Glass-ceramic compositions, articles and methods of making the same

Abstract

This document discloses glass-ceramic compositions, articles made from the disclosed glass-ceramic compositions, and methods for manufacturing the same. More specifically, this document discloses a glass-ceramic composition comprising: a) about 2 mol% to about 20 mol% Al₂O₃; b) about 2 mol% to about 45 mol% Li₂O; and c) about 48 mol% to about 80 mol% SiO₂; having a β-spodumene phase and a lithium silicate crystalline phase, and optionally a lithite phase.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 057,404, filed July 28, 2020, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention generally relates to glass-ceramic compositions, glass-ceramic articles comprising said compositions, and methods of manufacturing the same. Background Technology

[0004] Glass-ceramics, formed by the nucleation and crystallization of specific glass compositions, are renowned for their low thermal expansion, high mechanical strength, and good thermal stability. Glass-ceramics, such as the Li₂O-Al₂O₃-SiO₂ (LAS) system, combine the advantages of near-zero thermal expansion and good transparency with high fracture toughness and ion exchange potential. Li₂O-Al₂O₃-SiO₂ glass-ceramics are known to contain various phases, such as β-quartz solid solutions and β-spodumene solid solutions or penelope. It is also known that the properties of glass-ceramic compositions are strongly dependent on their phase composition.

[0005] It is known that glass-ceramics can be designed to have near-zero thermal expansion over a wide temperature range by balancing the negative expansion of β-quartz with the positive expansion of residual glass. Many commercial glass-ceramics containing β-quartz crystals (Vision (Corning [11-12]), Zerodur and Ceran (Schott [13-17]), Narumi and Neoceram) TM N=0 (Nippon Electric [18-19]) has been used to manufacture radiant stoves, transparent cookware, wooden oven windows and fire doors.

[0006] When β-quartz is heated to 850°C for eight hours, a β-spodumene solid solution is formed. Corning Ware® 9608, containing a β-spodumene main phase and a rutile minor phase, is a well-known glass-ceramic for low-cost kitchen applications. However, most β-spodumene glass-ceramics are opaque because they crystallize at relatively high temperatures and low viscosities.

[0007] Therefore, there is a need for alternative glass-ceramic compositions that possess improved mechanical properties while exhibiting transparent, opaque, or translucent properties, depending on specific requirements. This disclosure at least partially satisfies these and other needs. Summary of the Invention

[0008] This invention relates to a glass-ceramic composition comprising: a) about 2 mol% to about 20 mol% Al₂O₃; b) about 2 mol% to about 45 mol% Li₂O; and c) about 48 mol% to about 80 mol% SiO₂; having a β-spodumene phase and a lithium silicate phase, and optionally a petalite phase. In a further aspect, when Al₂O₃ is present at about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a petalite phase; and a secondary crystalline phase comprising up to about 10% of a lithium silicate phase. In other respects, when Al2O3 is present in the form of about 7 mol% to about 12 mol%, the glass-ceramic composition comprises a main crystalline phase comprising about 60% to about 90% of a β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of a lithium silicate phase.

[0009] In a further aspect, the disclosed glass-ceramic composition may also comprise: a) 0 mol% to about 8 mol% of B2O3, b) 0 mol% to about 8 mol% of ZrO2, c) 0 mol% to about 5 mol% of P2O5, and d) 0 mol% to about 5 mol% of Na2O.

