High strength glass-ceramics having petalite and lithium silicate structures

Abstract

To provide a transparent or translucent glass-ceramic material with fast ion-exchanging capability and high fracture toughness.SOLUTION: A precursor glass composition contains: about 55 wt.% to about 80 wt.% of SiO2; about 5 wt.% to about 20 wt.% of Al2O3; about 5 wt.% to about 20 wt.% of Li2O; about 2 wt.% to about 4 wt.% of P2O5; and about 0.2 wt.% to about 15 wt.% of ZrO2.SELECTED DRAWING: Figure 2

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Patent Application No. 62 / 061,385, filed October 8, 2014, and U.S. Provisional Patent Application No. 62 / 205,120, filed August 14, 2015, the contents of each of which are relied upon and incorporated by reference in their entirety into this application. [Technical Field]

[0002] Embodiments relate to glass and glass-ceramic compositions, and in particular to high strength glass-ceramic compositions having a combination of petalite and lithium silicate phases. [Background technology]

[0003] Lithium disilicate glass ceramics in the SiO2-Li2O-K2O-ZnO-P2O5-Al2O3-ZrO2 system have been developed and marketed for use as dental crowns, bridges, and overlays. The glass ceramic's microstructure of interconnected platelet crystals provides high mechanical strength and fracture toughness, as well as excellent chemical resistance. Compositions in this field were invented at Corning Incorporated and patented by Beall et al. in U.S. Patent No. 5,699,499 (the "'799 patent").

[0004] Furthermore, known glass-based materials often exhibit inherent brittleness, or low resistance to crack propagation, e.g., low inherent fracture toughness (e.g., 0.5-1.0 MPa m for oxide glasses and glass-ceramics). 1 / 2 ), oxide glasses are sensitive to small defects and scratches. For comparison, commercially available single crystal substrates have a thermal conductivity of about 2.4 to about 4.5 MPa m 1 / 2Chemical strengthening, for example, by ion exchange processes, can provide some resistance to crack penetration at the surface of a glass or glass-ceramic by imparting a compressive stress layer to the glass or glass-ceramic from the surface to a certain depth (e.g., 50-100 μm), but crack penetration resistance can be limited and is no longer effective after a crack penetrates through the compressive stress layer into the bulk of the glass or glass-ceramic. While such strengthening provides some resistance to crack penetration, the intrinsic properties (k1c) of the material are not affected by ion exchange. There continues to be a focus on improving the mechanical properties of glass-based materials, particularly with regard to damage tolerance and fracture toughness. Thus, there is a need to provide materials with improved damage tolerance and fracture toughness.

[0005] Ion-exchangeable, lithium-containing aluminosilicate glass-ceramic articles of the β-spodumene family are known, and they offer damage resistance and fracture toughness. However, β-spodumene-based glass-ceramics are generally opaque, which limits their use in display-related applications or other applications requiring transparency or translucency. Therefore, there is a need for transparent or translucent glass-ceramic materials that have rapid ion-exchangeability and high fracture toughness. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 5,219,799 Summary of the Invention [Means for solving the problem]

[0007] A first aspect includes a glass-ceramic article having a petalite crystalline phase and a lithium silicate crystalline phase, wherein the petalite crystalline phase and the lithium silicate crystalline phase have a higher weight percentage than other crystalline phases present in the glass-ceramic article. In some embodiments, the petalite crystalline phase comprises 20-70 weight percent of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-60 weight percent of the glass-ceramic article. In some embodiments, the petalite crystalline phase comprises 45-70 weight percent of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-50 weight percent of the glass-ceramic article. In some embodiments, the petalite crystalline phase comprises 40-60 weight percent of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-50 weight percent of the glass-ceramic article.

[0008] In some embodiments, the glass-ceramic article is transparent. In some embodiments, the glass-ceramic article has at least 85% transmittance for light in the wavelength range of 400 nm to 1000 nm. In some embodiments, the glass-ceramic article has at least 90% transmittance for light in the wavelength range of 400 nm to 1000 nm. In some embodiments, the glass-ceramic article is transparent. In some embodiments, the glass-ceramic article comprises grains having a longest dimension of 500 nm or less, or 100 nm or less.

[0009] In some embodiments, the glass-ceramic article has a composition comprising, in weight percent: SiO2: 55‐80%; Al2O3: 2‐20%; Li2O: 5‐20%; B2O3: 0‐10%; Na2O: 0‐5%; ZnO: 0‐10%; P2O5: 0.5-6%; and ZrO2: 0.2‐15%.

[0010] In some embodiments, the glass-ceramic article has a composition further comprising the following optional additional components in weight percent: K2O: 0‐4%; MgO: 0‐8%; TiO2: 0‐5%; CeO2: 0-0.4%; and SnO2: 0.05‐0.5%.

[0011] In some embodiments, the glass-ceramic article has a composition comprising, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; B2O3: 0‐2%; P2O5: 1.5-2.5%; and ZrO2: 2‐4%.

[0012] In some embodiments, the glass-ceramic article has a composition comprising, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; Na2O: 1‐2%; K2O: 1‐2%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2‐4%.

[0013] In some embodiments, the glass-ceramic article has a composition comprising, in weight percent: SiO2: 65‐80%; Al2O3: 5‐16%; Li2O: 8‐15%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐2%; P2O5: 0.5-4%; and ZrO2: 0.2‐6%.

[0014] In some embodiments, the glass-ceramic article has a composition comprising, in weight percent: SiO2: 60‐80%; Al2O3: 5‐20%; Li2O: 5‐20%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐4%; P2O5: 0.5-4%; and ZrO2: 0.2‐8%.

[0015] In some embodiments, the sum of the weight percentages of P2O5 and ZrO2 in the glass-ceramic composition is greater than 3.

[0016] In some embodiments, the glass-ceramic article comprises one or more of the following: 1 MPa m 1 / 2 Fracture toughness of approximately 600 kgf / mm 2 (approx. 5884N / mm 2 ) or greater; or a ring-on-ring strength of at least 300 MPa. In some embodiments, the glass-ceramic article has a compressive stress layer formed by ion exchange having a depth of layer (DOL) of at least about 30 μm. In some embodiments, the ion-exchanged glass-ceramic article is not brittle.

[0017] A second aspect includes a method of forming a glass-ceramic article, the method comprising: SiO2: 55‐80%; Al2O3: 2‐20%; Li2O: 5‐20%; B2O3: 0‐10%; Na2O: 0‐5%; ZnO: 0‐10%; P2O5: 0.5-6%; and ZrO2: 0.2-15% forming a glass composition comprising: ceramming the glass composition to form a glass-ceramic article comprising a petalite crystalline phase and a lithium silicate crystalline phase. Including, The petalite crystalline phase and the lithium silicate crystalline phase have a higher weight percentage than other crystalline phases present in the glass-ceramic article.

[0018] In some embodiments, the method includes forming a glass composition further comprising, in weight percentage: K2O: 0‐4%; MgO: 0‐8%; TiO2: 0‐5%; CeO2: 0-0.4%; and SnO2: 0.05‐0.5%.

[0019] In some embodiments, the method includes forming a glass composition further comprising, in weight percentage: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; B2O3: 0‐2%; P2O5: 1.5-2.5%; and ZrO2: 2‐4%.

[0020] In some embodiments, the method includes forming a glass composition further comprising, in weight percentage: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; Na2O: 1‐2%; K2O: 1‐2%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2‐4%.

[0021] In some embodiments, the method includes forming a glass composition further comprising, in weight percentage: SiO2: 65‐80%; Al2O3: 5‐16%; Li2O: 8‐15%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐2%; P2O5: 0.5-4%; and ZrO2: 0.2‐6%.

[0022] In some embodiments, the method includes forming a glass composition further comprising, in weight percentage: SiO2: 60‐80%; Al2O3: 5‐20%; Li2O: 5‐20%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐4%; P2O5: 0.5-4%; and ZrO2: 0.2‐8%.

[0023] In some embodiments, the sum of the weight percentages of P2O5 and ZrO2 in the glass-ceramic composition is greater than 3.

[0024] In some embodiments, the method further comprises ion-exchanging the glass-ceramic article to produce a compressive stress layer having a depth of layer of at least 30 μm, hi some embodiments, the ion-exchanged glass-ceramic article is not brittle.

[0025] In some embodiments, the ceramming step comprises the following sequential steps: heating the glass composition to a glass pre-nucleation temperature; maintaining the glass pre-nucleation temperature for a predetermined period of time; heating the composition to a nucleation temperature; maintaining the nucleation temperature for a predetermined period of time; heating the composition to a crystallization temperature; and maintaining the crystallization temperature for a predetermined period of time.

[0026] In some embodiments, the ceramming step comprises the following sequential steps: heating the composition to a nucleation temperature; maintaining the nucleation temperature for a predetermined period of time; heating the composition to a crystallization temperature; and maintaining the crystallization temperature for a predetermined period of time.

[0027] In some embodiments, the method forms a glass-ceramic article, wherein the petalite crystalline phase comprises 20-70 wt % of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-60 wt % of the glass-ceramic article.

[0028] Other features and advantages of the present invention will become apparent from the following detailed description when read in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0029] [Figure 1] Plots of differential scanning calorimetry (DSC) traces for exemplary glass-ceramic compositions [Figure 2] 1 is a plot of the transmittance of exemplary glass-ceramic compositions for light having wavelengths between 400 nm and 1000 nm at a sample thickness of 1 mm. [Figure 3A] Scanning electron microscope (SEM) images of exemplary glass-ceramic compositions at the 200 nm scale [Figure 3B]Scanning electron microscope (SEM) images of exemplary glass-ceramic compositions at the 100 nm scale [Figure 4] Ring-on-ring (RoR) and abraded ring-on-ring (aRoR) test results for exemplary non-ion-exchanged glass-ceramic compositions [Figure 5] Plot of NaO concentration (mole percent) versus sample thickness for exemplary glass-ceramic compositions. [Figure 6] RoR test results for exemplary glass-ceramic compositions before and after ion exchange [Figure 7] aRoR Test Results of Ion-Exchanged Exemplary Glass-Ceramic Compositions [Figure 8] RoR Test Results of Exemplary Glass-Ceramic Compositions Ion-Exchanged for Different Periods [Figure 9] aRoR test results for exemplary glass-ceramic compositions that were ion-exchanged and abraded under different pressures [Figure 10] Photographs showing ion-exchanged glass-ceramic sheets with different fracture patterns [Figure 11] Plots of differential scanning calorimetry (DSC) traces for exemplary glass-ceramic compositions [Figure 12] X-ray diffraction (XRD) spectra of the crystalline phase of exemplary glass-ceramic compositions [Figure 13] Ring-on-Ring (RoR) Test Results for Exemplary Glass-Ceramic Compositions [Figure 14] Plot of NaO concentration (weight percent) versus sample thickness for exemplary glass-ceramic compositions. DETAILED DESCRIPTION OF THE INVENTION

[0030] In the following detailed description, numerous specific details may be set forth to provide a thorough understanding of the embodiments described herein. However, it will be apparent to one of ordinary skill in the art that the embodiments may be practiced without some or all of these specific details. In other instances, well-known features or processes may not be described in detail so as not to unnecessarily obscure the present disclosure. Furthermore, similar or identical reference numbers may be used to identify common or similar elements. Furthermore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In the event of a conflict of meaning, the present specification, including definitions, will control.

