% NaNO2, greater than or equal to 0.40 wt% and less than or equal to 0.50 wt% NaNO2, or greater than or equal to 0.40 wt% and less than or equal to 0.50 wt% NaNO2. wt% and less than or equal to 0.45 wt%. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0179] In the embodiments, the ion exchange medium comprises greater than or equal to 0.40 wt% and less than or equal to 0.60 wt% of silicic acid, greater than or equal to 0.45 wt% and less than or equal to 0.60 wt% of silicic acid, greater than or equal to 0.50 wt% and less than or equal to 0.60 wt% of silicic acid, greater than or equal to 0.55 wt% and less than or equal to 0.40 wt% of silicic acid, greater than or equal to 0.45 wt% and less than or equal to 0.55 wt% of silicic acid, greater than or equal to 0.50 wt% and less than or equal to 0.50 wt% of silicic acid, greater than or equal to 0.40 wt% and less than or equal to 0.50 wt% of silicic acid, or greater than or equal to 0.40 wt% of silicic acid. wt% and less than or equal to 0.45 wt%. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0180] In the embodiments, the temperatures of the ion exchange media are greater than or equal to 430°C and less than or equal to 550°C, greater than or equal to 450°C and less than or equal to 550°C, greater than or equal to 475°C and less than or equal to 550°C, greater than or equal to 500°C and less than or equal to 550°C, greater than or equal to 525°C and less than or equal to 550°C, greater than or equal to 530°C and less than or equal to 550°C, greater than or equal to 430°C and less than or equal to 530°C, greater than or equal to 450°C and less than or equal to 530°C, greater than or equal to 475°C and less than or equal to 530°C, greater than or equal to 430°C and less than or equal to 530°C, greater than or equal to 475°C and less than or equal to 530°C, greater than or equal to 530°C, greater than or equal to 530°C, less ... The temperatures are defined as follows: 500℃ and less than or equal to 530℃; greater than or equal to 525℃ and less than or equal to 530℃; greater than or equal to 430℃ and less than or equal to 525℃; greater than or equal to 450℃ and less than or equal to 525℃; greater than or equal to 475℃ and less than or equal to 525℃; greater than or equal to 500℃ and less than or equal to 525℃; greater than or equal to 430℃ and less than or equal to 500℃; greater than or equal to 450℃ and less than or equal to 500℃; greater than or equal to 475℃ and less than or equal to 500℃; or greater than or equal to 450℃ and less than or equal to 475℃. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0181] According to embodiments, the glass-ceramic or glass-ceramic articles are in contact with the ion exchange medium for the following durations: greater than or equal to 1 hour and less than or equal to 16 hours, greater than or equal to 2 hours and less than or equal to 16 hours, greater than or equal to 4 hours and less than or equal to 16 hours, greater than or equal to 6 hours and less than or equal to 16 hours, greater than or equal to 8 hours and less than or equal to 16 hours, greater than or equal to 10 hours and less than or equal to 16 hours, greater than or equal to 12 hours and less than or equal to 16 hours, greater than or equal to 14 hours and less than or equal to 16 hours, greater than or equal to 1 hour and less than or equal to 14 hours, greater than or equal to 2 hours and less than or equal to 14 hours, greater than or equal to 4 hours and less than or equal to 14 hours, greater than or equal to 6 hours and less than or equal to 14 hours, greater than or equal to 8 hours and less than or equal to 14 hours, greater than or equal to 10 hours and less than or equal to 14 hours, greater than or equal to 12 hours and less than or equal to 14 hours, greater than or equal to 1 hour and less than or equal to 12 hours, greater than or equal to 2 hours and less than or equal to 16 hours. 12 hours, greater than or equal to 4 hours and less than or equal to 12 hours, greater than or equal to 6 hours and less than or equal to 12 hours, greater than or equal to 8 hours and less than or equal to 12 hours, greater than or equal to 10 hours and less than or equal to 12 hours, greater than or equal to 1 hour and less than or equal to 10 hours, greater than or equal to 2 hours and less than or equal to 10 hours, greater than or equal to 4 hours and less than or equal to 10 hours, greater than or equal to 6 hours and less than or equal to 10 hours, greater than or equal to 8 hours and less than or equal to 10 hours, greater than or equal to 1 hour and less than or equal to 8 hours, greater than or equal to 2 hours and less than or equal to 6 hours, greater than or equal to 4 hours and less than or equal to 6 hours, greater than or equal to 1 hour and less than or equal to 4 hours, greater than or equal to 2 hours and less than or equal to 4 hours, or greater than or equal to 1 hour and less than or equal to 2 hours. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0182] After an ion exchange process, it should be understood that the composition at the surface of the glass-ceramic may differ from that of the as-formed glass-ceramic (i.e., the glass-ceramic before the ion exchange process). This is because the as-formed glass-ceramic contains a certain type of alkali metal ion (e.g., Li₂O₃). + Or Na + ) are respectively subjected to larger alkali metal ions (e.g., Na) + or K +Replacement. However, in embodiments, the composition of the glass-ceramic at or near the center of the depth of the glass-ceramic may still have the composition of the newly formed glass-ceramic. In other embodiments, the composition of the glass-ceramic at or near the center of the depth of the glass-ceramic may differ from the composition of the newly formed glass-ceramic. As used herein, the center of a glass-ceramic article refers to any location in the glass-ceramic article at least 0.5t from each of its surfaces, where t is the thickness of the glass-ceramic or the glass-ceramic article.

[0183] Unless otherwise stated, the mechanical properties of the glass-ceramics disclosed herein are tested on strengthened glass-ceramic articles. By forming glass-ceramics having the composition disclosed and described herein, and using heat treatment and chemical strengthening as disclosed and described herein, glass-ceramics with phase combinations providing low haze and improved mechanical properties (as described in detail below) can be obtained. Although described in different paragraphs below, various mechanical properties are present in combination in the glass-ceramics of the examples. The balance of these mechanical properties provides durable, robust glass-ceramics that are difficult to achieve without sacrificing other mechanical properties. For example, and by way of example only, it is possible to achieve only high compressive stress, but achieving both high compressive stress and central tension may be more difficult.