[0010] This document also discloses a glass-ceramic composition comprising: a) Al₂O₃ present in the form of about 2 mol% to about 20 mol%, b) SiO₂ present in the form of about 48 mol% to about 80 mol%, and c) R'₂O present in the form of greater than 0 mol% to about 45 mol%; and wherein R'₂O comprises Li₂O, Na₂O, K₂O, Ag₂O, Cu₂O, CuO, or combinations thereof, wherein the composition comprises a host crystalline phase comprising a β-spodumene phase and optionally a petalite phase. In such an exemplary aspect, when Al₂O₃ is present in the form of about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprises a host crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a petalite phase. In other aspects, when Al₂O₃ is present in quantities of about 5 mol% to about 7.5 mol% and Li₂O is present in quantities of 20 mol% to about 25 mol%, the glass-ceramic composition comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a lithite phase; and a secondary phase comprising up to 10 mol% of a lithium silicate phase. In a further aspect, such compositions may also comprise: a) B₂O₃ present in quantities of about 0 mol% to about 8 mol%, b) ZrO₂ present in quantities of 0 mol% to about 8 mol%, and c) P₂O₅ present in quantities of 0 mol% to about 5 mol%. In a further aspect, the compositions disclosed herein may comprise a compressive stress layer.

[0011] This document also discloses a glass-ceramic article comprising any of the aforementioned compositions. In some aspects, a glass-ceramic article comprising a composition having a compression layer is also disclosed. In such exemplary aspects, an article is disclosed in which the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is from about 1 μm to about 100 μm.

[0012] A glass-ceramic article is also disclosed, comprising: a) about 2 mol% to about 20 mol% Al2O3; b) SiO2 present in about 48 mol% to about 80 mol%; and R'2O present in greater than 0 mol% to about 45 mol%; wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO, or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase. The articles disclosed herein may include hollow vessels, tableware, containers, plates, plates, float / flat glass, cookware, powders, fibers, cones, spheres, blades, or any combination thereof. In a further aspect, the articles disclosed herein may be formed by float or flat glass pressing processes, press-blown processes, blow-blown processes, or any combination thereof.

[0013] This document also discloses a method comprising the following steps: a) forming a mixture comprising about 2 mol% to about 20 mol% Al₂O₃, about 2 mol% to about 45 mol% Li₂O, and about 48 mol% to about 80 mol% SiO₂; b) forming a homogeneous composition; and c) ceramizing the homogeneous composition to form a glass-ceramic composition. In a further aspect, the method disclosed herein also includes an ion exchange treatment step, said step comprising placing the glass-ceramic composition in a molten salt bath containing sodium, potassium, silver, or copper (I) ions or combinations thereof, under conditions that effectively provide an ion-exchanged glass-ceramic composition. In such exemplary aspects, the formed ion-exchange glass-ceramic composition comprises: a) Al2O3 present in about 2 mol% to about 20 mol%; b) SiO2 present in about 48 mol% to about 80 mol%; c) R'2O present in greater than 0 mol% to about 45 mol%; and wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase.

[0014] This document also discloses methods for forming articles, comprising forming any of the above-disclosed compositions and subsequently forming the article, wherein the article includes hollow vessels, tableware, containers, plates, plates, float or flat plates, cookware, powders, fibers, cones, spheres, blades, or any combination thereof. In a further aspect, the steps for forming glass-ceramic articles include float or flat plate pressing processes, pressure blowing processes, blow blowing processes, or any combination thereof.

[0015] Further aspects of this disclosure will be set forth in part in the detailed description, the accompanying drawings, and the following claims, and will also be derived in part from the detailed description, or may be learned by practicing the invention. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and are not intended to limit the scope of the disclosed invention. Attached Figure Description

[0016] Figure 1 The phase diagram of Li2O-Al2O3-SiO2 is shown (based on reference [6]).

[0017] Figures 2A-2B The XRD pattern is depicted: Figure 2A An exemplary glass-ceramic XRD pattern is shown, in which lithium feldspar and LiAlSi3O8 are the two major phases, and Li2SiO3 is the minor phase; Figure 2BExemplary XRD patterns of other exemplary glass-ceramics are shown. The formation of the LiAlSi3O8 phase is advantageous when the Al2O3 content in the composition is too high. The formation of the Li2SiO3 phase is advantageous when the Al2O3 content in the composition is too low. The formation of the SiO2 phase is advantageous when the SiO2 content in the composition is too high.