[0031] Although other methods and materials can be used in the practice or testing of the embodiments, certain preferred methods and materials are described herein.

[0032] Disclosed are materials, compounds, compositions, and components that can be used with, can be used to prepare for, or are embodiments of the disclosed methods and compositions. Where these and other materials are disclosed herein, and combinations, subsets, interactions, groups, etc. of these materials are disclosed, it is understood that each of the various individual and collective combinations and permutations of these compounds is specifically contemplated and described herein, even though they may not each be explicitly mentioned.

[0033] Thus, if substituents A, B, and C are disclosed along with substituent classes D, E, and F, and an example combination embodiment A-D is disclosed, each is considered individually and collectively. Thus, in this example, from the disclosure of A, B, and / or C; D, E, and / or F; and the exemplary combination A-D, the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and considered disclosed. Likewise, any subset or combination of these is specifically contemplated and disclosed. Thus, for example, from the disclosure of A, B, and / or C; D, E, and / or F; and the exemplary combination A-D, the subgroups A-E, B-F, and C-E are also specifically contemplated and considered disclosed. This concept applies to all aspects of the present disclosure, including, but not limited to, any components of the compositions described above, as well as steps in methods of making and using the disclosed compositions. More specifically, the exemplary composition ranges set forth herein are to be considered part of the present specification, and further, the endpoints of the exemplary numerical ranges are to be considered to be provided in all respects as if they were specifically included in the text, with all combinations being specifically contemplated and disclosed. Furthermore, to the extent that there are various additional steps that can be performed, it is to be understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the present disclosure, and that each of such combinations is to be considered to be specifically contemplated and disclosed.

[0034] Furthermore, when a range of numerical values ​​including upper and lower limits is recited herein, unless otherwise specified under specific circumstances, the range is intended to include the endpoints, and all integers and fractions within the range. When a range is defined, it is not intended to limit the scope of the disclosure to the specific values ​​recited. Furthermore, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges, or a list of preferred upper and lower limits, this should be understood to specifically disclose all ranges formed from any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether such pairs are individually disclosed. Finally, when the term "about" is used in describing values ​​or range endpoints, the disclosure should be understood to include the specific value or endpoint referred to.

[0035] As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximate, and / or larger or smaller as needed, to reflect tolerances, conversion factors, rounding, measurement error, etc., and other factors known to those of ordinary skill in the art. In general, amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate," whether or not expressly stated as such.

[0036] As used herein, the term "or" is inclusive; more specifically, the phrase "A or B" means "A, B, or both A and B." An exclusive "or" is indicated herein, for example, by the terms "either A or B" and "one of A or B."

[0037] The indefinite articles "a" and "an" are used to describe elements and components of the present disclosure. The use of these articles means that there is one or at least one of these elements or components. Although these articles are conventionally used to mean that the modified noun is a singular noun, as used herein, the articles "a" and "an" also include the plural, unless specifically stated otherwise in the specific example. Similarly, as used herein, the definite article "the" also means that the modified noun may be singular or plural, again unless specifically stated otherwise in the specific example.

[0038] For purposes of describing embodiments, it should be noted that references herein to a variable being a "function" of a parameter or another variable are not intended to indicate that the variable is a function only of the listed parameter or variables. Rather, references to a variable being a "function" of a listed parameter are intended to be non-limiting, such that the variable may be a function of a single parameter or multiple parameters.

[0039] It should be noted that, as used herein, terms such as "preferably," "commonly," and "typically" are not used to limit the scope of the present disclosure or to imply that any particular feature is critical, essential, or even essential to the structure or function of the present disclosure. Rather, these terms are merely intended to identify particular aspects of certain embodiments of the present disclosure or to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the present disclosure.

[0040] One or more of the claims may use the term "wherein" as a transitional phrase. Note that for purposes of defining this disclosure, this term is introduced in the claims as an open-ended transitional phrase used to introduce the recitation of a series of features of a structure, and is to be interpreted in a similar manner to the more commonly used open-ended preamble term "comprising."

[0041] Due to the raw materials and / or equipment used to produce the glass or glass-ceramic compositions of the present disclosure, certain impurities or components not intentionally added may be present in the final glass or glass-ceramic composition. Such materials, present in trace amounts in the glass or glass-ceramic composition, are referred to herein as "tramp materials."

[0042] As used herein, a glass or glass-ceramic composition having 0 wt. % of a compound is defined to mean that the compound, molecule, or element was not intentionally added to the composition, but that the composition may still contain the compound, typically in trace or insignificant amounts. Similarly, "iron-free," "sodium-free," "lithium-free," "zirconium-free," "alkaline earth metal-free," or "heavy metal-free," etc., are defined to mean that the compound, molecule, or element was not intentionally added to the composition, but that the composition may still contain iron, sodium, lithium, zirconium, alkaline earth metals, heavy metals, etc., but in approximately trace or insignificant amounts.

[0043] Unless otherwise specified, all component concentrations described herein are expressed as weight percent (wt %).

[0044] Glass and glass ceramics As discussed above, it is desirable to obtain a transparent or translucent lithium-containing aluminosilicate glass-ceramic composition having petalite and lithium silicate as primary crystalline phases. The lithium silicate crystalline phase can be lithium disilicate or lithium metasilicate. Improved properties of the glass and glass-ceramic compositions disclosed herein include: 1) the glasses retain a low melting point (<1500°C) while offering a relatively high liquidus viscosity (>2000 poise) and a wide processing window compatible with conventional rolling, forming, and float processes; 2) lithium silicate is retained as the primary crystalline phase, which provides the glass-ceramic with inherently high mechanical strength and fracture toughness; and 3) petalite is the second primary crystalline phase, has a fine grain size that contributes to the transparency or translucency of the glass-ceramic, and can be ion-exchanged for additional mechanical strength. Furthermore, these materials can be cerammed into shapes with minimal distortion, easily machined into precise shapes, cut, drilled, chamfered, tapped, and polished to a high gloss using conventional ceramic machining tools, and can exhibit varying degrees of translucency depending on composition and heat treatment. These properties allow these glass-ceramics to be used in a wide variety of applications, including: countertops and other surfaces; covers for handheld, desktop, and wall-mounted consumer electronic devices; doors and exteriors for household appliances; floor tiles; wall paneling; ceiling paneling; whiteboards; material storage containers (hollowware) such as beverage bottles; food vending and storage containers; and machine parts requiring lightweight properties, good wear resistance, and precise dimensions. The relatively low viscosity of these glass-ceramics allows them to be formed into three-dimensional articles using a variety of methods.

[0045] Petalite, i.e. LiAlSiO 10is a monoclinic crystal with a layered three-dimensional framework structure with folded SiO layers connected by Li and Al tetrahedra. The inorganic petalite is a source of lithium and is used as a low thermal expansion phase to improve the thermal shock resistance of glass-ceramics or ceramic components. Furthermore, glass-ceramic articles based on the petalite phase can be chemically strengthened in a salt bath, during which Na + (and / or K + ) is Li in the petalite structure +In some embodiments, the weight percentage of the petalite crystalline phase in the glass-ceramic composition is about 20 to about 70 wt%, about 20 to about 65 wt%, about 20 to about 60 wt%, about 20 to about 55 wt%, about 20 to about 50 wt%, about 20 to about 45 wt%, about 20 to about 40 wt%, about 20 to about 35 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, or about 25 to about 70 wt%. , about 25 to about 65% by weight, about 25 to about 60% by weight, about 25 to about 55% by weight, about 25 to about 50% by weight, about 25 to about 45% by weight, about 25 to about 40% by weight, about 25 to about 35% by weight, about 25 to about 30% by weight, about 30 to about 70% by weight, about 30 to about 65% by weight, about 30 to about 60% by weight, about 30 to about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 30 to about 40% by weight, about 30 to about 35% by weight, about 35 to about 70% by weight, about 35 to about 65% by weight, about 35 to about 60% by weight, about 35 to about 55% by weight, about 35 to about 50% by weight, about 35 to about 45% by weight, about 35 to about 40 Weight%, about 40 to about 70% by weight, about 40 to about 65% by weight, about 40 to about 60% by weight, about 40 to about 55% by weight, about 40 to about 50% by weight, about 40 to about 45% by weight, about 45 to about 70% by weight, about 4 It can be within the range of 5 to about 65% by weight, about 45 to about 60% by weight, about 45 to about 55% by weight, about 45 to about 50% by weight, about 50 to about 70% by weight, about 50 to about 65% by weight, about 50 to about 60% by weight, about 50 to about 55% by weight, about 55 to about 70% by weight, about 55 to about 65% by weight, about 55 to about 60% by weight, about 60 to about 70% by weight, about 60 to about 65% by weight, or about 65 to about 70% by weight. In some embodiments, the glass-ceramic has about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 wt.% petalite crystalline phase.

[0046] As mentioned above, the lithium silicate crystalline phase can be lithium disilicate or lithium metasilicate. Lithium disilicate, or Li2SiO5, is an orthorhombic crystal based on wavy sheets of {SiO5} tetrahedral arrays. The crystals are typically plate- or lath-shaped and have pronounced cleavage planes. Lithium disilicate-based glass-ceramics offer highly desirable mechanical properties, including high bulk strength and fracture toughness, due to their randomly oriented, interconnected crystal microstructure—i.e., a crystal structure that allows cracks to propagate through the material via tortuous paths around these crystals. Lithium metasilicate, or Li2SiO3, has orthorhombic symmetry, with (SiO6) chains running parallel to the c-axis and linked together by lithium ions. Lithium metasilicate crystals can be readily dissolved from glass-ceramics in dilute hydrofluoric acid. In some embodiments, the weight percentage of the lithium silicate crystalline phase in the glass-ceramic composition is about 20 to about 60 wt%, about 20 to about 55 wt%, about 20 to about 50 wt%, about 20 to about 45 wt%, about 20 to about 40 wt%, about 20 to about 35 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, about 25 to about 60 wt%, about 25 to about 55 wt%, about 25 to about 50 wt%, about 25 to about 45 wt%, about 25 to about 40 wt%, about 25 to about 35 wt%, about 25 to about 30 wt%, about 30 to about 6 ... It can be within the range of about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 30 to about 40% by weight, about 30 to about 35% by weight, about 35 to about 60% by weight, about 35 to about 55% by weight, about 35 to about 50% by weight, about 35 to about 45% by weight, about 35 to about 40% by weight, about 40 to about 60% by weight, about 40 to about 55% by weight, about 40 to about 50% by weight, about 40 to about 45% by weight, about 45 to about 60% by weight, about 45 to about 55% by weight, about 45 to about 50% by weight, about 50 to about 60% by weight, about 50 to about 55% by weight, or about 55 to about 60% by weight.In some embodiments, the glass-ceramic has 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 wt. % lithium silicate crystalline phase.

[0047] There are two broad families of lithium disilicate glass-ceramics. The first group includes those doped with ceria and precious metals such as silver. These allow photosensitive nucleation with UV light, and subsequent heat treatment can produce tough glass-ceramics such as Fotoceram®. The second family of lithium disilicate glass-ceramics is nucleated by the addition of P2O5, where the nucleation phase is Li3PO4. P2O5-nucleated lithium disilicate glass-ceramics have been developed for a wide range of applications, including high-temperature sealing materials, computer hard drive disks, transparent protective clothing, and dental applications.