[0184] In the embodiments, the compression depths DOC and DOC' relative to each surface are respectively greater than or equal to 0.09t and less than or equal to 0.30t, greater than or equal to 0.10t and less than or equal to 0.30t, greater than or equal to 0.11t and less than or equal to 0.30t, greater than or equal to 0.12t and less than or equal to 0.30t, greater than or equal to 0.13t and less than or equal to 0.30t, greater than or equal to 0.14t and less than or equal to 0.30t, greater than or equal to 0.15t and less than or equal to 0.30t, greater than or equal to 0.16t and less than or equal to 0.30t, greater than or equal to 0.17t and less than or equal to 0.30t, and greater than or equal to 0.18t and less than or equal to 0.30t. 1. Greater than or equal to 0.19t and less than or equal to 0.30t; 2. Greater than or equal to 0.20t and less than or equal to 0.30t; 3. Greater than or equal to 0.21t and less than or equal to 0.30t; 4. Greater than or equal to 0.22t and less than or equal to 0.30t; 5. Greater than or equal to 0.23t and less than or equal to 0.30t; 6. Greater than or equal to 0.24t and less than or equal to 0.30t; 7. Greater than or equal to 0.09t and less than or equal to 0.25t; 8. Greater than or equal to 0.10t and less than or equal to 0.25t; 9. Greater than or equal to 0.11t and less than or equal to 0.25t; 10. Greater than or equal to 0.12t and less than or equal to 0.25t; 11. Greater than or equal to 0.13t and less than or equal to 0.25t; 12. Greater than or equal to 0.13t and less than or equal to 0.25t; 13. Greater than or equal to 0.25t; 14. Greater than or equal to 0.19t and less than or equal to 0.30t; 15. Greater than or equal to 0.21t and less than or equal to 0.30t; 16. Greater than or equal to 0.22t and less than or equal to 0.30t; 17. Greater than or equal to 0.23t and less than or equal to 0.30t; 18. Greater than or equal to 0.24t and less than or equal to 0.30t; 19. Greater than or equal to 0.09t and less than or equal to 0.25t; 0.14t and less than or equal to 0.25t, greater than or equal to 0.15t and less than or equal to 0.25t, greater than or equal to 0.16t and less than or equal to 0.25t, greater than or equal to 0.17t and less than or equal to 0.25t, greater than or equal to 0.18t and less than or equal to 0.25t, greater than or equal to 0.19t and less than or equal to 0.25t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.21t and less than or equal to 0.25t, greater than or equal to 0.22t and less than or equal to 0.25t, greater than or equal to 0.23t and less than or equal to 0.25t, greater than or equal to 0.24t and less than or equal to 0.25t, greater than or equal to 0.09t and Less than or equal to 0.24t, greater than or equal to 0.10t and less than or equal to 0.24t, greater than or equal to 0.11t and less than or equal to 0.24t, greater than or equal to 0.12t and less than or equal to 0.24t, greater than or equal to 0.13t and less than or equal to 0.24t, greater than or equal to 0.14t and less than or equal to 0.24t, greater than or equal to 0.15t and less than or equal to 0.24t, greater than or equal to 0.16t and less than or equal to 0.24t, greater than or equal to 0.17t and less than or equal to 0.24t, greater than or equal to 0.18t and less than or equal to 0.24t, greater than or equal to 0.19t and less than or equal to 0.24t, greater than or equal to 0.20t and less than or equal to 0.24t, greater than or equal to 0.21t and less than or equal to 0.24t, greater than or equal to 0.22t and less than or equal to 0.24t, greater than or equal to 0.23t and less than or equal to 0.24t, greater than or equal to 0.09t and less than or equal to 0.23t, greater than or equal to 0.10t and less than or equal to 0.23t, greater than or equal to 0.11t and less than or equal to 0.23t, greater than or equal to 0.12t and less than or equal to 0.23t, greater than or equal to 0.13t and less than or equal to 0.23t, greater than or equal to 0.14t and less than or equal to 0.23t, greater than or equal to 0.15t and less than or equal to 0.23t, greater than or equal to 0.16t and less than or equal to 0.23t, greater than or equal to... The values ​​are: 0.17t and less than or equal to 0.23t; greater than or equal to 0.18t and less than or equal to 0.23t; greater than or equal to 0.19t and less than or equal to 0.23t; greater than or equal to 0.20t and less than or equal to 0.23t; greater than or equal to 0.21t and less than or equal to 0.23t; greater than or equal to 0.22t and less than or equal to 0.23t; greater than or equal to 0.09t and less than or equal to 0.22t; greater than or equal to 0.10t and less than or equal to 0.22t; greater than or equal to 0.11t and less than or equal to 0.22t; greater than or equal to 0.12t and less than or equal to 0.22t; greater than or equal to 0.13t and less than or equal to 0.22t; greater than or equal to 0.14t and less than... The values ​​are: 0.22t or less, 0.15t or less, 0.16t or less, 0.22t or less, 0.17t or less, 0.18t or less, 0.22t or less, 0.19t or less, 0.20t or less, 0.22t or less, 0.21t or less, 0.09t or less, 0.10t or less, 0.21t or less, 0.11t or less, and 0.21t or less. The values ​​are: 0.21t or less, 0.12t or less, and 0.21t or less. t, greater than or equal to 0.13t and less than or equal to 0.21t, greater than or equal to 0.14t and less than or equal to 0.21t, greater than or equal to 0.15t and less than or equal to 0.21t, greater than or equal to 0.16t and less than or equal to 0.21t, greater than or equal to 0.17t and less than or equal to 0.21t, greater than or equal to 0.18t and less than or equal to 0.21t, greater than or equal to 0.19t and less than or equal to 0.21t, greater than or equal to 0.20t and less than or equal to 0.21t, greater than or equal to 0.09t and less than or equal to 0.20t, greater than or equal to 0.10t and less than or equal to 0.20t, greater than or equal to 0.11t and less than or equal to 0.20t, greater than or equal to 0.12t and less than or equal to 0.20t, greater than or equal to 0.13t and less than or equal to 0.20t, greater than or equal to 0.14t and less than or equal to 0.20t, greater than or equal to 0.15t and less than or equal to 0.20t, greater than or equal to 0.16t and less than or equal to 0.20t, greater than or equal to 0.17t and less than or equal to 0.20t, greater than or equal to 0.18t and less than or equal to 0.20t, greater than or equal to 0.19t and less than or equal to 0.20t, greater than or equal to 0.09t and less than or equal to 0.19t, greater than or equal to 0.10t and less than or equal to 0.19t, greater than or equal to 0.11t and less than or equal to 0.19t. t, greater than or equal to 0.12t and less than or equal to 0.19t, greater than or equal to 0.13t and less than or equal to 0.19t, greater than or equal to 0.14t and less than or equal to 0.19t, greater than or equal to 0.15t and less than or equal to 0.19t, greater than or equal to 0.16t and less than or equal to 0.19t, greater than or equal to 0.17t and less than or equal to 0.19t, greater than or equal to 0.18t and less than or equal to 0.19t, greater than or equal to 0.09t and less than or equal to 0.18t, greater than or equal to 0.10t and less than or equal to 0.18t, greater than or equal to 0.11t and less than or equal to 0.18t, greater than or equal to 0.12t and Less than or equal to 0.18t, greater than or equal to 0.13t and less than or equal to 0.18t, greater than or equal to 0.14t and less than or equal to 0.18t, greater than or equal to 0.15t and less than or equal to 0.18t, greater than or equal to 0.16t and less than or equal to 0.18t, greater than or equal to 0.17t and less than or equal to 0.18t, greater than or equal to 0.09t and less than or equal to 0.17t, greater than or equal to 0.10t and less than or equal to 0.17t, greater than or equal to 0.11t and less than or equal to 0.17t, greater than or equal to 0.12t and less than or equal to 0.17t, greater than or equal to 0.13t and less than or equal to 0.17t, greater than... The thickness can be 0.14t and less than or equal to 0.17t, greater than or equal to 0.15t and less than or equal to 0.17t, greater than or equal to 0.16t and less than or equal to 0.17t, greater than or equal to 0.09t and less than or equal to 0.16t, greater than or equal to 0.10t and less than or equal to 0.16t, greater than or equal to 0.11t and less than or equal to 0.16t, greater than or equal to 0.12t and less than or equal to 0.16t, greater than or equal to 0.13t and less than or equal to 0.16t, greater than or equal to 0.14t and less than or equal to 0.16t, or greater than or equal to 0.15t and less than or equal to 0.16t, where "t" is the thickness as defined in this paper.

[0185] Still referencing Figure 2Furthermore, as described herein, there exists a central tension region 110 with central tension (CT) between DOC and DOC'. Therefore, when measured from the surface of the reinforced glass-ceramic article toward the centerline, the stress changes from compressive stress to tensile stress at the aforementioned DOC and DOC'.