[0018] Figures 3A-3B The DSC pattern is depicted: Figure 3A Exemplary DSC patterns of samples with different amounts of Li2O and Al2O3 are shown; Figure 3B The glass transition temperature (T) is shown. g The value varies with the weight percentage of Al2O3.

[0019] Figure 4 The phase diagram of LiAlO2-SiO2 is shown, indicating the range of the spodumene and β-spodumene phases (according to reference

[25] ).

[0020] Figure 5A Viscosity-temperature profiles for LAS10, LAS11, and standard soda-lime silicate glass (SG80) were plotted. Figure 5B The MYEGA fit of the LAS11 sample was depicted.

[0021] Figure 6 The density of an exemplary glass sample with ZrO2 content is depicted.

[0022] Figure 7 The transmittance of different exemplary glass-ceramic samples is depicted.

[0023] Figures 8A-8C The opacity from SEM was depicted. Figure 8A ),translucent( Figure 8B ) and transparent ( Figure 8C Exemplary secondary electron micrographs of LAS glass-ceramics.

[0024] Figures 9A-9B The crack probability of different exemplary glass-ceramic samples under different loads was depicted.

[0025] Figure 10 CTEs of exemplary LAS11 glass and glass-ceramic samples are depicted. Detailed Implementation

[0026] The invention can be more readily understood by referring to the following detailed description, embodiments, drawings, and claims, as well as their preceding and following descriptions. However, it should be understood before disclosing and describing the articles, systems, and / or methods of the invention that, unless otherwise stated, the invention is not limited to the specific or exemplary aspects of the disclosed articles, systems, and / or methods, and therefore variations are naturally possible. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0027] The following description of the invention is provided as a teaching of the best known aspects of the invention. Therefore, those skilled in the art will recognize and understand that many changes can be made to the various aspects of the invention described herein while still obtaining the beneficial results of the invention. It will also be apparent that some desired benefits of the invention can be obtained by selecting some features of the invention without using others. Therefore, those skilled in the art will recognize that many modifications and adaptations can be made to the invention and may even be necessary and part of the invention in some cases. Therefore, the following description is again provided as an illustration of the principles of the invention and not as a limitation thereof.

[0028] definition

[0029] Unless otherwise expressly indicated by the context, as used herein, the singular forms “a,” “an,” and “the” include a plural of indicators. Thus, for example, unless otherwise expressly indicated by the context, a reference to an “article” includes aspects having two or more such articles.

[0030] It should be understood that certain features of this disclosure described in the context of a single aspect for the sake of brevity may also be provided in combination in a single aspect. Conversely, multiple features of this disclosure described in the context of a single aspect for the sake of brevity may also be provided individually or in any suitable combination.

[0031] As used herein, the terms “optional” or “optionally” mean that the event or situation described below may or may not occur, and the description includes both the possibility that the event or situation occurs and the possibility that it does not occur.

[0032] It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. As used in this specification and claims, the term "comprising" may include aspects "consisting of" and "substantially consisting of". 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 invention pertains. Reference will be made to several terms that are to be defined herein in this specification and the appended claims.

[0033] With respect to the terms “for example” and “such as” and their grammatical equivalents, unless otherwise expressly stated, the phrase “and not limited to” shall be understood as conforming to.

[0034] Although the wide range of numerical values ​​and parameters described in this disclosure are approximate, the values ​​described in specific examples are reported as precisely as possible. However, any numerical value inherently contains a certain degree of error, which is necessarily caused by the standard deviation found in their respective test measurements. Furthermore, when describing a range of values ​​herein, any combination of these values, including the stated values, is contemplated. Additionally, a range may be expressed herein as from “about” a particular value and / or to “about” another particular value. When such a range is expressed, it also includes, on the other hand, from one particular value and / or to another particular value.

[0035] Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the particular value forms another aspect. It should also be understood that each endpoint of a range is significant both relative to and independent of the other endpoint. Unless otherwise stated, the term “about” means within 5% (e.g., within 2% or 1%) of the particular value modified by the term “about.”