[0048] The glasses and glass-ceramics described herein are often generally described as lithium-containing aluminosilicate glasses or glass-ceramics and include SiO, AlO, and LiO. In addition to SiO, AlO, and LiO, the glasses and glass-ceramics described herein may further contain alkali salts such as NaO, KO, RbO, or CsO, as well as P0 and ZrO, and numerous other components described below. In one or more embodiments, the primary crystalline phases include petalite and lithium silicate, although β-spodumene ss, β-quartz ss, lithium phosphate, cristobalite, and rutile may also be present as minor phases, depending on the composition of the precursor glass. In some embodiments, the glass-ceramic composition has a residual glass content of about 5 to about 30 wt%, about 5 to about 25 wt%, about 5 to about 20 wt%, about 5 to about 15 wt%, about 5 to about 10 wt%, about 10 to about 30 wt%, about 10 to about 25 wt%, about 10 to about 20 wt%, about 10 to about 15 wt%, about 15 to about 30 wt%, about 15 to about 25 wt%, about 15 to about 20 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, or about 25 to about 30 wt%. In some embodiments, the residual glass content can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%.

[0049] SiO2, an oxide involved in glass formation, can function to stabilize the network structure of glasses and glass ceramics. In some embodiments, the glass or glass ceramic composition comprises about 55 to about 80 wt% SiO2. In some embodiments, the glass or glass ceramic composition comprises 69 to about 80 wt% SiO2. In some embodiments, the glass or glass ceramic composition comprises about 55 to about 80 wt%, about 55 to about 77 wt%, about 55 to about 75 wt%, about 55 to about 73 wt%, 60 to about 80 wt%, about 60 to about 77 wt%, about 60 to about 75 wt%, about 60 to about 73 wt%, 65 to about 80 wt%, about 65 to about 77 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, 69 to about 80 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, about 69 to about 80 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, about 69 to about 80 wt%, about 65 to about 73 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, about 69 to about 80 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, about 69 to about 80 wt%, about 65 to about 75 wt%, about 65 to about 73 wt%, about 69 to about 80 wt%, about 65 to about 73 ... The glass or glass ceramic composition may comprise about 80 wt%, about 69 to about 77 wt%, about 69 to about 75 wt%, about 69 to about 73 wt%, about 70 to about 80 wt%, about 70 to about 77 wt%, about 70 to about 75 wt%, about 70 to about 73 wt%, about 73 to about 80 wt%, about 73 to about 77 wt%, about 73 to about 75 wt%, about 75 to about 80 wt%, about 75 to about 77 wt%, or about 77 to about 80 wt% SiO2. In some embodiments, the glass or glass ceramic composition comprises about 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 wt% SiO2.

[0050] Regarding viscosity and mechanical performance, viscosity and mechanical performance are influenced by glass composition. In the glasses and glass-ceramics, SiO2 acts as a primary glass-forming oxide for the precursor glass and can function to stabilize the network structure of the glasses and glass-ceramics. The SiO2 concentration must be high enough to allow the formation of a petalite crystalline phase when the precursor glass is heat-treated to convert it to a glass-ceramic. Because the melting points of pure SiO2 or high-SiO2 glasses are undesirably high, the melting point (200 poise temperature) can be controlled by limiting the amount of SiO2.

[0051] Al2O3 can also provide stability to the network and provide improved mechanical properties and chemical resistance. However, if the amount of Al2O3 is too high, the proportion of lithium silicate crystals may decrease, possibly to the point where an interconnected structure cannot be formed. By adjusting the amount of Al2O3, viscosity can be controlled. Furthermore, if the amount of Al2O3 is too high, the viscosity of the melt generally increases. In some embodiments, the glass or glass-ceramic composition can include about 2 to about 20 wt.% Al2O3. In some embodiments, the glass or glass-ceramic composition can include about 6 to about 9 wt.% Al2O3. In some embodiments, the glass or glass ceramic composition comprises about 2 to about 20%, about 2 to about 18%, about 2 to about 15%, about 2 to about 12%, about 2 to about 10%, about 2 to about 9%, about 2 to about 8%, about 2 to about 5%, about 5 to about 20%, about 5 to about 18%, about 5 to about 15%, about 5 to about 12%, about 5 to about 10%, about 5 to about 9%, about 5 to about 8%, about 6 to about 20%, about 6 to about 15%, about 6 ...10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 10%, about 5 to about 1 About 18 wt%, about 6 to about 15 wt%, about 6 to about 12 wt%, about 6 to about 10 wt%, about 6 to about 9 wt%, about 8 to about 20%, about 8 to about 18 wt%, about 8 to about 15 wt%, about 8 to about 12 wt%, about 8 to about 10 wt%, about 10 to about 20%, about 10 to about 18 wt%, about 10 to about 15 wt%, about 10 to about 12 wt%, about 12 to about 20%, about 12 to about 18 wt%, or about 12 to about 15 wt% Al2O3. In some embodiments, the glass or glass-ceramic composition can comprise about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt% Al2O3.

[0052] In the glasses and glass-ceramics described herein, LiO supports the formation of both petalite and lithium silicate crystalline phases. In practice, it is desirable to have at least about 7 wt. % LiO in the composition to obtain petalite and lithium silicate as the predominant crystalline phases. Furthermore, it has been found that once too much LiO is present—about 15 wt. %—the composition becomes highly fluid. In some embodiments, the glass or glass-ceramic can include about 5 wt. % to about 20 wt. % LiO. In other embodiments, the glass or glass-ceramic can include about 10 wt. % to about 14 wt. % LiO. In some embodiments, the glass or glass ceramic composition comprises from about 5 to about 20 wt%, about 5 to about 18 wt%, about 5 to about 16 wt%, about 5 to about 14 wt%, about 5 to about 12 wt%, about 5 to about 10 wt%, about 5 to about 8 wt%, 7 to about 20 wt%, about 7 to about 18 wt%, about 7 to about 16 wt%, about 7 to about 14 wt%, about 7 to about 12 wt%, about 7 to about 10 wt%, or 10 to about 20 wt% , about 10 to about 18 wt%, about 10 to about 16 wt%, about 10 to about 14 wt%, about 10 to about 12 wt%, 12 to about 20 wt%, about 12 to about 18 wt%, about 12 to about 16 wt%, about 12 to about 14 wt%, 14 to about 20 wt%, about 14 to about 18 wt%, about 14 to about 16 wt%, about 16 to about 20 wt%, about 16 to about 18 wt%, or about 18 to about 20 wt% LiO. In some embodiments, the glass or glass-ceramic composition can comprise about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt% LiO.

[0053] As noted above, LiO is generally useful for forming glass-ceramics of embodiments, but other alkali oxides tend to degrade glass-ceramic formation and form aluminosilicate residual glass in the glass-ceramic. It has been found that greater than about 5 wt. % NaO or KO, or a combination thereof, results in an undesirable amount of residual glass, which can lead to deformation during crystallization and undesirable microstructures with respect to mechanical properties. Tailoring the composition of the residual glass can control viscosity during crystallization, minimize deformation or undesirable thermal expansion, or control microstructural characteristics. Therefore, the compositions described herein generally have small amounts of non-lithium alkali oxides. In some embodiments, the glass or glass-ceramic compositions can include about 0 to about 5 wt. % R2O, where R is one or more of the alkali cations Na and K. In some embodiments, the glass or glass-ceramic compositions can include about 1 to about 3 wt. % R2O, where R is one or more of the alkali cations Na and K. In some embodiments, the glass or glass ceramic composition can comprise 0 to about 5 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, >0 to about 5 wt%, >0 to about 4 wt%, >0 to about 3 wt%, >0 to about 2 wt%, >0 to about 1 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, about 3 to about 5 wt%, about 3 to about 4 wt%, or about 4 to about 5 wt% NaO or KO, or a combination thereof. In some embodiments, the glass or glass ceramic composition can comprise about 0, >0, 1, 2, 3, 4, or 5 wt% RO.

[0054] The glass and glass-ceramic compositions can include P2O5. P2O5 can function as a nucleating agent to generate bulk nucleation. If the P2O5 concentration is too low, the precursor glass will crystallize, but only from the surface inward at high temperatures (due to low viscosity), resulting in a brittle and potentially deformed object. However, if the P2O5 concentration is too high, devitrification after cooling during precursor glass formation can be difficult to control. Embodiments can include >0 to about 6 wt.% P2O5. Other embodiments can include about 2 to about 4 wt.% P2O5. Still other embodiments can include about 1.5 to about 2.5 wt.% P2O5.Compositions of embodiments may include 0 to about 6 wt%, 0 to about 5.5 wt%, 0 to about 5 wt%, 0 to about 4.5 wt%, 0 to about 4 wt%, 0 to about 3.5 wt%, 0 to about 3 wt%, 0 to about 2.5 wt%, 0 to about 2 wt%, 0 to about 1.5 wt%, 0 to about 1 wt%, >0 to about 6 wt%, >0 to about 5.5 wt%, >0 to about 5 wt%, >0 to about 4.5 wt%, >0 to about 4 wt%, >0 to about 3.5 wt%, >0 to about 3 wt%, >0 to about 2.5 wt%, >0 to about 2 wt%, >0 to about 1.5 wt%, >0 to about 1 wt%, about 0.5 to about 6 wt%, about 0.5 to about 5.5 wt%. %, about 0.5 to about 5% by weight, about 0.5 to about 4.5% by weight, about 0.5 to about 4% by weight, about 0.5 to about 3.5% by weight, about 0.5 to about 3% by weight, about 0.5 to about 2.5% by weight, about 0.5 to about 2% by weight, about 0.5 to about 1.5% by weight, about 0.5 to about 1% by weight, about 1 to about 6% by weight, about 1 ~about 5.5% by weight, about 1 to about 5% by weight, about 1 to about 4.5% by weight, about 1 to about 4% by weight, about 1 to about 3.5% by weight, about 1 to about 3% by weight, about 1 to about 2.5% by weight, about 1 to about 2% by weight, about 1 to about 1.5% by weight, about 1.5 to about 6% by weight, about 1.5 to about 5.5% by weight, about 1.5 to about 5 Weight%, about 1.5 to about 4.5 weight%, about 1.5 to about 4 weight%, about 1.5 to about 3.5 weight%, about 1.5 to about 3 weight%, about 1.5 to about 2.5 weight%, about 1.5 to about 2 weight%, about 2 to about 6 weight%, about 2 to about 5.5 weight%, about 2 to about 5 weight%, about 2 to about 4.5 weight%, about 2 to about 4% by weight, about 2 to about 3.5% by weight, about 2 to about 3% by weight, about 2 to about 2.5% by weight, about 2.5 to about 6% by weight, about 2.5 to about 5.5% by weight, about 2.5 to about 5% by weight, about 2.5 to about 4.5% by weight, about 2.5 to about 4% by weight, about 2.5 to about 3.5% by weight, about 2.5 to about 3% by weight, about The composition may contain 3 to about 6 wt%, about 3 to about 5.5 wt%, about 3 to about 5 wt%, about 3 to about 4.5 wt%, about 3 to about 4 wt%, about 3 to about 3.5 wt%, about 3.5 to about 6 wt%, about 3.5 to about 5.5 wt%, about 3.5 to about 5 wt%, about 3.5 to about 4.5 wt%, about 3.5 to about 4 wt%, about 4 to about 6 wt%, about 4 to about 5.5 wt%, about 4 to about 5 wt%, about 4 to about 4.5 wt%, about 4.5 to about 6 wt%, about 4.5 to about 5.5 wt%, about 4.5 to about 5 wt%, about 5 to about 6 wt%, about 5 to about 5.5 wt%, or about 5.5 to about 6 wt% P2O5.In some embodiments, the glass or glass-ceramic composition can include about 0, >0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 wt. % P2O5.