[0186] In embodiments, the surface compressive stress (CS) of the glass-ceramic article can be greater than or equal to 200 MPa and less than or equal to 550 MPa, such as greater than or equal to 225 MPa and less than or equal to 550 MPa, greater than or equal to 250 MPa and less than or equal to 550 MPa, greater than or equal to 275 MPa and less than or equal to 550 MPa, greater than or equal to 300 MPa and less than or equal to 550 MPa, greater than or equal to 325 MPa and less than or equal to 550 MPa, greater than or equal to 350 MPa and less than or equal to 550 MPa, greater than or equal to 375 MPa and less than or equal to 550 MPa, greater than or equal to 400 MPa and less than or equal to 550 MPa, greater than or equal to 425 MPa and less than or equal to 550 MPa, greater than or equal to 450 MPa and less than or equal to 550 MPa, greater than or equal to 475 MPa and less than or equal to 550 MPa, greater than or equal to 500 MPa, and greater than or equal to 500 MPa. The following pressures are specified: 550 MPa and less than or equal to 525 MPa; 200 MPa and less than or equal to 500 MPa; 225 MPa and less than or equal to 500 MPa; 250 MPa and less than or equal to 500 MPa; 275 MPa and less than or equal to 500 MPa; 300 MPa and less than or equal to 500 MPa; 325 MPa and less than or equal to 500 MPa; 350 MPa and less than or equal to 500 MPa; 375 MPa and less than or equal to 500 MPa; 400 MPa and less than or equal to 500 MPa; 425 MPa and less than or equal to 500 MPa; 450 MPa and less than or equal to 500 MPa; 475 MPa and less than or equal to 500 MPa. MPa, greater than or equal to 200 MPa and less than or equal to 475 MPaThe following are examples of pressure values: ≥225 MPa and ≤475 MPa; ≥250 MPa and ≤475 MPa; ≥275 MPa and ≤475 MPa; ≥300 MPa and ≤475 MPa; ≥325 MPa and ≤475 MPa; ≥350 MPa and ≤475 MPa; ≥375 MPa and ≤475 MPa; ≥400 MPa and ≤475 MPa; ≥425 MPa and ≤475 MPa; ≥450 MPa and ≤475 MPa; ≥200 MPa and ≤450 MPa; ≥225 MPa and ≤450 MPa; ≥250 MPa and ≤450 MPa; ≥275 MPa and ≤275 MPa. The following pressures are specified: MPa and less than or equal to 450 MPa, greater than or equal to 300 MPa and less than or equal to 450 MPa, greater than or equal to 325 MPa and less than or equal to 450 MPa, greater than or equal to 350 MPa and less than or equal to 450 MPa, greater than or equal to 375 MPa and less than or equal to 450 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, greater than or equal to 200 MPa and less than or equal to 425 MPa, greater than or equal to 225 MPa and less than or equal to 425 MPa, greater than or equal to 250 MPa and less than or equal to 425 MPa, greater than or equal to 275 MPa and less than or equal to 425 MPa, greater than or equal to 300 MPa and less than or equal to 425 MPa, greater than or equal to 325 MPa and less than or equal to 425 MPa, greater than or equal to 350 MPa and less than or equal to 425 MPa. MPa, greater than or equal to 375 MPa and less than or equal to 425 MPa, greater than or equal to 400 MPa and less than or equal to 425 MPa, greater than or equal to 200 MPa and less than or equal to 400 MPaThe following are examples of pressure values: greater than or equal to 225 MPa and less than or equal to 400 MPa; greater than or equal to 250 MPa and less than or equal to 400 MPa; greater than or equal to 275 MPa and less than or equal to 400 MPa; greater than or equal to 300 MPa and less than or equal to 400 MPa; greater than or equal to 325 MPa and less than or equal to 400 MPa; greater than or equal to 350 MPa and less than or equal to 400 MPa; greater than or equal to 375 MPa and less than or equal to 400 MPa; greater than or equal to 200 MPa and less than or equal to 375 MPa; greater than or equal to 225 MPa and less than or equal to 375 MPa; greater than or equal to 250 MPa and less than or equal to 375 MPa; greater than or equal to 275 MPa and less than or equal to 375 MPa; greater than or equal to 300 MPa and less than or equal to 375 MPa; greater than or equal to 325 MPa and less than or equal to 375 MPa; greater than or equal to 350 MPa and less than or equal to 40 ... MPa and less than or equal to 375 MPa, greater than or equal to 200 MPa and less than or equal to 350 MPa, greater than or equal to 225 MPa and less than or equal to 350 MPa, greater than or equal to 250 MPa and less than or equal to 350 MPa, greater than or equal to 275 MPa and less than or equal to 350 MPa, greater than or equal to 300 MPa and less than or equal to 350 MPa, greater than or equal to 325 MPa and less than or equal to 350 MPa, greater than or equal to 200 MPa and less than or equal to 325 MPa, greater than or equal to 275 MPa and less than or equal to 325 MPa, greater than or equal to 300 MPa and less than or equal to 325 MPa, greater than or equal to 200 MPa and less than or equal to 300 MPa, greater than or equal to 225 MPa and less than or equal to 300 MPa. MPa, greater than or equal to 250 MPa and less than or equal to 300 MPa, greater than or equal to 275 MPa and less than or equal to 300 MPa, greater than or equal to 200 MPa and less than or equal to 275 MPa, greater than or equal to 225 MPa and less than or equal to 275 MPa, greater than or equal to 250 MPa and less than or equal to 275 MPa, greater than or equal to 200 MPa and less than or equal to 250 MPa, greater than or equal to 225 MPa and less than or equal to 250 MPa, or greater than or equal to 200 MPa and less than or equal to 225 MPa. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0187] In the embodiments, the maximum central tension (CT) is greater than or equal to 150 MPa, greater than or equal to 160 MPa, greater than or equal to 170 MPa, greater than or equal to 180 MPa, greater than or equal to 190 MPa, greater than or equal to 200 MPa, greater than or equal to 210 MPa, or even greater than or equal to 220 MPa. In the embodiments, the maximum central tension is greater than or equal to 150 MPa and less than or equal to 230 MPa, greater than or equal to 160 MPa and less than or equal to 230 MPa, greater than or equal to 170 MPa and less than or equal to 230 MPa, greater than or equal to 180 MPa and less than or equal to 230 MPa, greater than or equal to 190 MPa and less than or equal to 230 MPa, greater than or equal to 200 MPa and less than or equal to 230 MPa, greater than or equal to 210 MPa and less than or equal to 230 MPa, greater than or equal to 220 MPa and less than or equal to 230 MPa, greater than or equal to 150 MPa and less than or equal to 220 MPa, greater than or equal to 160 MPa and less than or equal to 220 MPa, greater than or equal to 170 MPa and less than or equal to 220 MPa, greater than or equal to 180 MPa and less than or equal to 220 MPa, greater than or equal to 190 MPa and less than or equal to 220 MPa, greater than or equal to 200 MPa, and greater than or equal to 200 MPa. The following ranges are defined: 220 MPa and less than or equal to 220 MPa; 150 MPa and less than or equal to 210 MPa; 160 MPa and less than or equal to 210 MPa; 170 MPa and less than or equal to 210 MPa; 180 MPa and less than or equal to 210 MPa; 190 MPa and less than or equal to 210 MPa; 200 MPa and less than or equal to 210 MPa; 150 MPa and less than or equal to 200 MPa; 160 MPa and less than or equal to 200 MPa; 170 MPa and less than or equal to 200 MPa; 180 MPa and less than or equal to 200 MPa; or even greater than or equal to 190 MPa and less than or equal to 200 MPa. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0188] In the embodiments, the CS to CT ratio (CS / CT) of the glass-ceramic is greater than or equal to 0.87 and less than or equal to 3.6. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0189] According to an embodiment, at the following depths measured from the surface of the glass-ceramic article toward its centerline, the stress in the glass-ceramic article changes from compressive stress to tensile stress: greater than or equal to 0.09t and less than or equal to 0.30t, greater than or equal to 0.09t and less than or equal to 0.30t, greater than or equal to 0.10t and less than or equal to 0.30t, greater than or equal to 0.11t and less than or equal to 0.30t, greater than or equal to 0.12t and less than or equal to 0.30t, greater than or equal to 0.13t and less than or equal to 0.30t, greater than or equal to 0.14t and less than or equal to 0.30t, greater than or equal to 0.15t and less than or equal to 0.30t, greater than or equal to 0.16t and... Less than or equal to 0.30t, greater than or equal to 0.17t and less than or equal to 0.30t, greater than or equal to 0.18t and less than or equal to 0.30t, greater than or equal to 0.19t and less than or equal to 0.30t, greater than or equal to 0.20t and less than or equal to 0.30t, greater than or equal to 0.21t and less than or equal to 0.30t, greater than or equal to 0.22t and less than or equal to 0.30t, greater than or equal to 0.23t and less than or equal to 0.30t, greater than or equal to 0.24t and less than or equal to 0.30t, greater than or equal to 0.25t and less than or equal to 0.30t, greater than or equal to 0.09t and less than or equal to 0.25t, greater than or equal to 0.10t and less than or equal to 0. 0.25t, greater than or equal to 0.11t and less than or equal to 0.25t, greater than or equal to 0.12t and less than or equal to 0.25t, greater than or equal to 0.13t and less than or equal to 0.25t, greater than or equal to 0.14t and less than or equal to 0.25t, greater than or equal to 0.15t and less than or equal to 0.25t, greater than or equal to 0.16t and less than or equal to 0.25t, greater than or equal to 0.17t and less than or equal to 0.25t, greater than or equal to 0.18t and less than or equal to 0.25t, greater than or equal to 0.19t and less than or equal to 0.25t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.21t and less than or equal to 0.25t, and larger than... The following values ​​are considered equal to or greater than 0.22t and less than or equal to 0.25t: greater than or equal to 0.23t and less than or equal to 0.25t; greater than or equal to 0.24t and less than or equal to 0.25t; greater than or equal to 0.09t and less than or equal to 0.24t; greater than or equal to 0.10t and less than or equal to 0.24t; greater than or equal to 0.11t and less than or equal to 0.24t; greater than or equal to 0.12t and less than or equal to 0.24t; greater than or equal to 0.13t and less than or equal to 0.24t; greater than or equal to 0.14t and less than or equal to 0.24t; greater than or equal to 0.15t and less than or equal to 0.24t; greater than or equal to 0.16t and less than or equal to 0.24t; greater than or equal to 0.17t and less than or equal to 0.24t, greater than or equal to 0.18t and less than or equal to 0.24t, greater than or equal to 0.19t and less than or equal to 0.24t, greater than or equal to 0.20t and less than or equal to 0.24t, greater than or equal to 0.21t and less than or equal to 0.24t, greater than or equal to 0.22t and less than or equal to 0.24t, greater than or equal to 0.23t and less than or equal to 0.24t, greater than or equal to 0.09t and less than or equal to 0.23t, greater than or equal to 0.10t and less than or equal to 0.23t, greater than or equal to 0.11t and less than or equal to 0.23t, greater than or equal to 0.12t and less than or equal to 0.23t, greater than or equal to 0.13t and less than or equal to 0.24t. The values ​​are: 0.23t, greater than or equal to 0.14t and less than or equal to 0.23t, greater than or equal to 0.15t and less than or equal to 0.23t, greater than or equal to 0.16t and less than or equal to 0.23t, greater than or equal to 0.17t and less than or equal to 0.23t, greater than or equal to 0.18t and less than or equal to 0.23t, greater than or equal to 0.19t and less than or equal to 0.23t, greater than or equal to 0.20t and less than or equal to 0.23t, greater than or equal to 0.21t and less than or equal to 0.23t, greater than or equal to 0.22t and less than or equal to 0.23t, greater than or equal to 0.09t and less than or equal to 0.22t, greater than or equal to 0.10t and less than or equal to 0.22t, and greater than... The values ​​are equal to or greater than 0.11t and less than or equal to 0.22t, greater than or equal to 0.12t and less than or equal to 0.22t, greater than or equal to 0.13t and less than or equal to 0.22t, greater than or equal to 0.14t and less than or equal to 0.22t, greater than or equal to 0.15t and less than or equal to 0.22t, greater than or equal to 0.16t and less than or equal to 0.22t, greater than or equal to 0.17t and less than or equal to 0.22t, greater than or equal to 0.18t and less than or equal to 0.22t, greater than or equal to 0.19t and less than or equal to 0.22t, greater than or equal to 0.20t and less than or equal to 0.22t, greater than or equal to 0.21t and less than or equal to 0.22t, and greater than or equal to 0.09t. The values ​​of t are ≤0.21t, ≥0.10t, ≥0.11t, ≥0.21t, ≥0.12t, ≥0.13t, ≥0.14t, ≥0.15t, ≥0.21t, ≥0.16t, ≥0.17t, ≥0.18t, ≥0.19t, and ≥0.21t. The values ​​of t and t are ≤0.20t and ≤0.21t.21t, greater than or equal to 0.09t and less than or equal to 0.20t, greater than or equal to 0.10t and less than or equal to 0.20t, greater than or equal to 0.11t and less than or equal to 0.20t, greater than or equal to 0.12t and less than or equal to 0.20t, greater than or equal to 0.13t and less than or equal to 0.20t, greater than or equal to 0.14t and less than or equal to 0.20t, greater than or equal to 0.15t and less than or equal to 0.20t, greater than or equal to 0.16t and less than or equal to 0.20t, greater than or equal to 0.17t and less than or equal to 0.20t, greater than or equal to 0.18t and less than or equal to 0.20t, greater than or equal to 0.19 The values ​​of t are defined as follows: t ≤ 0.20t, ≥ 0.09t ≤ 0.19t, ≥ 0.10t ≤ 0.19t, ≥ 0.11t ≤ 0.19t, ≥ 0.12t ≤ 0.19t, ≥ 0.13t ≤ 0.19t, ≥ 0.14t ≤ 0.19t, ≥ 0.15t ≤ 0.19t, ≥ 0.16t ≤ 0.19t, ≥ 0.17t ≤ 0.19t, or ≥ 0.18t ≤ 0.19t. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0190] According to an embodiment, the glass-ceramic article has a maximum central tension (mCT), and the absolute value of the surface compressive stress measured at the surface of the glass-ceramic article is greater than or equal to 0.87 mCT and less than or equal to 3.6 mCT, greater than or equal to 0.9 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.0 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.1 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.2 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.3 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.4 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.5 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.6 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.7 mCT and less than or equal to 3.6 mCT, greater than or equal to 1.8 mCT and less than or equal to 3.6 mCT, and greater than or equal to 1.9 mCT and less than or equal to 3.6 mCT. The ranges are defined as follows: mCT, greater than or equal to 2.0 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.1 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.2 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.3 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.4 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.5 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.6 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.7 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.8 mCT and less than or equal to 3.6 mCT, greater than or equal to 2.9 mCT and less than or equal to 3.6 mCT, or greater than or equal to 3.0 mCT and less than or equal to 3.6 mCT. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0191] In the embodiments, the stored strain energy of the glass-ceramic article is greater than or equal to 22 J / m. 2 And less than or equal to 62 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 62 J / m 2 ≥30 J / m 2 And less than or equal to 62 J / m 2 ≥35 J / m 2 And less than or equal to 62 J / m 2 ≥40 J / m 2 And less than or equal to 62 J / m 2 ≥45 J / m 2And less than or equal to 62 J / m 2 ≥50 J / m 2 And less than or equal to 62 J / m 2 ≥55 J / m 2 And less than or equal to 62 J / m 2 ≥22 J / m 2 And less than or equal to 60 J / m 2 ≥25J / m 2 And less than or equal to 60 J / m 2 ≥30 J / m 2 And less than or equal to 60 J / m 2 ≥35 J / m 2 And less than or equal to 60 J / m 2 ≥40 J / m 2 And less than or equal to 60 J / m 2 ≥45 J / m 2 And less than or equal to 60 J / m 2 ≥50 J / m 2 And less than or equal to 60 J / m 2 ≥55 J / m 2 And less than or equal to 60 J / m 2 ≥22 J / m 2 And less than or equal to 55 J / m 2 For example, greater than or equal to 25 J / m2 and less than or equal to 55 J / m2, greater than or equal to 30 J / m2 and less than or equal to 55 J / m2, greater than or equal to 35 J / m2 and less than or equal to 55 J / m2, greater than or equal to 40 J / m2 and less than or equal to 55 J / m2, greater than or equal to 45 J / m2, and less than or equal to 55 J / m2. 2 And less than or equal to 55 J / m 2 ≥50 J / m 2 And less than or equal to 55 J / m 2 ≥22 J / m 2 And less than or equal to 50 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 50 J / m 2 ≥30 J / m 2 And less than or equal to 50 J / m 2 ≥35 J / m 2 And less than or equal to 50 J / m 2 ≥40 J / m2 And less than or equal to 50 J / m 2 ≥45 J / m 2 And less than or equal to 50 J / m 2 ≥22 J / m 2 And less than or equal to 45 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 45 J / m 2 ≥30 J / m 2 And less than or equal to 45 J / m 2 ≥35J / m 2 And less than or equal to 45 J / m 2 ≥40 J / m 2 And less than or equal to 45 J / m 2 ≥22 J / m 2 And less than or equal to 40 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 40 J / m 2 ≥30 J / m 2 And less than or equal to 40 J / m 2 ≥35 J / m 2 And less than or equal to 40 J / m 2 ≥22 J / m 2 And less than or equal to 35 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 35 J / m 2 ≥30 J / m 2 And less than or equal to 35 J / m 2 ≥22 J / m 2 And less than or equal to 30 J / m 2 If greater than or equal to 25 J / m 2 And less than or equal to 30 J / m 2 Or greater than or equal to 22 J / m 2 And less than or equal to 25 J / m 2 It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope. The glass-ceramic achieves the aforementioned stored strain energy, and the crack pattern does not branch.