[0036] In this disclosure, various aspects of the invention may be presented in a range format. It should be understood that the range format description is merely for convenience and simplicity and should not be construed as an inflexible limitation of the scope of the invention. Therefore, the description of the range should be considered as having specifically disclosed all possible subranges and individual numerical values ​​within said ranges. For example, a description of a range such as 1 to 6 should be considered as having specifically disclosed subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numbers within said ranges, such as 1, 2, 2.7, 3, 4, 5, 5.3, 6, and any integral and partial increments therebetween. This applies regardless of the breadth of the range.

[0037] As used herein, the term "composition" is intended to cover products containing specified amounts of specified ingredients, and any products directly or indirectly produced from combinations of specified amounts of specified ingredients.

[0038] Unless otherwise stated, the weight percentage (wt.%) of a component is based on the total weight of the formulation or composition including the component. In the description of glass compositions, unless otherwise stated, the concentration of constitutive components (e.g., SiO2, Al2O3, B2O3, etc.) is given as a mole percentage (mol%) based on the oxide.

[0039] It should be understood that when an element is referred to as “connected” or “coupled” to another element, it may be directly connected or coupled to the other element, or there may be intermediate elements. Conversely, when an element is referred to as “directly connected” or “directly coupled” to another element, there are no intermediate elements. Other terms used to describe relationships between elements or layers should be interpreted in a similar manner (e.g., “between” vs. “directly between,” “adjacent” vs. “directly adjacent,” “on” vs. “directly on”). As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0040] It should be understood that, although the terms “first,” “second,” etc., may be used herein to describe various elements, components, regions, layers, and / or portions, these elements, components, regions, layers, and / or portions should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or portion from another. Therefore, without departing from the teachings of the exemplary embodiments, the first element, component, region, layer, or portion discussed below may be referred to as the second element, component, region, layer, or portion.

[0041] Spatial relative terms (such as "below," "below," "down," "above," "up," etc.) may be used herein for descriptive purposes, thereby describing the relationship of one element or feature to another, as illustrated in the figures. It should be understood that spatial relative terms are intended to cover different orientations of the device in use or operation other than those depicted in the figures. For example, if the device in the figures is flipped, then an element described as "below" or "below" of other elements or features is then oriented "above" of those elements or features. Thus, the term "below" can encompass both above and below orientations. The device may be oriented in other ways (rotated 90 degrees or in other orientations), and the spatial relative descriptors used herein shall be interpreted accordingly.

[0042] As used herein, the term “substantially” means that the events or circumstances subsequently described occurred completely, or that the events or circumstances subsequently described typically, generally, or substantially occurred.

[0043] Furthermore, the term "substantially" in some respects may refer to at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% of the property, component, composition, or other condition used to characterize or otherwise quantify the amount.

[0044] In other respects, as used herein, when used in the context of a composition or a component of a composition that is substantially absent, the term "substantially absent" is intended to mean that the component is not intentionally incorporated and added to the composition, but may be present as an impurity along with other components added to the composition. In such respects, the term "substantially absent" is intended to mean that trace amounts of the incorporated component may be present, for example, less than about 1% by weight, such as less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.05% by weight, or less than about 0.01% by weight of the material based on the total weight of the composition.

[0045] In other respects, as used herein, when used in the context of a surface that is substantially free of defects, the term “substantially free of defects” is intended, for example, to mean a surface having less than about 5% defects, less than about 4.5% defects, less than about 4% defects, less than about 3.5% defects, less than about 3% defects, less than about 2.5% defects, less than about 2% defects, less than about 1.5% defects, less than about 1% defects, less than about 0.5% defects, less than about 0.1% defects, less than about 0.05% defects, or less than about 0.01% defects on the total surface.

[0046] As used herein, the term “substantially” in contexts such as “substantially identical” or “substantially similar” means a method, system, or component that is at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% similar to the method, system, or component being compared.