[0055] In the glasses and glass-ceramics described herein, it has generally been found that ZrO can improve the stability of LiO-AlO-SiO-P O glasses by significantly reducing devitrification and lowering the liquidus temperature of the glass during formation. At concentrations greater than 8 wt. %, ZrSiO can form a primary liquid phase at high temperatures, which significantly reduces the liquidus viscosity. When glasses contain greater than 2 wt. % ZrO, transparent glasses can be formed. The addition of ZrO can also help reduce the petalite grain size, which aids in the formation of transparent glass-ceramics. In some embodiments, the glass or glass-ceramic composition can include about 0.2 to about 15 wt. % ZrO. In some embodiments, the glass or glass-ceramic composition can include about 2 to about 4 wt. % ZrO. In some embodiments, the glass or glass ceramic composition comprises from about 0.2 to about 15 wt%, about 0.2 to about 12 wt%, about 0.2 to about 10 wt%, about 0.2 to about 8 wt%, about 0.2 to 6 wt%, about 0.2 to about 4 wt%, 0.5 to about 15 wt%, about 0.5 to about 12 wt%, about 0.5 to about 10 wt%, about 0.5 to about 8 wt%, about 0.5 to 6 wt%, about 0.5 to about 4 wt%, 1 to about 15 wt%, about 1 to about 12 wt%, about 1 to about 10 wt%, about 1 to about 8 wt%, about 1 to 6 wt%, about 1 to about 4 wt%, 2 to about 15 wt%, %, about 2 to about 12 weight%, about 2 to about 10 weight%, about 2 to about 8 weight%, about 2 to 6 weight%, about 2 to about 4 weight%, about 3 to about 15 weight%, about 3 to about 12 weight%, about 3 to about 10 weight%, about 3 to about 8 weight%, about 3 to 6 weight%, about 3 to about 4 weight%, about 4 to about 15 weight%, about 4 to about 12 weight%, about 4 to about 10 weight%, about 4 to about 8 weight%, about 4 to 6 weight%, about 8 to about 15 weight%, about 8 to about 12 weight%, about 8 to about 10 weight%, about 10 to about 15 weight%, about 10 to about 12 weight%, or about 12 to about 15 weight% ZrO2. In some embodiments, the glass or glass-ceramic composition can include about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt. % ZrO2.

[0056] B2O3 contributes to providing a low melting point for the precursor glass. Furthermore, the addition of B2O3 to the precursor glass, and thus the glass-ceramic, can help achieve an interconnected crystalline microstructure and improve the damage resistance of the glass-ceramic. When the boron in the residual glass is not in charge balance with alkali oxides or divalent cation oxides, the boron is trigonally coordinated (i.e., tricoordinated boron), which opens up the glass structure. The network around these tricoordinated boron atoms is less rigid than tetracoordinated (i.e., tetracoordinated) boron. Without being bound by theory, it is believed that precursor glasses and glass-ceramics containing tricoordinated boron can withstand a certain degree of deformation before cracks form. Withstanding a certain degree of deformation increases the Vickers indentation crack initiation value. The fracture toughness of precursor glasses and glass-ceramics containing tricoordinated boron may also increase. Without being bound by theory, it is believed that the presence of boron in the residual glass (and precursor glass) of the glass-ceramic reduces the viscosity of the residual glass (or precursor glass), thereby promoting the growth of lithium silicate crystals, particularly large crystals with high aspect ratios. Higher amounts of tricoordinated boron (relative to tetracoordinated boron) are believed to result in glass-ceramics that exhibit higher Vickers indentation crack initiation loads. In some embodiments, the amount of tricoordinated boron (as a percentage of total B2O3) can be about 40% or more, 50% or more, 75% or more, about 85% or more, or even 95% or more. In general, the amount of boron must be controlled to maintain the chemical resistance and mechanical strength of the cerammed bulk glass-ceramic.

[0057] In one or more embodiments, the glasses and glass ceramics described herein can comprise 0 to about 10 wt. % or 0 to about 2 wt. % B2O3. In some embodiments, the glass or glass ceramic composition can comprise 0 to about 10 wt. %, 0 to about 9 wt. %, 0 to about 8 wt. %, 0 to about 7 wt. %, 0 to about 6 wt. %, 0 to about 5 wt. %, 0 to about 4 wt. %, 0 to about 3 wt. %, 0 to about 2 wt. %, 0 to about 1 wt. %, >0 to about 10 wt. %, >0 to about 9 wt. %, >0 to about 8 wt. %, >0 to about 7 wt. %, >0 to about 6 wt. %, >0 to about 5 wt. %, >0 to about 4 wt. %, >0 to about 3 wt. %, >0 to about 2 wt. %, > ... or about % to about 10 wt%, about 1 to about 8 wt%, about 1 to about 6 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 2 wt%, about 2 to about 10 wt%, about 2 to about 8 wt%, about 2 to about 6 wt%, about 2 to about 4 wt%, about 3 to about 10 wt%, about 3 to about 8 wt%, about 3 to about 6 wt%, about 3 to about 4 wt%, about 4 to about 5 wt%, about 5 wt% to about 8 wt%, about 5 wt% to about 7.5 wt%, about 5 wt% to about 6 wt%, or about 5 wt% to about 5.5 wt% B2O3. In some embodiments, the glass or glass-ceramic composition can comprise about 0, >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% B2O3.

[0058] MgO can enter petalite crystals in partial solid solution. In one or more embodiments, the glasses and glass-ceramics described herein can include 0 to about 8 wt. % MgO. In some embodiments, the glass or glass-ceramic composition can include 0 to about 8 wt. %, 0 to about 7 wt. %, 0 to about 6 wt. %, 0 to about 5 wt. %, 0 to about 4 wt. %, 0 to about 3 wt. %, 0 to about 2 wt. %, 0 to about 1 wt. %, about 1 to about 8 wt. %, about 1 to about 7 wt. %, about 1 to about 6 wt. %, about 1 to about 5 wt. %, about 1 to about 4 wt. %, about 1 to about 3 wt. %, about 1 to about 2 wt. %, about 2 to about 8 wt. %, about 2 to about 7 wt. %, about 2 to about 6 wt. % MgO. %, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, about 3 to about 8 wt%, about 3 to about 7 wt%, about 3 to about 6 wt%, about 3 to about 5 wt%, about 3 to about 4 wt%, about 4 to about 8 wt%, about 4 to about 7 wt%, about 4 to about 6 wt%, about 4 to about 5 wt%, about 5 to about 8 wt%, about 5 to about 7 wt%, about 5 to about 6 wt%, about 6 to about 8 wt%, about 6 to about 7 wt%, or about 7 wt% to about 8 wt% MgO. In some embodiments, the glass or glass-ceramic composition can comprise about 0, >0, 1, 2, 3, 4, 5, 6, 7, or 8 wt% MgO.

[0059] ZnO can enter the petalite crystallites in partial solid solution. In one or more embodiments, the glasses and glass-ceramics described herein can include 0 to about 10 wt. % ZnO. In some embodiments, the glass or glass ceramic composition comprises 0 to about 10 wt%, 0 to about 9 wt%, 0 to about 8 wt%, 0 to about 7 wt%, 0 to about 6 wt%, 0 to about 5 wt%, 0 to about 4 wt%, 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, about 1 to about 10 wt%, about 1 to about 9 wt%, about 1 to about 8 wt%, about 1 to about 7 wt%, about 1 to about 6 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, about 2 to about 10 wt%, about 2 to about 9 wt%, about 2 to about 8 wt%, about 2 to about 7 wt%, about 2 to about 6 wt%, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, or about 3 to about 10% by weight, about 3 to about 9% by weight, about 3 to about 8% by weight, about 3 to about 7% by weight, about 3 to about 6% by weight, about 3 to about 5% by weight, about 3 to about 4% by weight, about 4 to about 10% by weight, about 4 to about 9% by weight, about 4 to about 8% by weight, about 4 to about 7% by weight, about 4 to about 6% by weight, about 4 to about 5% by weight, about 5 to about 10% by weight, about 5 to about 9% by weight, about 5 to about 8% by weight, about 5 to about 7% by weight, about 5 to about 6% by weight, about 6 to about 10% by weight, about 6 to about 9% by weight, about 6 to about 8% by weight, about 6 to about 7% by weight, about 7 to about 10% by weight, about 7 to about 9% by weight, about 7% to about 8% by weight, about 8 to about 10% by weight, about 8 to about 9% by weight, or about 9 to about 10% by weight of ZnO. In some embodiments, the glass or glass-ceramic composition can include about 0, >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt. % ZnO.

[0060] In one or more embodiments, the glasses and glass ceramics described herein can comprise 0 to about 5 wt. % TiO. In some embodiments, the glass or glass ceramic composition can comprise 0 to about 5 wt. %, 0 to about 4 wt. %, 0 to about 3 wt. %, 0 to about 2 wt. %, 0 to about 1 wt. %, about 1 to about 5 wt. %, about 1 to about 4 wt. %, about 1 to about 3 wt. %, about 1 to about 2 wt. %, about 2 to about 5 wt. %, about 2 to about 4 wt. %, about 2 to about 3 wt. %, about 3 to about 5 wt. %, about 3 to about 4 wt. %, or about 4 to about 5 wt. % TiO. In some embodiments, the glass or glass ceramic composition can comprise about 0, >0, 1, 2, 3, 4, or 5 wt. % TiO.

[0061] In one or more embodiments, the glasses and glass ceramics described herein can comprise 0 to about 0.4 wt. % CeO. In some embodiments, the glass or glass ceramic compositions can comprise 0 to about 0.4 wt. %, 0 to about 0.3 wt. %, 0 to about 0.2 wt. %, 0 to about 0.1 wt. %, about 0.1 to about 0.4 wt. %, about 1 to about 0.3 wt. %, about 1 to about 0.2 wt. %, about 0.2 to about 0.4 wt. %, about 0.2 to about 0.3 wt. %, or about 0.3 to about 0.4 wt. % CeO. In some embodiments, the glass or glass ceramic compositions can comprise about 0, >0, 0.1, 0.2, 0.3, or 0.4 wt. % CeO.

[0062] In one or more embodiments, the glasses and glass-ceramics described herein can include 0 to about 0.5 wt. % SnO2. In some embodiments, the glass or glass-ceramic composition can comprise from 0 to about 0.5 wt %, from 0 to about 0.4 wt %, from 0 to about 0.3 wt %, from 0 to about 0.2 wt %, from 0 to about 0.1 wt %, from about 0.05 to about 0.5 wt %, from 0.05 to about 0.4 wt %, from 0.05 to about 0.3 wt %, from 0.05 to about 0.2 wt %, from 0.05 to about 0.1 wt %, from about 0.1 to about 0.5 wt %, from about 0.1 to about 0.4 wt %, from about 0.1 to about 0.3 wt %, from about 0.1 to about 0.2 wt %, from about 0.2 to about 0.5 wt %, from about 0.2 to about 0.4 wt %, from about 0.2 to about 0.3 wt %, from about 0.3 to about 0.5 wt %, from about 0.3 to about 0.4 wt %, or from about 0.4 to about 0.5 wt % SnO. In some embodiments, the glass or glass-ceramic composition can include about 0, >0, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5 wt. % SnO2.