[0192] The Knoop hardness (under a 200 g load) of the glass-ceramic according to the embodiment is greater than or equal to 550 kg on unstrengthened glass-ceramic. f / mm2 And less than or equal to 610 kg f / mm 2 If greater than or equal to 560 kg f / mm 2 And less than or equal to 610 kg f / mm 2 570 kg or more f / mm 2 And less than or equal to 610 kg f / mm 2 580 kg or more f / mm 2 And less than or equal to 610 kg f / mm 2 590 kg or more f / mm 2 And less than or equal to 610 kg f / mm 2 Or even greater than or equal to 600 kg f / mm 2 And less than or equal to 610 kg f / mm 2 It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0193] The glass-ceramic according to the embodiment has a Knoop hardness (under a 200 g load) greater than 610 kg when measured on reinforced glass-ceramic. f / mm 2 And less than or equal to 640 kg f / mm 2 If greater than or equal to 615 kg f / mm 2 And less than or equal to 640 kg f / mm 2 ≥620 kg f / mm 2 And less than or equal to 640 kg f / mm 2 ≥625 Kg f / mm 2 And less than or equal to 640 kg f / mm 2 ≥630 kg f / mm 2 And less than or equal to 640 kg f / mm 2 Or even greater than or equal to 635 kg f / mm2 And less than or equal to 640 kg f / mm 2 In an embodiment, the Knoop hardness (under a 200 g load) measured on the reinforced glass-ceramic can be greater than 610 kg. f / mm 2 And less than or equal to 635 kg f / mm 2 If greater than 610 kg f / mm 2 And less than or equal to 630 kg f / mm 2 Greater than 610 kg f / mm 2 And less than or equal to 625 kg f / mm 2 Greater than 610 kg f / mm 2 And less than or equal to 620 kg f / mm 2 Oven weight greater than 610 kg f / mm 2 And less than or equal to 615 kg f / mm 2 It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0194] In the embodiments, the thickness t of the glass-ceramic article is greater than or equal to 0.1 mm and less than or equal to 2.0 mm, greater than or equal to 0.3 mm and less than or equal to 2.0 mm, greater than or equal to 0.5 mm and less than or equal to 2.0 mm, greater than or equal to 0.8 mm and less than or equal to 2.0 mm, greater than or equal to 1.0 mm and less than or equal to 2.0 mm, greater than or equal to 1.3 mm and less than or equal to 2.0 mm, greater than or equal to 1.5 mm and less than or equal to 2.0 mm, greater than or equal to 1.8 mm and less than or equal to 2.0 mm, greater than or equal to 0.1 mm and less than or equal to 1.8 mm, greater than or equal to 0.3 mm and less than or equal to 1.8 mm, greater than or equal to 0.5 mm and less than or equal to 1.8 mm, greater than or equal to 0.8 mm and less than or equal to 1.8 mm, greater than or equal to 1.0 mm and less than or equal to 1.8 mm, greater than or equal to 1.3 mm and less than or equal to 1.8 mm, greater than or equal to 1.5 mm, and greater than or equal to 1.5 mm. mm and less than or equal to 1.8 mm, greater than or equal to 0.1 mm and less than or equal to 1.5 mm, greater than or equal to 0.3 mm and less than or equal to 1.5 mm, greater than or equal to 0.5 mm and less than or equal to 1.5 mm, greater than or equal to 0.8 mm and less than or equal to 1.5 mm, greater than or equal to 1.0 mm and less than or equal to 1.5 mm, greater than or equal to 1.3 mm and less than or equal to 1.5 mm, greater than or equal to 0.1 mm and less than or equal to 1.3 mm, greater than or equal to 0.3 mm and less than or equal to 1.3 mm, greater than or equal to 0.5 mm and less than or equal to 1.0 mm, greater than or equal to 0.8 ... The ranges are defined as follows: mm and less than or equal to 1.0 mm, greater than or equal to 0.1 mm and less than or equal to 0.8 mm, greater than or equal to 0.3 mm and less than or equal to 0.8 mm, greater than or equal to 0.5 mm and less than or equal to 0.8 mm, greater than or equal to 0.1 mm and less than or equal to 0.5 mm, greater than or equal to 0.3 mm and less than or equal to 0.5 mm, or greater than or equal to 0.1 mm and less than or equal to 0.3 mm. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0195] In the embodiments, the fracture toughness of the non-chemically strengthened glass-ceramic articles is greater than or equal to 1.0 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.1 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.1 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.3 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.6 MPa√m, and greater than or equal to 1.1 MPa√m. MPa√m less than or equal to 1.6 MPa√m, greater than or equal to 1.2 MPa√m less than or equal to 1.6 MPa√m, greater than or equal to 1.3 MPa√m less than or equal to 1.6 MPa√m, greater than or equal to 1.4 MPa√m less than or equal to 1.6 MPa√m, greater than or equal to 1.5 MPa√m less than or equal to 1.6 MPa√m, greater than or equal to 1.0 MPa√m less than or equal to 1.5 MPa√m, greater than or equal to 1.1 MPa√m less than or equal to 1.5 MPa√m, greater than or equal to 1.2 MPa√m less than or equal to 1.5 MPa√m, greater than or equal to 1.3 MPa√m less than or equal to 1.5 MPa√m, greater than or equal to 1.4 MPa√m less than or equal to 1.5 MPa√m, greater than or equal to 1.0 MPa√m less than or equal to 1.4 MPa√m, greater than or equal to 1.1 MPa√m. MPa√m and less than or equal to 1.4 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.4 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.3 MPa√m, greater than or equal to 1.1 MPa√m and less than or equal to 1.3 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.3 MPa√m, or even greater than or equal to 1.0 MPa√m and less than or equal to 1.2 MPa√m. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0196] In the embodiments, the Young's modulus (also known as the elastic modulus) of the non-chemically strengthened glass-ceramic articles is greater than or equal to 90 GPa and less than or equal to 130 GPa, such as greater than or equal to 95 GPa and less than or equal to 130 GPa, greater than or equal to 100 GPa and less than or equal to 130 GPa, greater than or equal to 105 GPa and less than or equal to 130 GPa, greater than or equal to 90 GPa and less than or equal to 120 GPa, greater than or equal to 95 GPa and less than or equal to 120 GPa, greater than or equal to 100 GPa and less than or equal to 120 GPa, greater than or equal to 105 GPa and less than or equal to 120 GPa, greater than or equal to 90 GPa and less than or equal to 110 GPa, greater than or equal to 95 GPa and less than or equal to 110 GPa, greater than or equal to 105 GPa and less than or equal to 110 GPa, or greater than or equal to 90 GPa and less than or equal to 105 GPa. GPa. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0197] In the embodiments, the Poisson's ratio of the non-chemically strengthened glass-ceramic articles is greater than or equal to 0.15 and less than or equal to 0.25, greater than or equal to 0.17 and less than or equal to 0.25, greater than or equal to 0.20 and less than or equal to 0.25, greater than or equal to 0.22 and less than or equal to 0.25, greater than or equal to 0.15 and less than or equal to 0.22, greater than or equal to 0.17 and less than or equal to 0.22, greater than or equal to 0.20 and less than or equal to 0.22, greater than or equal to 0.15 and less than or equal to 0.20, and greater than or equal to 0.17 and less than or equal to 0.20. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0198] In the embodiments, the shear modulus of the non-chemically strengthened glass-ceramic articles is greater than or equal to 40 GPa and less than or equal to 50 GPa, greater than or equal to 41 GPa and less than or equal to 50 GPa, greater than or equal to 42 GPa and less than or equal to 50 GPa, greater than or equal to 40 GPa and less than or equal to 48 GPa, greater than or equal to 41 GPa and less than or equal to 48 GPa, greater than or equal to 42 GPa and less than or equal to 48 GPa, greater than or equal to 43 GPa and less than or equal to 45 GPa, or greater than or equal to 40 GPa and less than or equal to 43 GPa. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0199] Fracture strength was measured by applying fracture stress to failure using a four-point bend test after introducing defects with 80-grit Al2O3 sandpaper. The test was performed using an apparatus comprising a simple pendulum-based four-point bend test with surfaces ranging from flat to curved. A glass-ceramic test sample was mounted on the pendulum's measuring hammer, which then brought the sample into contact with a rough impact surface. The apparatus is described in detail in International Application Publication No. WO2017 / 100646, which is hereby incorporated by reference in its entirety. To perform the test, the sample is loaded onto a support, and then pulled back and released from the pendulum's equilibrium position to generate a dynamic impact on the impact surface.