[0047] As used herein, the term glass transition temperature or T g They are interchangeable and are defined as the inflection point of the differential scanning calorimetry (DSC) curve during the second heating period, in which the cooling and heating of the sample occur at a rate of 10 °C / min, and are plotted as heat flow in mW versus temperature in °C.

[0048] As used herein, the term "liquidline viscosity" refers to the shear viscosity of a glass composition at its liquidus temperature.

[0049] As used herein, the term “liquidline temperature” refers to the highest temperature at which devitrification occurs in a glass composition.

[0050] As used herein, the term “CTE” refers to the average coefficient of thermal expansion of a glass composition over a temperature range of about 25°C to about 300°C.

[0051] As used herein, the term "ion-exchanged" refers to glass-ceramics chemically strengthened by an ion-exchange process in which the glass-ceramic composition is treated with a heated salt bath, spray, or paste containing ions having a different ionic radius than those present on the glass-ceramic surface and / or in the bulk. The ions in the bath (or spray or paste) replace the ions in the glass-ceramic, and their radii may be smaller (or vice versa, depending on temperature conditions). Glass-ceramics subjected to this ion-exchange treatment are referred to herein as "ion-exchanged glass-ceramic compositions (or articles)." It should also be understood that the ion-exchange process described herein is not limited to salt baths, sprays, or pastes, and may include any other process that ensures ion exchange within the glass-ceramic, such as, but not limited to, steam-assisted, plasma-assisted, or sol-gel processes. Furthermore, in some exemplary and non-limiting aspects, for example, when a heated salt bath is used in the ion-exchange process, such a process can be further accelerated by applying an electric field to the bath.

[0052] While aspects of the invention may be described and claimed in specific legal categories (such as the systems category), this is for convenience only, and it will be understood by those skilled in the art that each aspect of the invention may be described and claimed in any legal category. Unless expressly stated otherwise, it should never be construed that any method or aspect set forth herein requires its steps to be performed in a particular order. Therefore, in the claims or description, where a method claim does not specifically state that the steps are limited to a particular order, no inference of order is intended in any aspect. This applies to any possible non-expressive basis of interpretation, including logical questions concerning the arrangement of steps or operational procedures, simple meanings derived from grammatical organization or punctuation, or the number or type of aspects described in this specification.

[0053] The invention can be more readily understood by referring to the following detailed description of various aspects of the invention and the examples included therein, as well as to the accompanying drawings and the description preceding and following them.

[0054] The invention can be more readily understood by referring to the following detailed description of various aspects of the invention and the examples included therein, as well as to the accompanying drawings and the description preceding and following them.

[0055] Composition

[0056] In some aspects, this document describes a glass-ceramic composition comprising: a) about 2 mol% to about 20 mol% Al₂O₃; b) about 2 mol% to about 45 mol% Li₂O; and c) about 48 mol% to about 80 mol% SiO₂; having a β-spodumene phase and a lithium silicate crystalline phase, and optionally a petrified phase. In a further aspect, a glass-ceramic composition comprising: a) about 3 mol% to about 12 mol% Al₂O₃; b) about 13 mol% to about 45 mol% Li₂O; and c) about 48 mol% to about 75 mol% SiO₂; having a β-spodumene phase and a lithium silicate crystalline phase, and optionally a petrified phase.

[0057] It should be understood that SiO2 represents the largest component of the disclosed glass composition. SiO2 is one of the most frequently studied glass-forming oxides. Without wishing to be bound by any theory, it should be understood that a high percentage of SiO2 can lead to high mechanical strength in the composition because SiO2 stabilizes the network structure of both glass and glass-ceramic materials. In some respects, when the amount of SiO2 is insufficient, β-spodumene (Li2O·Al2O3·4SiO2) and β-spodumene solid solutions (Li2O·Al2O3·nSiO2, 410) are preferably formed, rather than penelandite (Li2O·Al2O3·8SiO2) crystals. However, in cases where the amount of SiO2 is excessively high, the ratio of crystalline to amorphous components may be relatively low, resulting in a high melting temperature of the glass.