[0063] In some embodiments, the combined weight percentage of P2O5 and ZrO2 in the glasses and glass-ceramics disclosed herein can be about 3 wt%, 4 wt%, or 5 wt% or greater, which increases nucleation, which can result in the production of smaller particles.

[0064] In some embodiments, the glass-ceramic exhibits transparency across the visible light range (i.e., the glass-ceramic is transparent). In some embodiments, the transparency of the glass-ceramic can be achieved by creating crystals smaller than the interrogating wavelength of light and by matching the refractive index of the residual glass to the refractive index of petalite (1.51) and lithium disilicate (1.55). In some embodiments, the transparent glass-ceramic having a thickness of 1 mm can have a transmittance of ≥ 90% (including surface reflection losses) of light over a wavelength range of about 400 nm to about 1000 nm. In one or more embodiments, the average transmittance for a transparent glass-ceramic article is about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, about 92% or greater, or about 93% or greater (including surface reflection losses) of light over a wavelength range of about 400 nm to about 1000 nm for a 1 mm thick glass-ceramic article. In other embodiments, the glass-ceramic may be translucent across the visible light range. In some embodiments, the translucent glass-ceramic may have an average transmittance of about 20% to less than about 85% for light over a wavelength range of about 400 nm to about 1000 nm for a 1 mm thick glass-ceramic article. In embodiments where the glass-ceramic is translucent, the glass-ceramic may have a white color.

[0065] In some embodiments, the size of particles in the glass ceramic can affect transparency or translucency. In some embodiments, the particles of the transparent glass ceramic can have a longest dimension less than about 100 nm. In some embodiments, the particles of the translucent glass ceramic can have a longest dimension in the range of about 100 nm to about 500 nm. In some embodiments, the particles of the transparent glass ceramic can have an aspect ratio of about 2 or greater. In some embodiments, the particles of the translucent glass ceramic can have an aspect ratio of about 2 or less.

[0066] Due to the raw materials and / or equipment used to produce the glass or glass-ceramic compositions of the present disclosure, certain impurities or components not intentionally added may be present in the final glass or glass-ceramic composition. Such materials may be present in trace amounts in the glass or glass-ceramic composition and are referred to herein as "contaminants."

[0067] As used herein, a glass or glass-ceramic composition having 0 wt. % of a compound is defined to mean that the compound, molecule, or element was not intentionally added to the composition, but that the composition may still contain the compound, typically in trace or insignificant amounts. Similarly, "iron-free," "sodium-free," "lithium-free," "zirconium-free," "alkaline earth metal-free," or "heavy metal-free," etc., are defined to mean that the compound, molecule, or element was not intentionally added to the composition, but that the composition may still contain iron, sodium, lithium, zirconium, alkaline earth metals, heavy metals, etc., but in approximately trace or insignificant amounts. Trace compounds that may be found in the glasses or glass-ceramics of embodiments herein include, but are not limited to, Na2O, TiO2, MnO, ZnO, Nb2O5, MoO3, Ta2O5, WO3, ZrO2, YO3, La2O3, HfO2, CdO, SnO2, Fe2O3, CeO2, As2O3, Sb2O3, sulfur-based compounds such as sulfuric acid, halogens, or combinations thereof.

[0068] In some embodiments, an antimicrobial component may be added to the glass or glass-ceramic composition. This is particularly advantageous because the glass-ceramics of embodiments herein can be used in applications where exposure to harmful bacteria may occur, such as kitchen or dining countertops. Antimicrobial components that can be added to the glass or glass-ceramic include, but are not limited to, Ag, AgO, Cu, CuO, CuO, and the like. In some embodiments, the concentration of the antimicrobial component is maintained at a level of about 3, 2, 1, or 0.5, or >0 wt. %. In some embodiments, the antimicrobial component is >0 to about 3 wt. %. In some embodiments, the antimicrobial component is >0 to about 1 wt. %.

[0069] In some embodiments, the glass or glass-ceramic may further comprise a chemical fining agent. Such fining agents include, but are not limited to, SnO2, As2O3, Sb2O3, F, Cl, and Br. In some embodiments, the concentration of the chemical fining agent is maintained at a level of 3, 2, 1, or 0.5, or >0 wt%. In some embodiments, the amount of the fining agent is >0 to about 3 wt%. Chemical fining agents also include oxides of other transition metals, such as CeO2, Fe2O3, and MnO2. Because these oxides may introduce undesirable color into the glass or glass-ceramic due to visible light absorption in one or more of their final valence states in the glass, the concentration of these oxides, when present, is typically maintained at a level of 0.5, 0.4, 0.3, 0.2, 0.1, or >0 wt%.

[0070] The glass or glass-ceramic may also contain SnO2, for example, by batching tin-containing materials such as SnO2, SnO, SnCO3, SnCO2, etc., as a result of Joule-heated melting using tin oxide electrodes, or by adding SnO2 as an agent to adjust various physical, melting, coloring, or forming attributes. The glass or glass-ceramic may contain 0 to about 3 wt.%, 0 to about 2 wt.%, 0 to about 1 wt.%, 0 to 0.5 wt.%, or 0 to 0.1 wt.% SnO2.

[0071] In some embodiments, the glass or glass-ceramic can be substantially free of SbO, AsO, or a combination thereof. For example, the glass or glass-ceramic can include 0.05 weight percent or less of SbO or AsO, or a combination thereof, the glass or glass-ceramic can include 0 weight percent of SbO or AsO, or a combination thereof, or the glass or glass-ceramic can be free of any intentionally added SbO or AsO, or a combination thereof, for example.

[0072] Additional components can be introduced into the glass composition to provide additional benefits, or the additional components may further include contaminants typically found in commercially prepared glasses. For example, various physical, melting, and forming properties can be adjusted by adding additional components. According to some embodiments, the glass may also include contaminants (e.g., ZrO) associated with batch materials and / or introduced into the glass by the melting, fining, and / or forming equipment used to produce the glass. In some embodiments, the glass may include one or more compounds useful as ultraviolet radiation transorber. In some embodiments, the glass may include up to 3 wt. % of TiO, MnO, ZnO, NbO, MoO, TaO, WO, ZrO, YO, LaO, HfO, CdO, FeO, CeO, or combinations thereof. In some embodiments, the glass can include 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, 0 to 0.5 wt%, 0 to 0.1 wt%, 0 to 0.05 wt%, or 0 to 0.01 wt% of TiO2, MnO, ZnO, Nb2O5, MoO3, Ta2O5, WO3, ZrO2, YO3, La2O3, HfO2, CdO, SnO2, Fe2O3, CeO2, As2O3, Sb2O3, or combinations thereof.

[0073] In some embodiments, the glasses described herein can be fabricated into sheets by processes including, but not limited to, slot draw, float, rolling, and other sheet forming processes known to those skilled in the art. Alternatively, the glass compositions may be formed by float or rolling processes known in the art.

[0074] In some embodiments, the glass compositions described herein may be adapted for float-type forming processes by adjusting their liquidus viscosity. In some embodiments, the glass compositions can have a liquidus viscosity of about 1500 P (150 Pa·s) to about 3000 P (300 Pa·s). In some embodiments, the glass compositions can have a liquidus viscosity of about 1000, 1200, 1500, 2000, 2500, or 3000 P (about 100, 120, 150, 200, 250, or 300 Pa·s). In some embodiments, the glass is about 50×10 ‐7 / K or more, approximately 50×10 ‐7 / K or more, approximately 60×10 ‐7 / K or more, approximately 61×10 ‐7 / K or more, approximately 62×10 ‐7 / K or more, approximately 63×10 ‐7 / K or more, approximately 64×10 ‐7 / K or more, approximately 65×10 ‐7 / K or more, approximately 66×10 ‐7 / K or more, approximately 67×10 ‐7 / K or more, approximately 68×10 ‐7 / K or more, approximately 69×10 ‐7 / K or more, approximately 70×10 ‐7 / K or more, approximately 71×10 ‐7 / K or more, approximately 72×10 ‐7 / K or more, approximately 73×10 ‐7 / K or more, approximately 74×10 ‐7 / K or more, approximately 75×10 ‐7 / K or more, approximately 76×10 ‐7 / K or more, approximately 77×10 ‐7 / K or more, approximately 78×10 ‐7 / K or more, approximately 79×10 ‐7 / K or more, or approximately 80 x 10 ‐7The thermal expansion coefficient may be 1 / K or more.

[0075] Articles formed from the glasses and glass ceramics described herein can be of any reasonably usable thickness. Glass sheet and / or glass ceramic embodiments may have a thickness of anywhere from about 0.8 mm to about 10 mm. Some embodiments have a thickness of about 6 mm or less, about 5 mm or less, about 3 mm or less, about 1.0 mm or less, about 750 μm or less, about 500 μm or less, or about 250 μm or less. Some glass or glass ceramic sheet embodiments may have a thickness of about 200 μm to about 5 mm, about 500 μm to about 5 mm, about 200 μm to about 4 mm, about 200 μm to about 2 mm, about 400 μm to about 5 mm, or about 400 μm to about 2 mm. In some embodiments, the thickness may be about 3 mm to about 6 mm or about 0.8 mm to about 3 mm.

[0076] In some embodiments, the glass-ceramic has an equibiaxial flexural strength of about 300 MPa or more, about 325 MPa or more, about 350 MPa or more, about 375 MPa or more, about 400 MPa or more, about 425 MPa or more, or about 450 MPa or more at a thickness of 1 mm. Equibiaxial flexural strength can also be referred to as ring-on-ring (RoR) strength, which is measured according to the procedure set forth in ASTM C1499-05, with minor modifications to the test apparatus and test conditions, as outlined in paragraph

[0027] of U.S. Patent Publication No. 2013 / 0045375 (incorporated herein by reference). Abraded ring-on-ring (aRoR) strength can also be measured using the above procedure if the glass-ceramic is first subjected to friction, typically with silicon carbide particles. Some embodiments also include chemically strengthenable glass-ceramics with a petalite phase, which provides increased flexural strength. In such embodiments, the RoR strength can be about 500 MPa or greater, about 550 MPa or greater, about 600 MPa or greater, about 650 MPa or greater, about 700 MPa or greater, about 750 MPa or greater, or about 800 MPa or greater.

[0077] Some embodiments of the glass-ceramic exhibit high fracture toughness and inherent damage tolerance. As described above, some embodiments of the glass-ceramic comprise interconnected lithium silicate crystals, which provide high fracture toughness. One or more embodiments of the glass-ceramic may comprise boron, which may be present as tricoordinated boron in the residual glass phase of the glass-ceramic. In such embodiments, the tricoordinated boron is provided by including B2O3 in a precursor glass. The tricoordinated boron provides a densification mechanism when the glass or glass-ceramic is subjected to an indenter load.