[0200] The fracture strength of the glass-ceramic according to the embodiment, measured using 80-grit Al2O3 sandpaper damage introduced onto an ion-exchange strengthened glass-ceramic article with a thickness of 0.5 mm, is greater than or equal to 250 MPa and less than or equal to 450 MPa, greater than or equal to 275 MPa and less than or equal to 450 MPa, greater than or equal to 300 MPa and less than or equal to 450 MPa, greater than or equal to 325 MPa and less than or equal to 450 MPa, greater than or equal to 350 MPa and less than or equal to 450 MPa, greater than or equal to 375 MPa and less than or equal to 450 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, greater than or equal to 250 MPa and less than or equal to 450 MPa, greater than or equal to 275 MPa and less than or equal to 450 MPa, greater than or equal to 300 MPa and less than or equal to 425 MPa, greater than or equal to 325 MPa and less than or equal to 450 ... MPa and less than or equal to 425 MPa, greater than or equal to 350 MPa and less than or equal to 425 MPa, greater than or equal to 375 MPa and less than or equal to 425 MPa, or even greater than or equal to 400 MPa and less than or equal to 425 MPa. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0201] The fracture strength of the glass-ceramic according to the embodiment, measured using 80-grit Al2O3 sandpaper on a glass-ceramic article strengthened by ion exchange and with a thickness of 0.6 mm, is greater than or equal to 250 MPa and less than or equal to 450 MPa, greater than or equal to 275 MPa and less than or equal to 450 MPa, greater than or equal to 300 MPa and less than or equal to 450 MPa, greater than or equal to 325 MPa and less than or equal to 450 MPa, greater than or equal to 350 MPa and less than or equal to 450 MPa, greater than or equal to 375 MPa and less than or equal to 450 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, greater than or equal to 250 MPa and less than or equal to 425 MPa, greater than or equal to 275 MPa and less than or equal to 425 MPa, greater than or equal to 300 MPa and less than or equal to 425 MPa, greater than or equal to 325 ... MPa and less than or equal to 425 MPa, greater than or equal to 350 MPa and less than or equal to 425 MPa, greater than or equal to 375 MPa and less than or equal to 425 MPa, or even greater than or equal to 400 MPa and less than or equal to 425 MPa. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0202] Drop testing methods are used to determine the maximum height from which a precursor glass or glass-ceramic can be dropped without catastrophic failure (i.e., drop height). Drop testing methods involve performing a face-drop test on a test puck to which the precursor glass or glass-ceramic article is attached. The thickness of the precursor glass or glass-ceramic article to be tested is similar to or equal to the thickness that would be used in a given handheld consumer electronics device. A test puck is a structure designed to mimic the size, shape, and weight distribution of a given device, such as a cellular phone. In the following text, the term "test puck" refers to a structure weighing 126.0 grams, with a length of 133.1 mm, a width of 68.2 mm, and a height of 9.4 mm.

[0203] Exemplary devices that can be used for drop testing methods include drop machines, such as drop testers. Figure 3 As indicated by reference numeral 10 in the accompanying drawings. The drop tester 10 includes a chuck 12 with chuck jaws 14. A test block 16 is placed in the chuck jaws 14, with a precursor glass or glass-ceramic article attached to the chuck jaws and facing downwards. The chuck 12 is prepared to drop from, for example, an electromagnetic chuck lifter. Now refer to... Figure 4 The chuck 12 is released, and during its descent, the chuck jaws 14 are opened, for example, triggered by a proximity sensor. When the chuck jaws 14 open, the test block 16 is released. Now refer to... Figure 5The falling test block 16 impacts the drop surface 18. The drop surface 18 can be sandpaper, such as 80-grit sandpaper (however, other grit sandpaper can also be used). If the precursor glass or glass-ceramic product attached to the test block withstands the drop (i.e., without cracking), the chuck 12 is set at a higher height, and the test is repeated. The failure height is then the lowest height from which the test block, including the precursor glass or glass-ceramic product, can be dropped and cause the precursor glass or glass-ceramic product to fail.