[0058] In the aspects disclosed herein, SiO2 may be present in any amount from about 48 mol% to about 80 mol%, including exemplary values ​​of about 50 mol%, about 51 mol%, about 52 mol%, about 53 mol%, about 54 mol%, about 55 mol%, about 56 mol%, about 57 mol%, about 58 mol%, about 59 mol%, about 60 mol%, about 61 mol%, about 62 mol%, about 63 mol%, about 64 mol%, about 65 mol%, about 66 mol%, about 67 mol%, about 68 mol%, about 69 mol%, about 70 mol%, about 71 mol%, about 72 mol%, about 73 mol%, about 74 mol%, about 75 mol%, about 76 mol%, about 77 mol%, about 78 mol%, and about 79 mol%. It should be understood that SiO2 can exist in any amount between any two of the aforementioned values, for example, about 45 mol% to about 75 mol%, or about 55 mol% to about 80 mol%, or about 65 mol% to about 80 mol%, or about 65 mol% to about 75 mol%.

[0059] In a further aspect, it should be understood that Al2O3 can also be a stabilizing component of the glass network structure. The presence of Al2O3 can also improve the mechanical properties of the glass (or glass-ceramic) composition. In some aspects, when the amount of Al2O3 is too high, the fraction of the lepidolite phase decreases according to the phase diagram. However, when the amount of Al2O3 is too low, a lithium silicate phase may be formed instead of a β-spodumene solid solution. In the aspects disclosed herein, Al2O3 may be present in any amount from about 2 mol% to about 20 mol%, including exemplary values ​​of about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, and about 19 mol%. It should be understood that Al2O3 can exist in any amount between any two of the aforementioned values, for example, about 3 mol% to about 12 mol%, or about 5 mol% to about 15 mol%, or about 6 mol% to about 14 mol%.

[0060] In glass and glass-ceramics, Li₂O can be added to form solid solution crystals of spodumene and β-spodumene. Without being bound by any theory, it is assumed that a high percentage of Li₂O increases the ion exchange potential of the glass-ceramics because Li atoms are relatively small compared to Na and K, which are available for ion exchange. However, if the amount of Li₂O is too high, the composition becomes very fluid, thus affecting production costs. In the respect disclosed herein, Li₂O can be any amount from about 2 mol% to about 45 mol%, including about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, about 20 mol%, about 21 mol%, about 22 mol%, about 23 mol%, about 24 mol%, about 25 mol%, about 26 mol%, about 27 mol%, about 28 mol%, about 29 mol%, about 30 mol%, about 31 mol%, about 32 mol%, about 33 mol%, about 34 mol%, about 35 mol%, about 36 mol%, about 37 mol%, about 38 mol%, about 39 mol%, about 40 mol%. Exemplary values ​​of about 41 mol%, about 42 mol%, about 43 mol%, and about 44 mol% are present. It should be understood that Li2O may be present in any amount between any two of the foregoing values, for example, about 13 mol% to about 45 mol%, or about 5 mol% to about 15 mol%, or about 8 mol% to about 12 mol%.

[0061] In a further aspect, when Al₂O₃ is present in quantities of approximately 5 mol% to approximately 7.5 mol%, including approximately 5.1 mol%, approximately 5.2 mol%, approximately 5.3 mol%, approximately 5.4 mol%, approximately 5.5 mol%, approximately 5.6 mol%, approximately 5.7 mol%, approximately 5.8 mol%, approximately 5.9 mol%, approximately 6.0 mol%, approximately 6.1 mol%, approximately 6.2 mol%, approximately 6.3 mol%, approximately 6.4 mol%, approximately 6.5 mol%, approximately 6.6 mol%, approximately 6.7 mol%, approximately 6.8 mol%, approximately 6.9 mol%, approximately 6.9 mol%, approximately 7.0 mol%, approximately 7.1 mol%, approximately 7.2 mol%, approximately 7.3 mol%, and approximately 7.4 mol%,... When an exemplary value of mol% is present, the glass-ceramic composition comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a lepidolite phase; and a secondary crystalline phase comprising up to about 10% of a lithium silicate phase.