[0078] In one or more embodiments, the glass-ceramic has a viscosity of about 1.0 MPa m 1 / 2 Approximately 1.1MPa m 1 / 2 More than 1.2MPa m 1 / 2 More than 1.3MPa m 1 / 2 More than 1.4MPa m 1 / 2 More than 1.5MPa m 1 / 2 More than 1.6MPa m 1 / 2 More than 1.7MPa m 1 / 2 More than 1.8MPa m 1 / 2 Over 1.9 MPa m 1 / 2 or more, or 2.0 MPa m 1 / 2 In some embodiments, the fracture toughness is about 1 to about 2 MPa m 1 / 2 The fracture toughness may be measured using methods known in the art, for example, using chevron-notched specimens according to ASTM C1421-10 "Standard Test Method for Determination of Fracture Toughness of Fine Ceramics at Ambient Temperature."

[0079] In one or more embodiments, the glass-ceramics exhibit a Vickers hardness of about 600 to about 900 kgf / mm, thereby providing high crack and scratch resistance. In some embodiments, the non-ion-exchanged glass-ceramics exhibit a Vickers hardness of about 600 to about 900 kgf / mm 2 (Approx. 5884~8826N / mm 2 ), approx. 600 to approx. 875 kgf / mm 2 (Approx. 5884~8581N / mm 2), approx. 600 to approx. 850 kgf / mm 2 (approx. 5884~approx. 8335N / mm 2 ), approx. 600 to approx. 825 kgf / mm 2 (Approx. 5884~8090N / mm 2 ), approximately 600 to 800 kgf / mm 2 (Approx. 5884~7845N / mm 2 ), approx. 600~775kgf / mm 2 (Approx. 5884~7600N / mm 2 ), approx. 600~750kgf / mm 2 (Approx. 5884~7355N / mm 2 ), approx. 600~725kgf / mm 2 (Approx. 5884~7110N / mm 2 ), approx. 600~700kgf / mm 2 (Approx. 5884~6865N / mm 2 ), approximately 700 to 900 kgf / mm 2 (Approx. 6865~8826N / mm 2 ), approx. 700 to approx. 875 kgf / mm 2 (Approx. 6865~8581N / mm 2 ), approx. 700~850kgf / mm 2 (Approx. 6865~8335N / mm 2 ), approx. 700 to approx. 825 kgf / mm 2 (approx. 6865~8090N / mm 2 ), or about 700 to about 800 kgf / mm 2 (Approx. 6865~7845N / mm 2 In some embodiments, the Vickers hardness is 600 kgf / mm 2 (approx. 5884N / mm 2 ) or more, 625kgf / mm 2 (Approx. 6129N / mm 2 ) or more, 650kgf / mm 2 (Approx. 6374N / mm 2 ) or more, 675kgf / mm 2 (approx. 6619N / mm 2 ) or more, 700kgf / mm 2 (Approx. 6865N / mm 2 ) or more, 725kgf / mm2 (approx. 7110N / mm 2 ) or more, 750kgf / mm 2 (approx. 7355N / mm 2 ) or more, 775kgf / mm 2 (approx. 7600N / mm 2 ) or more, 800kgf / mm 2 (approx. 7845N / mm 2 ) or more, 825kgf / mm 2 (approx. 8090N / mm 2 ) or more, 850kgf / mm 2 (approx. 8335N / mm 2 ) or more, 875kgf / mm 2 (approx. 8581N / mm 2 ) or more, or 900kgf / mm 2 (approx. 8826N / mm 2 ) or greater. Vickers hardness may be measured using ASTM C1326 and C1327 (and its subparagraphs, all of which are incorporated herein by reference) "Standard Test Methods for Vickers Indentation Hardness of Fine Ceramics" (ASTM International, Conshohocken, PA, USA). In some embodiments, the glass-ceramics exhibit such Vickers crack initiation load values ​​after chemical strengthening by ion exchange.

[0080] In some embodiments, the glass-ceramics disclosed herein are not brittle after ion-exchange. As used herein, the terms "frangible" and "frangibilty" refer to energetic fracture of a glass-ceramic plate or sheet when subjected to a point impact by an object or dropped onto a hard surface with sufficient force to break the glass-ceramic plate into multiple pieces, which can include: multiple crack branches in the glass (i.e., 5 or more crack branches from an initial crack); a piece protruding at least 2 inches (about 5 cm) from its original position; or about 5 or more fragments / cm of the plate. 2or any combination of these three conditions. Conversely, a glass-ceramic plate is considered not brittle if, when subjected to a point impact by an object or dropped onto a solid surface with sufficient force to break the plate into multiple pieces, it either does not fracture or fractures with fewer than five crack branches from the initial crack and the pieces protruding less than 2 inches (about 5 cm) from their original position.

[0081] The brittle and non-brittle behavior observed for 5 cm x 5 cm glass-ceramic plates, each 0.5 mm thick, is shown in Figure 10. Glass-ceramic plate a exhibits brittle behavior, evidenced by multiple small pieces protruding more than 2 inches (approximately 5 cm) and a high degree of crack branching from the initial crack that produced the small pieces. In contrast to glass-ceramic plate a, glass-ceramic plates b, c, and d do not exhibit brittle behavior. In these examples, the glass-ceramic plate fractures into a few large pieces that do not sharply protrude 2 inches (approximately 5 cm) from the original position ("X" is the approximate center of the glass plate before fracture). Glass-ceramic plate b fractures into two large pieces without any crack branching; glass-ceramic plate c fractures into four pieces with two crack branches from the initial crack; and glass-ceramic plate d fractures into four pieces with two crack branches from the initial crack.

[0082] Additionally, all compositions and glass and / or glass-ceramic compositions are ion-exchangeable by methods well known in the art. In a typical ion-exchange process, relatively small metal ions in a glass are replaced or "exchanged" with relatively larger metal ions of the same valence in a layer near the outer surface of the glass and / or glass-ceramic. The replacement of relatively small metal ions with relatively larger metal ions creates compressive stresses within the layer of the glass and / or glass-ceramic. In one embodiment, these metal ions are monovalent alkali metal ions (e.g., Na). + , K. + , Rb + , Cs +etc.), and ion exchange is accomplished by immersing the glass and / or glass-ceramic in a bath containing a molten salt of at least one of the larger metal ions that will replace the smaller metal ions in the glass. Alternatively, monovalent ions can be substituted with Ag + , Tl + , Cu + The glass and / or glass ceramic may be ion-exchanged with other monovalent ions, such as NaO. The one or more ion-exchange processes used to strengthen the glass and / or glass ceramic may include, but are not limited to, immersion in a single bath or multiple baths of similar or different compositions, with washing and / or annealing steps between immersions. In one or more embodiments, the glass and / or glass ceramic may be ion-exchanged by exposure to molten NaNO at about 430°C. In such embodiments, Na ions replace a portion of the Li ions in the glass ceramic, developing a surface compressive layer that exhibits high crack resistance. The resulting compressive stress layer may have a depth (also referred to as "depth of layer") of at least 100 μm on the surface of the glass in about 2 hours. In such embodiments, the depth of layer can be determined from the NaO concentration profile. In another example, an embodiment may be ion-exchanged by exposure to molten KNO at 410°C for 2 hours, which produces a compressive stress layer having a depth of layer of at least about 100 μm. In some embodiments, the glass ceramic may be ion-exchanged to achieve a depth of layer of about 30 μm or more, about 40 μm or more, about 50 μm or more, about 60 μm or more, about 70 μm or more, about 80 μm or more, about 90 μm or more, or about 100 μm or more. In other embodiments, a central tension of at least 10 MPa is achieved by ion-exchanging the glass. The development of this surface compressive layer is beneficial for achieving better crack resistance and higher flexural strength compared to non-ion-exchanged materials. The surface compressive layer has a higher concentration of ions exchanged into the glass-ceramic article compared to the concentration of ions exchanged into the glass-ceramic article for the bulk of the glass-ceramic article (i.e., regions not including the surface compressive layer).

[0083] In some embodiments, the glass ceramic has a viscosity of about 100 MPa to about 500 MPa, about 100 MPa to about 450 MPa, about 100 MPa to about 400 MPa, about 100 MPa to about 350 MPa, about 100 MPa to about 300 MPa, about 100 MPa to about 250 MPa, about 100 MPa to about 200 MPa, about 100 MPa to about 150 MPa, 150 MPa to about 500 MPa, about 150 MPa to about 450 MPa, about 150 MPa to about 400 MPa, about 150 MPa to about 350 MPa, about 150 MPa to about 300 MPa, about 150 MPa to about 250 MPa, about 150 MPa to about 200 MPa, 200 MPa to about 500 MPa, about 200 MPa to about 450 MPa, or about 200 MPa to about 400 MPa. a, about 200 MPa to about 350 MPa, about 200 MPa to about 300 MPa, about 200 MPa to about 250 MPa, 250 MPa to about 500 MPa, about 250 MPa to about 450 MPa, about 250 MPa to about 400 MPa, about 250 MPa to about 350 MPa, about 250 MPa to about 300 MPa, 300 MPa to about 500 MPa, about 300 MPa to about 450 MPa, about 300 MPa to about 400 MPa, about 300 MPa to about 350 MPa, 350 MPa to about 500 MPa, about 350 MPa to about 450 MPa, about 350 MPa to about 400 MPa, 400 MPa to about 500 MPa, about 400 MPa to about 450 MPa, or about 450 MPa to about 500 MPa. In some embodiments, the glass-ceramic can have a surface compressive stress of about 100 MPa or more, about 150 MPa or more, about 200 MPa or more, about 250 MPa or more, about 300 MPa or more, about 350 MPa or more, about 400 MPa or more, about 450 MPa or more, or about 500 MPa or more. The compressive stress and depth of the compressive stress layer ("DOL") are measured using means known in the art.DOL is determined by a surface stress meter (FSM), such as a commercially available instrument, such as the FSM-6000 manufactured by Luceo Co., Ltd. (Tokyo, Japan). Methods for measuring CS and depth of layer are described in ASTM 1422C-99, "Standard Specification for Chemically Tempered Flat Glass," and ASTM 1279.19779, "Standard Test Method for Nondestructive Photoelastic Measurement of Edge and Surface Stresses of Annealed, Thermally Tempered, and Fully Tempered Flat Glass," the contents of which are incorporated herein by reference in their entireties. Surface stress measurement relies on accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is measured by methods known in the art, such as the fiber and four-point bending methods described in ASTM Standard C770-98 (2008), "Standard Test Method for Measurement of the Stress Optical Coefficient of Glass," and the bulk cylinder method, the contents of which are incorporated herein by reference in their entireties.