[0204] In the embodiments, the height from which a 0.6 mm thick glass-ceramic product is dropped onto 80-grit sandpaper is greater than or equal to 170 cm and less than or equal to 250 cm, greater than or equal to 180 cm and less than or equal to 250 cm, greater than or equal to 190 cm and less than or equal to 250 cm, greater than or equal to 200 cm and less than or equal to 250 cm, greater than or equal to 210 cm and less than or equal to 250 cm, greater than or equal to 220 cm and less than or equal to 250 cm, greater than or equal to 170 cm and less than or equal to 240 cm, greater than or equal to 180 cm and less than or equal to 240 cm, greater than or equal to 190 cm and less than or equal to 240 cm, greater than or equal to 200 cm and less than or equal to 240 cm, greater than or equal to 210 cm and less than or equal to 240 cm, greater than or equal to 220 cm and less than or equal to 240 cm, greater than or equal to 170 cm and less than or equal to 230 cm, and greater than or equal to 180 cm and less than or equal to 230 cm. cm, greater than or equal to 190 cm and less than or equal to 230 cm, greater than or equal to 200 cm and less than or equal to 230 cm, greater than or equal to 210 cm and less than or equal to 230 cm, greater than or equal to 220 cm and less than or equal to 230 cm, greater than or equal to 170 cm and less than or equal to 220 cm, greater than or equal to 180 cm and less than or equal to 220 cm, greater than or equal to 190 cm and less than or equal to 220 cm, greater than or equal to 200 cm and less than or equal to 220 cm, or even greater than or equal to 210 cm and less than or equal to 220 cm. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0205] In the embodiments, the height from which a 0.5 mm thick glass-ceramic product is dropped onto 80-grit sandpaper is greater than or equal to 150 cm and less than or equal to 240 cm, greater than or equal to 160 cm and less than or equal to 240 cm, greater than or equal to 170 cm and less than or equal to 240 cm, greater than or equal to 180 cm and less than or equal to 240 cm, greater than or equal to 190 cm and less than or equal to 240 cm, greater than or equal to 200 cm and less than or equal to 240 cm, greater than or equal to 180 cm and less than or equal to 230 cm, greater than or equal to 150 cm and less than or equal to 230 cm, greater than or equal to 160 cm and less than or equal to 230 cm, greater than or equal to 170 cm and less than or equal to 230 cm, greater than or equal to 180 cm and less than or equal to 230 cm, greater than or equal to 190 cm and less than or equal to 230 cm, greater than or equal to 200 cm and less than or equal to 230 cm, and greater than or equal to 150 cm and less than or equal to 220 cm. cm, greater than or equal to 160 cm and less than or equal to 220 cm, greater than or equal to 170 cm and less than or equal to 220 cm, greater than or equal to 180 cm and less than or equal to 220 cm, greater than or equal to 190 cm and less than or equal to 220 cm, greater than or equal to 200 cm and less than or equal to 220 cm, greater than or equal to 150 cm and less than or equal to 210 cm, greater than or equal to 160 cm and less than or equal to 210 cm, greater than or equal to 170 cm and less than or equal to 220 cm, greater than or equal to 180 cm and less than or equal to 210 cm, greater than or equal to 190 cm and less than or equal to 210 cm, greater than or equal to 200 cm and less than or equal to 210 cm, greater than or equal to 150 cm and less than or equal to 200 cm, greater than or equal to 160 cm and less than or equal to 200 cm, greater than or equal to 170 cm and less than or equal to 200 cm, greater than or equal to 180 cm and less than or equal to 200 cm cm or even greater than or equal to 190 cm and less than or equal to 200 cm. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0206] According to the embodiments, the refractive index of the glass ceramic (measured at a wavelength of 598 nm) is greater than or equal to 1.500 and less than or equal to 1.600, greater than or equal to 1.520 and less than or equal to 1.600, greater than or equal to 1.540 and less than or equal to 1.600, greater than or equal to 1.550 and less than or equal to 1.600, greater than or equal to 1.500 and less than or equal to 1.580, greater than or equal to 1.520 and less than or equal to 1.580, greater than or equal to 1.540 and less than or equal to 1.580, greater than or equal to 1.550 and less than or equal to 1.580, greater than or equal to 1.500 and less than or equal to 1.560, greater than or equal to 1.520 and less than or equal to 1.560, greater than or equal to 1.540 and less than or equal to 1.560, and greater than or equal to 1.550 and less than or equal to 1.560. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0207] The stress optical coefficients (measured at a wavelength of 546 nm) of the glass-ceramics according to the embodiments are greater than or equal to 25.5 nm / cm / MPa and less than or equal to 28.5 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 28.5 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 28.5 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 28.5 nm / cm / MPa, greater than or equal to 26.4 nm / cm / MPa and less than or equal to 28.5 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 28.0 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 28.0 nm / cm / MPa, and greater than or equal to 26.0 nm / cm / MPa and less than or equal to 28.0 nm / cm / MPa. nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 28.0 nm / cm / MPa, greater than or equal to 26.4 nm / cm / MPa and less than or equal to 28.0 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 26.4 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 27.0 nm / cm / MPa, greater than or equal to 25.8 ...4 nm / cm / MPa and less than or equal to 27.6 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 27.0 nm nm / cm / MPa and less than or equal to 27.0 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 27.0 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 27.0 nm / cm / MPa, greater than or equal to 26.4 nm / cm / MPa and less than or equal to 27.0 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 25.The ranges are defined as follows: 5 nm / cm / MPa less than or equal to 26.4 nm / cm / MPa; greater than or equal to 25.8 nm / cm / MPa less than or equal to 26.4 nm / cm / MPa; greater than or equal to 26.0 nm / cm / MPa less than or equal to 26.4 nm / cm / MPa; greater than or equal to 25.5 nm / cm / MPa less than or equal to 26.2 nm / cm / MPa; or greater than or equal to 25.8 nm / cm / MPa less than or equal to 26.2 nm / cm / MPa. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0208] The annealing points of the precursor glass embodiments described herein are greater than or equal to 490°C and less than or equal to 530°C, greater than or equal to 500°C and less than or equal to 520°C, or even greater than or equal to 510°C and less than or equal to 520°C. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0209] The strain point of the precursor glass according to the embodiment is greater than or equal to 450°C and less than or equal to 500°C, greater than or equal to 460°C and less than or equal to 490°C, or even greater than or equal to 470°C and less than or equal to 480°C. It should be understood that the above range includes all sub-ranges within the explicitly disclosed range.

[0210] The annealing points of the glass-ceramic embodiments described herein are greater than or equal to 730°C and less than or equal to 770°C, greater than or equal to 735°C and less than or equal to 770°C, greater than or equal to 740°C and less than or equal to 770°C, greater than or equal to 745°C and less than or equal to 770°C, greater than or equal to 745°C and less than or equal to 765°C, greater than or equal to 745°C and less than or equal to 760°C, or even greater than or equal to 745°C and less than or equal to 755°C. It should be understood that the above scope includes all sub-scopes within the explicitly disclosed scope.

[0211] The strain points of the glass-ceramics according to the embodiments are greater than or equal to 700°C and less than or equal to 750°C, greater than or equal to 710°C and less than or equal to 740°C, greater than or equal to 715°C and less than or equal to 730°C, or even greater than or equal to 720°C and less than or equal to 730°C. It should be understood that the above ranges include all sub-ranges within the explicitly disclosed range.

[0212] In the embodiments described herein, the CTE of the glass-ceramic is less than 8 × 10⁻⁶. -6 ℃ -1 In this embodiment, the coefficient of thermal expansion of the glass-ceramic is greater than or equal to 6 × 10⁻⁶. -6 ℃ -1 And less than or equal to 8 × 10 -6℃ -1 ≥6.5 ×10 -6 ℃ -1 And less than or equal to 7.5 × 10 -6 ℃ -1 Or even greater than or equal to 7 × 10 -6 ℃ -1 And less than or equal to 7.5 × 10 -6 ℃ -1 Compared to glass-ceramics with higher CTE, these relatively lower CTE values ​​improve the survivability of glass-ceramics under thermal cycling or thermal stress conditions.

[0213] As described herein, the addition of CaO and ZrO2 is thought to increase the density of the precursor glass and glass-ceramic, and thus slow down ion diffusion into the glass-ceramic during chemical strengthening. This slowdown in diffusion reduces the ion exchange process, but the glass-ceramic exhibits greater compressive stress and central tensile stress compared to the lower-density glass. In the examples, the density of the precursor glass and glass-ceramic is greater than 2.51 g / cm³. 3 ≥2.52 g / cm 3 ≥2.53 g / cm 3 ≥2.54 g / cm 3 Or even greater than or equal to 2.55 g / cm³ 3 .

[0214] In some embodiments, the precursor glass described herein can be made compatible with the float-type forming process by adjusting its liquidus viscosity. In some embodiments, the liquidus viscosity of the precursor glass can be greater than or equal to 0.5 kpoise (kP) to less than or equal to 3.5 kP, greater than or equal to 0.5 kpoise (kP) to less than or equal to 3 kP, greater than or equal to 0.5 kP to less than or equal to 2.5 kP, greater than or equal to 0.5 kP to less than or equal to 2.0 kP, greater than or equal to 0.5 kP to less than or equal to 1.5 kP, or even greater than or equal to 0.5 kP to less than or equal to 1.0 kP. In some embodiments, the liquidus viscosity of the precursor glass can be about 500 P, 1000 P, 1200 P, 1500 P, 2000 P, 2500 P, 3000 P, or 3500 P.

[0215] The precursor glass and glass-ceramic articles disclosed herein can be incorporated into another article, such as articles having a display (or display articles) (e.g., consumer electronic devices, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches), etc.), building articles, transportation articles (e.g., automobiles, trains, airplanes, ships, etc., for example, used as internal display covers, windows or windshields), electrical articles, or any article that may benefit from a certain transparency, scratch resistance, abrasion resistance or a combination thereof. Figure 6A and 6B The illustration shows an exemplary article incorporating any of the reinforced glass-ceramic articles disclosed herein.

[0216] Specifically, Figure 6A and 6B A consumer electronic device 200 is shown, comprising: a housing 202 having a front surface 204, a rear surface 206, and a side surface 208; electrical components (not shown) at least partially or entirely located within the housing, and including at least a controller, memory, and a display 210 located at or adjacent to the front surface of the housing; and a cover plate substrate 212 located at or above the front surface of the housing such that it is positioned above the display 210. In some embodiments, at least one of the cover plate substrate 212 or a portion of the housing 202 (such as the rear surface 206) may comprise any of the reinforced glass-ceramics disclosed herein.