[0062] In such exemplary aspects, the main crystalline phase may comprise about 20% to about 80% of a β-spodumene phase, including exemplary values ​​of about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, and about 75% of the β-spodumene phase. In such exemplary aspects, the main phase may also comprise about 20% to about 80% of a β-spodumene phase, including exemplary values ​​of about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, and about 75% of the lithite phase. Furthermore, the subcrystalline phase may contain up to about 10% (including exemplary values ​​of about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 9.5% and about 9.99%) of lithium silicate phase.

[0063] In a further exemplary aspect, when Al2O3 is present at about 5 mol% to about 7.5 mol%, Li2O may be present at about 20 mol% to about 25 mol%, including exemplary values ​​of about 21 mol%, about 21.5 mol%, about 22 mol%, about 22.5 mol%, about 23 mol%, about 23.5 mol%, about 24 mol%, and about 24.5 mol%.

[0064] In a further aspect, when Al₂O₃ is present in quantities of approximately 7 mol% to approximately 12 mol%, including approximately 7.1 mol%, approximately 7.2 mol%, approximately 7.3 mol%, approximately 7.4 mol%, approximately 7.5 mol%, approximately 7.6 mol%, approximately 7.7 mol%, approximately 7.8 mol%, approximately 7.9 mol%, approximately 8.0 mol%, approximately 8.1 mol%, approximately 8.2 mol%, approximately 8.3 mol%, approximately 8.4 mol%, approximately 8.5 mol%, approximately 8.6 mol%, approximately 8.7 mol%, approximately 8.8 mol%, approximately 8.9 mol%, approximately 9.0 mol%, approximately 9.1 mol%, approximately 9.2 mol%, approximately 9.3 mol%, and approximately 9.4 mol%, approximately 9.5 mol%, approximately 9.6 mol%, approximately 9.7 mol%, approximately 9.8 mol%, approximately 9.9 mol%, approximately 10.0 mol%, approximately 10.1 mol%, and approximately 10.2 mol%. When exemplary values ​​of mol%, about 10.3 mol%, about 10.4 mol%, about 10.5 mol%, about 10.6 mol%, about 10.7 mol%, about 10.8 mol%, about 10.9 mol%, about 11.00 mol%, about 11.1 mol%, about 11.2 mol%, about 11.3 mol%, about 11.4 mol%, about 11.5 mol%, about 11.6 mol%, about 11.7 mol%, about 11.8 mol%, and about 11.9 mol% are present, the glass-ceramic composition comprises a main crystalline phase comprising about 60% to about 90% of a β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of a lithium silicate phase. In such respects, the primary crystalline phase may comprise about 60% to about 90% of a β-spodumene phase, including exemplary values ​​of about 65%, about 70%, about 75%, about 80%, and about 85% of the β-spodumene phase. In other respects, the secondary crystalline phase comprises up to about 10% (including exemplary values ​​greater than 0%, about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 9.5%, about 9.9%, and about 9.99%) of a lithium silicate phase.

[0065] In a further exemplary and non-limiting aspect, when a lithium silicate crystalline phase is present, such phase may include a lithium metasilicate crystalline phase.

[0066] In a further aspect, the molar ratio of β-spodumene solid solution Li2O:Al2O3:SiO2 can be in the range of about 1:1:4 to 1:1:8, including exemplary values ​​of about 1:1:5, about 1:1:6 and about 1:1:7.