[0084] In one or more embodiments, the process for making the glass-ceramic includes heat-treating a precursor glass at one or more preselected temperatures for one or more preselected times to induce homogenization of the glass 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, etc.). In some embodiments, the heat treatment can include: (i) heating a precursor glass at a rate of 1-10°C / min to a glass pre-nucleation temperature; (ii) maintaining the crystallizable glass at the glass pre-nucleation temperature for a time period of about 1 / 4 hour to about 4 hours to produce a pre-nucleated crystallizable glass; (iii) heating the pre-nucleated crystallizable glass at a rate of 1-10°C / min to a nucleation temperature (Tn); (iv) maintaining the crystallizable glass at the nucleation temperature for a time period of about 1 / 4 hour to about 4 hours to produce a nucleated crystallizable glass; (v) heating the nucleated crystallizable glass at a rate of about 1°C / min to about 10°C / min to a crystallization temperature (Tc); (vi) maintaining the nucleated crystallizable glass at the crystallization temperature for a time period of about 1 / 4 hour to about 4 hours to produce a glass-ceramic described herein; and (vii) cooling the formed glass-ceramic to room temperature. As used herein, the term "crystallization temperature" may be used interchangeably with "ceramming temperature." Furthermore, in these embodiments, the term "ceramming" may be used to collectively refer to steps (v), (vi), and optionally (vii). In some embodiments, the glass pre-nucleation temperature may be 540°C, the nucleation temperature may be 600°C, and the crystallization temperature may be in the range of 630°C to 730°C. In other embodiments, the heat treatment does not include maintaining the crystallizable glass at a glass pre-nucleation temperature.Thus, the heat treatment may include: (i) heating the precursor glass to a nucleation temperature (Tn) at a rate of 1-10°C / min; (ii) maintaining the crystallizable glass at the nucleation temperature for a time period of about 1 / 4 hour to about 4 hours to produce a nucleated crystallizable glass; (iii) heating the nucleated crystallizable glass to a crystallization temperature (Tc) at a rate of about 1°C / min to about 10°C / min; (iv) maintaining the nucleated crystallizable glass at the crystallization temperature for a time period of about 1 / 4 hour to about 4 hours to produce a glass-ceramic described herein; and (v) cooling the formed glass-ceramic to room temperature. In these embodiments, the term "ceramming" may be used collectively to refer to steps (iii), (iv), and optionally (v). In some embodiments, the nucleation temperature may be about 700°C, and the crystallization temperature may be about 800°C. In some embodiments, higher crystallization temperatures produce more β-spodumene ss as a minor crystalline phase.

[0085] In addition to the precursor glass composition, the temperature-time profile of the heat treatment step of heating to and maintaining the temperature at the crystallization temperature can be carefully formulated to produce one or more of the following desired attributes: one or more crystalline phases of the glass-ceramic; the proportion of one or more major crystalline phases and / or one or more minor crystalline phases and residual glass; the composition of one or more predominant crystalline phases and / or one or more minor crystalline phases and residual glass crystalline phases; and the grain size or grain size distribution of one or more major crystalline phases and / or one or more minor crystalline phases, which can affect the ultimate integrity, quality, color, and / or opacity of the resulting glass-ceramic.

[0086] The resulting glass-ceramic can be provided as a sheet, which can subsequently be reshaped into a curved or bent piece of uniform thickness by pressing, blowing, bending, sagging, vacuum forming, or other means. The reshaping can occur before heat treating, or the forming step can also serve as a heat treating step, with forming and heat treating occurring substantially simultaneously.

[0087] In yet other embodiments, the precursor glass composition used to form the glass ceramic can be formulated, for example, to enable chemical strengthening of the glass ceramic using one or more ion exchange techniques. In these embodiments, ion exchange can be performed by subjecting one or more surfaces of the glass ceramic to one or more ion exchange baths having specific compositions and temperatures for specified periods of time, thereby imparting one or more compressive stress layers to the one or more surfaces. The compressive stress layers can include one or more average surface compressive stresses (CS) and / or one or more depths of layer. [Example]

[0088] Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be expected. Unless otherwise indicated, temperatures are in °C or are at ambient temperature, and pressures are at or near atmospheric. The compositions themselves are given in weight percent on an oxide basis and are normalized to 100%. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions, which can be used to optimize the purity and yield of products obtained from the processes described herein. Optimization of such process conditions requires no more than reasonable and routine experimentation.

[0089] Example 1 Exemplary glass and glass-ceramic compositions (by weight) and properties for obtaining transparent glass-ceramics are listed in Table 1 and were determined according to conventional techniques in the glass art. Precursor glasses having compositions 1-16 listed in Table 1 were formed. These precursor glasses were then subjected to a ceramming cycle, which included a 4-hour hold at 540°C for glass homogenization, a 4-hour hold at 600°C for nucleation, and a 4-hour hold in the temperature range of 630-730°C for crystallization. Table 1 uses the following terminology to describe the ceramming cycle: glass homogenization temperature-hold time / nucleation temperature-hold time / crystallization temperature-hold time.

[0090] The liquidus temperature is the temperature at which the first crystals are observed in the standard gradient boat liquidus measurement (ASTM C829-81 and its subparagraphs). This involves placing crushed glass particles in a platinum boat, placing the boat in a furnace with a gradient temperature range, heating the boat over the appropriate temperature range for 24 or 72 hours, and determining by microscopic examination the maximum temperature at which crystals appear within the glass. More specifically, a piece of glass sample is removed from the Pt boat and examined using a polarized light microscope to identify the location and nature of the crystals formed relative to the Pt / air interface and within the sample. Because the furnace gradient is well known, the temperature versus location can be well estimated to within 5-10°C. The temperature at which crystals are observed within the sample is taken to represent the liquidus of the glass (with respect to the corresponding test duration). In some cases, tests are run for longer periods (e.g., 72 hours) to observe more slowly growing phases. The liquidus viscosity (poise) was determined from the liquidus temperature and the coefficients of the Flucher equation.

[0091] [Table 1-1]

[0092] [Table 1-2]

[0093] Multiple tests were performed on composition 2 after ceramming to determine various properties of the glass-ceramic of composition 2. Differential scanning calorimetry (DSC) traces were performed on composition 2 and plotted as DSC / (mW / mg) versus temperature (°C), as shown in Figure 1. This trace was used to demonstrate that a fine-grained microstructure can be achieved by ceramming at low temperatures relative to the crystallization temperature.

[0094] The transmittance of glass-ceramic composition 2 with a thickness of 1 mm was measured for light from 400 nm to 1000 nm. As shown in Figure 2, the average transmittance of glass-ceramic composition 2 at visible light wavelengths is over 90%.

[0095] A scanning electron microscope (SEM) was used to observe a sample of glass-ceramic composition 2 and determine the petalite particle size. Figure 3A shows the SEM at a 200 nm scale, and Figure 3B shows the SEM at a 100 nm scale. The petalite particles are on the order of 50-100 nm. The fineness of the particles is believed to contribute to the transparency of the glass-ceramic, as evidenced in Figure 2.

[0096] Two 50 mm x 50 mm x 1 mm specimens of glass-ceramic composition 2 were subjected to the ring-on-ring test as described above to determine the strength of the specimens. One specimen was subjected to abrasion (15 psi (103,421.4 Pa)) and the other specimen was not subjected to abrasion. Figure 4 shows the results of this ring-on-ring test. A strength of 514 MPa was achieved for the ring-on-ring test.

[0097] The fracture toughness of the glass-ceramic composition 2 specimen was measured using chevron notch specimen measurements. The fracture toughness was 1.13 MPa m 1 / 2 It was.

[0098] The hardness of the glass-ceramic composition samples was measured using a Model 5948 MicroTester available from Instron, Inc., to determine the Vickers hardness as described above. The Vickers hardness was approximately 750 kgf / mm 2 (approx. 7355N / mm 2 ) was.

[0099] A glass-ceramic of composition 2 was subjected to an ion-exchange process in which the sample was placed in a bath of molten NaNO at 430°C for 2, 4, 8, and 16 hours. As shown in Figure 5, a depth of layer of over 100 μm was achieved. Figure 5 also shows a plot of the NaO concentration (mole percent) versus sample thickness for each ion-exchange treatment. As can be seen, the depth of layer increased with increasing duration of the ion-exchange treatment. Also, a parabolic NaO profile was achieved after 16 hours of ion-exchange.

[0100] Two 50 mm × 50 mm × 1 mm samples of glass-ceramic composition 2 were ion-exchanged. One sample was ion-exchanged in a molten NaNO bath at 430 °C for 2 hours, and the other sample was ion-exchanged in a molten KNO bath at 430 °C for 2 hours. These two 50 mm × 50 mm × 1 mm samples of the ion-exchanged glass-ceramic composition 2 were subjected to ring-on-ring testing as described above. The results are shown in Figure 6. The strength of this glass-ceramic increased by approximately 30% after ion-exchange with NaNO and approximately doubled after ion-exchange with KNO. It is believed that ion-exchange with a KNO bath results in a greater depth of layer (DOL) of the compressive stress layer formed on the sample surface during ion-exchange.

[0101] A 50 mm × 50 mm × 1 mm sample of glass ceramic of composition 2 was ion-exchanged in a molten NaNO bath at 430 °C for 2 hours. A 50 mm × 50 mm × 1 mm sample of Glass A was ion-exchanged in a molten KNO bath at 420 °C for 5.5 hours. A 50 mm × 50 mm × 1 mm sample of Glass B was ion-exchanged in a 32% KNO bath at 540 °C for 8 hours, followed by a 100% KNO bath at 390 °C for 15 minutes. All of these samples were abraded at 15 psi (103,421.4 Pa) and subjected to the abrasion ring-on-ring test described above. The results are shown in Figure 7. The glass ceramic had higher strength than Glass A and similar strength to Glass B. Therefore, this ion-exchanged glass ceramic can have strength comparable to, or slightly higher than, the ion-exchanged glasses.

[0102] 50 mm x 50 mm x 1 mm samples of glass-ceramic of composition 2 were ion-exchanged in a molten NaNO bath at 430 °C for 2, 4, 8, and 16 hours. The ion-exchanged samples and non-ion-exchanged glass-ceramic samples of composition 2 were then subjected to ring-on-ring testing as described above. The results are shown in Figure 8. The strength of the glass-ceramic increased based on the duration of ion exchange.

[0103] 50 mm × 50 mm × 1 mm specimens of glass-ceramic composition 2 were ion-exchanged in a molten NaNO bath at 430 °C for 16 hours. The specimens were abraded at 15 psi (103,421.4 Pa), 25 psi (172,369 Pa), or 45 psi (310,264.2 Pa) and subjected to the abrasion ring-on-ring test described above. The results are shown in Figure 9. The specimen abraded at 15 psi (103,421.4 Pa) failed at a load of approximately 253 MPa, the specimen abraded at 25 psi (172,369 Pa) failed at a load of approximately 240 MPa, and the specimen abraded at 45 psi (310,264.2 Pa) failed at a load of approximately 201 MPa.

[0104] Example 2 Exemplary glass and glass-ceramic compositions (by weight) and properties for obtaining translucent glass-ceramics are listed in Table 2 and were determined according to conventional techniques in the glass art. Precursor glasses were formed having compositions 17-29 listed in Table 2. These precursor glasses were then subjected to the ceramming cycles shown in Table 2 below.

[0105] [Table 2-1]

[0106] [Table 2-2]

[0107] The fracture toughness of glass-ceramic compositions 17, 18, and 22 was measured using chevron notch specimens. The fracture toughness was 1.2 MPa m 1 / 2 , 1.13 MPa m 1 / 2 , and 1.2 MPa·m 1 / 2 It was.

[0108] A differential scanning calorimetry (DSC) trace was performed on composition 18 and plotted as DSC / (mW / mg) versus temperature (°C), as shown in Figure 11. Figure 12 is an X-ray diffraction (XRD) spectrum of the crystalline phases formed in composition 18. The XRD spectrum confirms that petalite and lithium disilicate are the predominant crystalline phases.