[0217] Furthermore, the precursor glass disclosed herein can be ceramicized into other shapes (i.e., shapes other than plates or sheets) with minimal deformation, is easily processed into precision shapes, and can be cut, drilled, chamfered, tapped, and polished to achieve a high gloss using conventional ceramic processing tools. It can even exhibit varying degrees of translucency depending on its composition and heat treatment. These properties enable glass-ceramics to be used in a wide range of applications beyond those defined herein, including but not limited to worktops and other surfaces, appliance doors and exteriors, floor tiles, wall panels, ceiling tiles, whiteboards, material storage containers (hollowware) such as beverage bottles, food sales and storage containers, and machine parts requiring lightweight, wear-resistant, and dimensionally accurate properties. Due to the low viscosity of glass-ceramics, they can be formed into three-dimensional articles using various methods.

[0218] Therefore, the various embodiments described herein can be used to produce glass-ceramic articles with excellent optical quality and reduced warpage, while without adversely affecting, or even increasing, the stress in the glass-ceramic articles compared to glass articles ceramized according to conventional techniques. Such glass-ceramic articles are particularly suitable for portable electronic devices due to their strength properties and high transmittance values.

[0219] Example

[0220] The embodiments described herein will be further illustrated by the following examples.

[0221] The compositions listed in Tables 1A-1C were melted and formed into precursor glass plates with thicknesses ranging from 0.5 mm to 4.5 mm. The liquidus viscosity and liquidus temperature of the precursor glass plates were measured. The precursor glass plates were then ceramized according to the ceramization cycles shown in Tables 1A-1C to produce glass-ceramic articles, particularly glass-ceramic plates. Various properties of the glass-ceramic plates were then measured, including fracture toughness, Young's modulus, shear modulus, Poisson's ratio, refractive index (using a PerkinElmer 950 spectrometer), haze, and phase composition (by Rietveld x-ray diffraction). The properties of the glass-ceramics are reported in Tables 1A-1C.

[0222] Table 1A

[0223]

[0224] Table 1B

[0225]

[0226] Table 1C

[0227]

[0228]

[0229] Subsequently, glass-ceramic plates with compositions of Examples 1, 2, 3, and Comparative Example B were chemically strengthened by ion exchange at 530 °C in a molten salt bath containing 40 wt% sodium nitrate (NaNO3), 60 wt% potassium nitrate (KNO3), and 0.12 wt% lithium nitrate (LiNO3) for a series of different times (i.e., IOX times ranging from 3 to 12 hours). The maximum central tension established in each glass-ceramic plate due to ion exchange was measured. The results, including ion exchange time, measured maximum central tension, and glass-ceramic plate thickness, are reported in Table 2 below. Figure 7 The central tension (CT) of the examples listed in Table 2 is depicted as a function of time (hours).

[0230] Table 2

[0231]

[0232]

[0233] As shown in Table 2 and Figure 7 As shown, compared to glass-ceramic plates with Li2O:Al2O3 and Li2O:ZrO2 ratios falling outside these ranges, glass-ceramic plates with Li2O:Al2O3 ratios greater than 2 and less than or equal to 4 and Li2O:ZrO2 ratios greater than or equal to 1.2 and less than or equal to 1.7 (such as glass-ceramic plates formed from the compositions of Examples 1-3) can achieve higher CT values ​​in a shorter ion exchange time. This indicates that combining Li2O, Al2O3, ZrO2, and CaO in specified amounts and ratios has a synergistic effect on enhancing the ion exchange properties of glass-ceramics.

[0234] in addition, Figure 8 A plot showing the change in maximum CT with increasing ZrO2 concentration is shown. Figure 8 As shown, the maximum CT increases with the increase of ZrO2 concentration in the glass ceramic.

[0235] The glass-ceramic plates formed from the compositions of Example 5 and Comparative Example B were chemically strengthened according to the ion exchange conditions (i.e., “IOX conditions” W, X, Y, and Z) listed in Table 3. As an example, “60Na / 40K + 0.12Li (530°C - 3 hours 10 minutes)” corresponds to ion exchange at 530°C for 3 hours and 10 minutes in a salt bath comprising 60 wt% sodium nitrate (NaNO3), 40 wt% potassium nitrate (KNO3), and 0.12 wt% lithium nitrate (LiNO3). Subsequently, the surface compressive stress (CS), maximum central tension (CT), and depth of compression (DOC) of each glass-ceramic plate were measured. The results are provided in Table 3.

[0236] Table 3

[0237]

[0238]

[0239] Subsequently, four-point bending tests (as described herein) were performed on the glass-ceramic plates from Table 3 to determine fracture strength, and drop tests (as described herein) were performed to determine the maximum drop height (i.e., drop height) before failure. As described herein, the four-point bending tests were performed using 80-grit Al2O3 sandpaper to introduce defects. Figure 9 (For glass-ceramic plates with a thickness of 0.5 mm) and Figure 10 The results are depicted graphically (for a glass-ceramic plate with a thickness of 0.6 mm). The drop test was conducted on 80-grit SiC sandpaper. Figure 11 (For glass-ceramic plates with a thickness of 0.5 mm) and Figure 12 The results are depicted graphically (for a glass-ceramic plate with a thickness of 0.6 mm).

[0240] like Figure 9 As shown, compared to a glass-ceramic plate with a thickness of 0.5 mm formed from the composition of Comparative Example B and strengthened according to ion exchange condition W, a glass-ceramic plate with a thickness of 0.5 mm formed from the composition of Example 5 and strengthened according to ion exchange condition Y generally exhibits higher fracture strength. While not wishing to be bound by theory, it is believed that the increase in fracture strength is due to the higher central tension (CT) established in the glass-ceramic plate formed from the composition of Example 5 subjected to ion exchange according to condition Y. As described herein, it is believed that a relatively higher central tension allows for higher compressive stress at a greater depth from the surface of the glass-ceramic plate compared to a glass-ceramic plate with a relatively low central tension, thereby improving the mechanical properties of the glass-ceramic.

[0241] like Figure 10 As shown, compared to a glass-ceramic plate with a thickness of 0.6 mm formed from the composition of Comparative Example B and strengthened according to ion exchange condition X, a glass-ceramic plate with a thickness of 0.6 mm formed from the composition of Example 5 and strengthened according to ion exchange condition Z generally exhibits higher fracture strength. As described herein, the increase in fracture strength is thought to be due to the higher central tension (CT) established in the glass-ceramic plate formed from the composition of Example 5 subjected to ion exchange according to condition Z, because the relatively higher central tension allows for higher compressive stress at a deeper depth from the surface of the glass-ceramic plate compared to glass-ceramic plates with relatively lower central tension, thereby improving the mechanical properties of the glass-ceramic.

[0242] like Figure 11 As shown, compared to a glass-ceramic plate with a thickness of 0.5 mm formed from the composition of Comparative Example B and strengthened according to ion exchange condition W, a glass-ceramic plate with a thickness of 0.5 mm formed from the composition of Example 5 and strengthened according to ion exchange condition Y generally exhibits a higher maximum drop height. While not wishing to be bound by theory, it is believed that the increase in maximum drop height is due to the higher center tension (CT) established in the glass-ceramic plate formed from the composition of Example 5 subjected to ion exchange according to condition Y. As described herein, it is believed that a relatively higher center tension allows for higher compressive stress at a greater depth from the surface of the glass-ceramic plate compared to a glass-ceramic plate with a relatively low center tension, thereby improving the mechanical properties of the glass-ceramic.

[0243] like Figure 12As shown, compared to a glass-ceramic plate with a thickness of 0.6 mm formed from the composition of Comparative Example B and strengthened according to ion exchange condition X, a glass-ceramic plate with a thickness of 0.6 mm formed from the composition of Example 5 and strengthened according to ion exchange condition Z generally exhibits a higher maximum drop height. While not wishing to be bound by theory, it is believed that the increase in maximum drop height is due to the higher center tension (CT) established in the glass-ceramic plate formed from the composition of Example 5 subjected to ion exchange according to condition Z. As described herein, it is believed that a relatively higher center tension allows for higher compressive stress at a greater depth from the surface of the glass-ceramic plate compared to glass-ceramic plates with relatively low center tension, thereby improving the mechanical properties of the glass-ceramic.

[0244] Now for reference Figure 13 , Figure 13 The transmittance of a 0.5 mm thick glass-ceramic plate as a function of wavelength is graphically depicted. The glass-ceramic plate is formed from the composition of Example 5. Figure 13 As shown, with a product thickness of 0.5 mm, the glass-ceramic plate has a transmittance of more than 90% for light wavelengths in the range of greater than or equal to 400 nm to less than or equal to 800 nm.

[0245] The glass-ceramic plates were formed from the composition of Example 5. Some plates of each composition were reinforced by ion exchange. The Knoop hardness of both the reinforced and unreinforced plates was then determined according to the methods described herein. The average hardness values ​​are reported in Table 4 below.

[0246] Table 4

[0247]

[0248] As described herein, the annealing point, strain point, and CTE of the glass-ceramic plate formed from the composition of Example 5 were determined. The values ​​are reported in Table 5 below.

[0249] Table 5

[0250]

[0251] As described herein, the thermal diffusivity, thermal conductivity, and thermal capacity of the glass-ceramic plate formed from the composition of Example 5 were determined. The values ​​are reported in Tables 6-8 below.

[0252] Table 6

[0253]

[0254] Table 7

[0255]

[0256] Table 8

[0257]

[0258] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and variations to the various embodiments described herein, provided that such modifications and variations fall within the scope of the appended claims and their equivalents.

Claims

1. A glass-ceramic comprising: Greater than or equal to 55 wt% to less than or equal to 75 wt% SiO2; Greater than or equal to 2 wt% to less than or equal to 10 wt% Al2O3; Greater than or equal to 8 wt% to less than or equal to 15 wt% Li2O; Greater than or equal to 2 wt% to less than or equal to 4 wt% P2O5; Greater than or equal to 0.05 wt% and less than or equal to 4.0 wt% CaO; Greater than or equal to 5 wt% to less than or equal to 15 wt% ZrO2; as well as A phase assembly comprising at least one crystalline phase and a residual amorphous glassy phase, wherein: The ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 4; and The ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.2 and less than or equal to 1.

7.

2. The glass-ceramic according to claim 1, wherein the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 3.

5.

3. The glass-ceramic according to any one of claims 1 to 2, wherein the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.35 and less than or equal to 1.

7.

4. The glass-ceramic according to any one of claims 1 to 3, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0 and less than or equal to 1.

5. The glass-ceramic according to any one of claims 1 to 4, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0.35 and less than or equal to 0.

65.

6. The glass-ceramic according to any one of claims 1 to 5, further comprising greater than 0 wt% and less than or equal to 2 wt% Na2O.

7. The glass-ceramic according to any one of claims 1 to 6, further comprising greater than 0.1 wt% and less than or equal to 1 wt% K2O.

8. The glass-ceramic according to any one of claims 1 to 7, further comprising greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% HfO2.

9. The glass-ceramic according to any one of claims 1 to 8, comprising more than or equal to 10 wt% to less than or equal to 14 wt% Li2O.

10. The glass-ceramic according to any one of claims 1 to 9, comprising more than or equal to 6 wt% to less than or equal to 10 wt% ZrO2.

11. The glass-ceramic according to any one of claims 1 to 10, comprising greater than or equal to 3 wt% to less than or equal to 8 wt% Al2O3.

12. The glass-ceramic according to any one of claims 1 to 11, comprising more than or equal to 0.10 wt% to less than or equal to 1.00 wt% CaO.

13. The glass-ceramic according to any one of claims 1 to 12, wherein the phase assembly comprises: Lithium disilicate crystalline phase; The crystalline phase of petalite; and The residual amorphous glass phase.

14. The glass-ceramic of claim 13, comprising 15 wt% to 35 wt% of the residual amorphous glass phase.

15. The glass-ceramic according to claim 13 or claim 14, comprising greater than or equal to 20 wt% to less than or equal to 45 wt% of the said lepidolite crystalline phase.

16. The glass-ceramic according to any one of claims 13 to 15, comprising 35 wt% to 50 wt% of the lithium disilicate crystalline phase.

17. The glass-ceramic according to any one of claims 1 to 16, further comprising: A compressive stress layer extending from the surface of the glass-ceramic to a certain compression depth; and Central tension, wherein the central tension is greater than 170 MPa.

18. The glass-ceramic according to claim 17, wherein the surface compressive stress of the compressive stress layer is greater than or equal to 200 MPa and less than or equal to 550 MPa.

19. The glass-ceramic according to claim 17 or claim 18, wherein the glass-ceramic is ion-exchange strengthened.

20. The glass-ceramic according to any one of claims 17 to 19, wherein the glass-ceramic has a thickness t, and the compression depth is greater than or equal to 0.09*t and less than or equal to 0.30*t.

21. The glass-ceramic according to any one of claims 1 to 20, wherein, with an article thickness of 0.5 mm, the glass-ceramic has a transmittance of greater than 90% for light wavelengths in the range of greater than or equal to 400 nm to less than or equal to 800 nm.

22. The glass-ceramic according to any one of claims 1 to 21, wherein the glass-ceramic has a fracture toughness greater than or equal to 1.0 MPa·m before being strengthened by ion exchange. 1 / 2 And less than or equal to 2.0 MPa·m 1 / 2 .

23. The glass-ceramic according to any one of claims 1 to 22, wherein the elastic modulus of the glass-ceramic is greater than or equal to 90 GPa and less than or equal to 130 GPa.

24. An electronic device comprising a cover plate substrate, the cover plate substrate comprising glass-ceramic according to any one of claims 1 to 23.

25. A glass-ceramic comprising: Lithium disilicate crystalline phase; The crystalline phase of petalite; and The remaining amorphous glassy phase, in which: The ratio of Li2O (wt%) to Al2O3 (wt%) in the glass-ceramic is greater than 2 and less than or equal to 4; and The ratio of Li2O (wt%) to ZrO2 (wt%) in the glass ceramic is greater than or equal to 1.2 and less than or equal to 1.

7.

26. The glass-ceramic of claim 25, comprising 15 wt% to 35 wt% of the residual amorphous glass phase.

27. The glass-ceramic according to any one of claims 25 to 26, comprising more than or equal to 20 wt% to less than or equal to 45 wt% of the said lepidolite crystalline phase.

28. The glass-ceramic according to any one of claims 25 to 27, comprising 35 wt% to 50 wt% of the lithium disilicate crystalline phase.

29. The glass-ceramic according to any one of claims 25 to 28, further comprising: A compressive stress layer extending from the surface of the glass-ceramic to a certain compression depth; and Central tension, wherein the central tension is greater than 170 MPa.

30. The glass-ceramic according to claim 29, wherein the surface compressive stress of the compressive stress layer is greater than or equal to 200 MPa and less than or equal to 550 MPa.

31. The glass-ceramic according to any one of claims 29 to 30, wherein the glass-ceramic is ion-exchange strengthened.

32. The glass-ceramic according to any one of claims 29 to 31, wherein the glass-ceramic has a thickness t, and the compression depth is greater than or equal to 0.09*t and less than or equal to 0.30*t.

33. The glass-ceramic according to any one of claims 25 to 32, wherein, with an article thickness of 0.5 mm, the glass-ceramic has a transmittance of greater than 90% for light wavelengths in the range of greater than or equal to 400 nm to less than or equal to 800 nm.

34. An electronic device comprising a cover plate substrate, the cover plate substrate comprising glass-ceramic according to any one of claims 25 to 33.

35. The glass-ceramic according to any one of claims 25 to 34, wherein the glass-ceramic has a fracture toughness greater than or equal to 1.0 MPa·m before being strengthened by ion exchange. 1 / 2 And less than or equal to 2.0 MPa·m 1 / 2 .

36. The glass-ceramic according to any one of claims 25 to 35, wherein the elastic modulus of the glass-ceramic is greater than or equal to 90 GPa and less than or equal to 130 GPa.

37. A precursor glass comprising: Greater than or equal to 55 wt% to less than or equal to 75 wt% SiO2; Greater than or equal to 2 wt% to less than or equal to 10 wt% Al2O3; Greater than or equal to 8 wt% to less than or equal to 15 wt% Li2O; Greater than or equal to 2 wt% to less than or equal to 4 wt% P2O5; Greater than or equal to 0.05 wt% and less than or equal to 4.0 wt% CaO; as well as Greater than or equal to 5 wt% to less than or equal to 15 wt% ZrO2; The ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 4; and The ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.2 and less than or equal to 1.

7.

38. The precursor glass according to claim 37, wherein the ratio of Li2O (wt%) to Al2O3 (wt%) is greater than 2 and less than or equal to 3.

5.

39. The precursor glass according to claim 37 or claim 38, wherein the ratio of Li2O (wt%) to ZrO2 (wt%) is greater than or equal to 1.35 and less than or equal to 1.

7.

40. The precursor glass according to any one of claims 37 to 39, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0 and less than or equal to 1.

41. The precursor glass according to any one of claims 37 to 40, wherein the ratio of Al2O3 (wt%) to ZrO2 (wt%) is greater than 0.35 and less than or equal to 0.

65.

42. The precursor glass according to any one of claims 37 to 41, further comprising greater than 0 wt% and less than or equal to 2 wt% Na2O.

43. The precursor glass according to any one of claims 37 to 42, further comprising greater than 0.1 wt% and less than or equal to 1 wt% K2O.

44. The precursor glass according to any one of claims 37 to 43, further comprising greater than or equal to 0.1 wt% to less than or equal to 1.0 wt% HfO2.

45. The precursor glass according to any one of claims 37 to 44, comprising more than or equal to 10 wt% to less than or equal to 14 wt% Li2O.

46. ​​The precursor glass according to any one of claims 37 to 45, comprising more than or equal to 6 wt% to less than or equal to 10 wt% ZrO2.

47. The precursor glass according to any one of claims 37 to 46, comprising greater than or equal to 3 wt% to less than or equal to 8 wt% Al2O3.

48. The precursor glass according to any one of claims 37 to 47, comprising greater than or equal to 0.10 wt% to less than or equal to 1.00 wt% CaO.

49. The precursor glass according to any one of claims 37 to 48, wherein the liquidus viscosity of the precursor glass is greater than or equal to 0.5 kP and less than or equal to 3.5 kP.

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