[0109] 50 mm x 50 mm x 1 mm samples of glass-ceramic compositions 19, 20, and 21 were subjected to ring-on-ring testing as described above to determine the strength of the samples. Figure 13 shows the results of the ring-on-ring testing. Strengths of 352 MPa, 304 MPa, and 313 MPa, respectively, were achieved for the ring-on-ring tests. Thus, strengths of over 300 MPa are achievable for the translucent glass-ceramics disclosed herein.

[0110] A glass-ceramic of composition 18, formed by batching a 1.4 mol% concentration of NaO into a bulk glass, was subjected to an ion-exchange process in which the sample was placed in a bath of molten NaNO at 430°C for 4 hours. A layer depth of over 100 μm was achieved, as shown in Figure 14, which also shows a plot of the concentration of NaO (weight percent) versus the thickness of the sample.

[0111] While several embodiments and examples have been provided for illustrative purposes, the foregoing description should not be deemed a limitation on the scope of the present disclosure or the appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to those skilled in the art without departing from the spirit and scope of the present disclosure or the appended claims.

[0112] Preferred embodiments of the present invention will be described below in detail.

[0113] Embodiment 1 Petalite crystalline phase; and Lithium silicate crystalline phase 1. A glass-ceramic article comprising: The glass-ceramic article, wherein the petalite crystalline phase and the lithium silicate crystalline phase have a higher weight percentage than other crystalline phases present in the glass-ceramic article.

[0114] Embodiment 2 2. The glass-ceramic article of claim 1, wherein the petalite crystalline phase comprises 20-70 wt. % of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-60 wt. % of the glass-ceramic article.

[0115] Embodiment 3 3. The glass-ceramic article of claim 2, wherein the petalite crystalline phase comprises 45-70 wt. % of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-50 wt. % of the glass-ceramic article.

[0116] Embodiment 4 3. The glass-ceramic article of claim 2, wherein the petalite crystalline phase comprises 40-60 wt. % of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-50 wt. % of the glass-ceramic article.

[0117] Embodiment 5 5. The glass-ceramic article of any one of embodiments 1-4, wherein the lithium silicate crystalline phase is a lithium disilicate crystalline phase or a lithium metasilicate crystalline phase.

[0118] Embodiment 6 6. The glass-ceramic article of any one of embodiments 1 to 5, wherein the article is transparent.

[0119] Embodiment 7 7. The glass-ceramic article of embodiment 6, wherein the article has a transmittance of at least 85% for light in the wavelength range of 400 nm to 1000 nm at a thickness of 1 mm.

[0120] Embodiment 8 7. The glass-ceramic article of claim 6, wherein the article has a transmittance of at least 90% for light in the wavelength range of 400 nm to 1000 nm at a thickness of 1 mm.

[0121] Embodiment 9 6. The glass-ceramic article of any one of claims 1 to 5, wherein the article is translucent and has a transmittance at a thickness of 1 mm for light in the wavelength range of 400 nm to 1000 nm in the range of 20 to less than 85%.

[0122] Embodiment 10 The glass-ceramic article comprises, in weight percent: SiO2: 55‐80%; Al2O3: 2‐20%; Li2O: 5‐20%; B2O3: 0‐10%; Na2O: 0‐5%; ZnO: 0‐10%; P2O5: 0.5-6%; and ZrO2: 0.2-15% 10. The glass-ceramic article of any one of claims 1-9, having a composition comprising:

[0123] Embodiment 11 The glass-ceramic article comprises, in weight percent: K2O: 0‐4%; MgO: 0‐8%; TiO2: 0‐5%; CeO2: 0-0.4%; and SnO2: 0.05-0.5% 11. The glass-ceramic article of claim 10, having a composition further comprising:

[0124] Embodiment 12 The glass-ceramic article comprises, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2-4% 11. The glass-ceramic article of claim 10, having a composition comprising:

[0125] Embodiment 13 The glass-ceramic article comprises, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; Na2O: 1‐2%; K2O: 1‐2%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2-4% 11. The glass-ceramic article of claim 10, having a composition comprising:

[0126] Embodiment 14 The glass-ceramic article comprises, in weight percent: SiO2: 65‐80%; Al2O3: 5‐16%; Li2O: 8‐15%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐2%; P2O5: 0.5-4%; and ZrO2: 0.2-6% 11. The glass-ceramic article of claim 10, having a composition comprising:

[0127] Embodiment 15 The glass-ceramic article comprises, in weight percent: SiO2: 60‐80%; Al2O3: 5‐20%; Li2O: 5‐20%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐4%; P2O5: 0.5-4%; and ZrO2: 0.2-8% 11. The glass-ceramic article of claim 10, having a composition comprising:

[0128] Embodiment 16 11. The glass-ceramic article of embodiment 10, wherein the sum of the weight percentages of P2O5 and ZrO2 is greater than 3.

[0129] Embodiment 17 The glass-ceramic article has a resistance of 1 MPa m 1 / 2 17. The glass-ceramic article of any one of embodiments 1 to 16, having a fracture toughness of at least 100%.

[0130] Embodiment 18 The glass-ceramic article has a resistance of about 600 kgf / mm 2 (approx. 5884N / mm 2 18. The glass-ceramic article of any one of claims 1 to 17, having a Vickers hardness of 1.5 or greater.

[0131] Embodiment 19 19. The glass-ceramic article of any one of embodiments 1 to 18, wherein the glass-ceramic article has a surface compressive stress in the range of about 100 MPa to about 500 MPa.

[0132] Embodiment 20 20. The glass-ceramic article of any one of embodiments 1-19, further comprising a compressive stress layer having a depth of layer (DOL) of at least about 30 μm.

[0133] Embodiment 21 21. The glass-ceramic article of claim 20, wherein the glass-ceramic article is not brittle.

[0134] Embodiment 22 22. The glass-ceramic article of any one of the preceding embodiments, further comprising particles having a longest dimension of 500 nm or less.

[0135] Embodiment 23 23. The glass-ceramic article of any one of embodiments 1 to 22, further comprising particles having a longest dimension of 100 nm or less.

[0136] Embodiment 24 24. The glass-ceramic article of any one of claims 1 to 23, wherein the glass-ceramic article has a ring-on-ring strength of at least 300 MPa.

[0137] Embodiment 25 1. A method of forming a glass-ceramic article, comprising: The above method: By weight: SiO2: 55‐80%; Al2O3: 2‐20%; Li2O: 5‐20%; B2O3: 0‐10%; Na2O: 0‐5%; ZnO: 0‐10%; P2O5: 0.5-6%; and ZrO2: 0.2-15% forming a glass composition comprising: ceramming the glass composition to form a glass-ceramic article comprising a petalite crystalline phase and a lithium silicate crystalline phase. Including, The method of claim 1, wherein the petalite crystalline phase and the lithium silicate crystalline phase have a higher weight percentage than other crystalline phases present in the glass-ceramic article.

[0138] Embodiment 26 The glass composition comprises, in weight percent: K2O: 0‐4%; MgO: 0‐8%; TiO2: 0‐5%; CeO2: 0-0.4%; and SnO2: 0.05-0.5% 26. The method of embodiment 25, further comprising:

[0139] Embodiment 27 The glass composition comprises, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2-4% 26. The method of embodiment 25, comprising:

[0140] Embodiment 28 The glass composition comprises, in weight percent: SiO2: 69‐80%; Al2O3: 6‐9%; Li2O: 10‐14%; Na2O: 1‐2%; K2O: 1‐2%; B2O3: 0‐12%; P2O5: 1.5-2.5%; and ZrO2: 2-4% 26. The method of embodiment 25, comprising:

[0141] Embodiment 29 The glass composition comprises, in weight percent: SiO2: 65‐80%; Al2O3: 5‐16%; Li2O: 8‐15%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐2%; P2O5: 0.5-4%; and ZrO2: 0.2-6% 26. The method of embodiment 25, comprising:

[0142] Embodiment 30 The glass composition comprises, in weight percent: SiO2: 60‐80%; Al2O3: 5‐20%; Li2O: 5‐20%; Na2O: 0‐3%; K2O: 0‐3%; B2O3: 0‐6%; ZnO: 0‐4%; P2O5: 0.5-4%; and ZrO2: 0.2-8% 26. The method of embodiment 25, comprising:

[0143] Embodiment 31 31. The method of any one of embodiments 25-30, wherein the sum of the weight percentages of P2O5 and ZrO2 is greater than 3.

[0144] Embodiment 32 32. The method of any one of embodiments 25-31, further comprising ion-exchanging the glass-ceramic article to produce a compressive stress layer having a depth of layer of at least 30 μm.

[0145] Embodiment 33 The ceramming step comprises the following successive steps: heating the glass composition to a glass prenucleation temperature; maintaining the glass pre-nucleation temperature for a predetermined period of time; heating the composition to a nucleation temperature; maintaining the nucleation temperature for a predetermined period of time; heating the composition to a crystallization temperature; and maintaining the crystallization temperature for a predetermined period of time. 33. The method of any one of embodiments 25 to 32, comprising:

[0146] Embodiment 34 The ceramming step comprises the following successive steps: heating the composition to a nucleation temperature; maintaining the nucleation temperature for a predetermined period of time; heating the composition to a crystallization temperature; and maintaining the crystallization temperature for a predetermined period of time. 31. The method of any one of embodiments 25 to 30, comprising:

[0147] Embodiment 35 34. The method of any one of embodiments 25-33, wherein the petalite crystalline phase comprises 20-70 wt. % of the glass-ceramic article, and the lithium silicate crystalline phase comprises 20-60 wt. % of the glass-ceramic article.

Claims

1. 55% to 80% by weight of SiO ２ ; 2% to 20% by weight of Al ２ O ３ ; 5% to 20% by weight of Li ２ O; 0 to 5% by weight of Na ２ O; greater than 0% and up to 6% by weight of P ２ O ５ and 0.2% to 15% by weight of ZrO ２ 1. A glass-ceramic article comprising: ZrO ２ and P ２ O ５ The total of is 3% by weight or more, The glass-ceramic article is made of lithium disilicate (Li ２ SiO ５ ) crystalline phase, the lithium disilicate comprises from 40% to 60% by weight of the glass-ceramic article; the particles of the glass ceramic have a longest dimension of less than 100 nm; A glass-ceramic article having an average transmittance of 85% or more for light in the wavelength range of 400 nm to 1000 nm when the glass-ceramic article is 1 mm thick.

2. The lithium disilicate particles are randomly oriented and interconnected, and the glass-ceramic article has a viscosity of 1 MPa m １／２ The glass-ceramic article of claim 1 having greater fracture toughness.

3. 0 to 2% by weight of K ２ The glass-ceramic article of any one of claims 1 to 2, comprising O.

4. More than 1% by weight and up to 5% by weight of Na ２ The glass-ceramic article of any one of claims 1 to 2, comprising O.

5. 3. The glass-ceramic article of claim 1, wherein the glass-ceramic article has a compressive stress greater than 100 MPa and a depth of layer greater than or equal to 30 μm.

6. 8% to 15% by weight of Li ２ The glass-ceramic article of any one of claims 1 to 2, comprising O.

7. 3% to 6% by weight of P ２ O ５ The glass-ceramic article of claim 6, comprising:

8. The glass-ceramic article further comprises petalite (LiAlSi ４ O １０ 3. The glass-ceramic article of claim 1, wherein the glass-ceramic article comprises a crystalline phase of Li(II)-Li(II) and Li(II)-Li ...

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