[0067] In some exemplary aspects, the glass-ceramic compositions disclosed herein may further comprise a) 0 mol% to about 8 mol% of B₂O₃, b) 0 mol% to about 8 mol% of ZrO₂, c) 0 mol% to about 5 mol% of P₂O₅, and d) 0 mol% to about 5 mol% of Na₂O. In other aspects, the glass-ceramic compositions disclosed herein may further comprise a) 0 mol% to about 5 mol% of B₂O₃, b) 0 mol% to about 3 mol% of ZrO₂, c) 0 mol% to about 3 mol% of P₂O₅, and d) 0 mol% to about 3 mol% of Na₂O.

[0068] In such exemplary aspects, B₂O₃ may be present in any amount from about 0 mol% to about 8 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, and about 7 mol%. It should be understood that B₂O₃ may be present in any amount between any two of the foregoing values, for example, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 3 mol%, or about 0.1 mol% to about 2 mol%. It should be understood that, in some aspects, B₂O₃ may reduce the viscosity of the composition at crystal growth temperatures and provide a tricoordinate network when boron is not charged and balanced by alkali metal oxides. Without wishing to be bound by any theory, it is assumed that this exemplary structure lowers the activation barrier for the movement of atoms from liquid to crystal, and thus lowers the crystal growth temperature and increases the ratio of crystalline to amorphous atoms. Furthermore, B2O3 can increase the chemical durability and glass-forming ability of the composition.

[0069] In a further aspect, ZrO2 can be present in any amount from 0 mol% to about 8 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, and about 7 mol%. It should be understood that ZrO2 can be present in any amount between any two of the foregoing values, for example, 0 mol% to about 3 mol%, or about 0.1 mol% to about 6 mol%, or about 2 mol% to about 6 mol%. Again, without being bound by any theory, it is assumed that ZrO2 can increase the transparency of LAS glass-ceramics. Without being bound by any theory, it is assumed that due to the larger Zr atoms, the activation barrier can be increased, resulting in a lower frequency of successful transitions of atoms from the liquid to the crystal. It is assumed that high concentrations of ZrO2 will lower the crystal growth temperature. However, in other respects, the presence of a larger amount of ZrO2 can increase the melting temperature of the glass.

[0070] In a further aspect, P2O5 may be present in any amount from 0 mol% to about 5 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, and about 4 mol%. It should be understood that P2O5 may be present in any amount between any two of the foregoing values, for example, 0 mol% to about 3 mol%, or about 0.1 mol% to about 5 mol%, or about 1 mol% to about 5 mol%. In an even further aspect, P2O5 may be a nucleating agent that produces bulk nucleation. Without wishing to be bound by any theory, it is assumed that if the concentration of P2O5 is low, crystals may grow on a surface rather than in bulk. In such aspects, a low crystal growth rate is also assumed. Without wishing to be bound by theory, it is further assumed that if the concentration of P2O5 is high, transparency will be affected because the crystal growth rate may be rapid and difficult to control.

[0071] In a further aspect, Na₂O can be present in any amount from 0 mol% to about 5 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, and about 4 mol%. It should be understood that Na₂O can be present in any amount between any two of the foregoing values, for example, 0 mol% to about 3 mol%, or about 0.1 mol% to about 2 mol%, or about 1 mol% to about 5 mol%. Without wishing to be bound by any theory, it is assumed that Na₂O can reduce the viscosity of the glass and increase its glass-forming ability. However, in other respects, large amounts of Na₂O can reduce the ratio of crystalline to amorphous components, and thus affect the toughness of the glass-ceramic.

[0072] In a further aspect, this document discloses a glass-ceramic composition comprising: a) Al2O3 present in about 2 mol% to about 20 mol%, b) SiO2 present in about 48 mol% to about 80 mol%, c) R'2O present in greater than 0 mol% to about 45 mol%; and wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO, or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a lepidolite phase. In other respects, this document discloses glass-ceramic compositions comprising: a) Al₂O₃ present in amounts from about 3 mol% to about 12 mol%, b) SiO₂ present in amounts from about 48 mol% to about 75 mol%, and c) R'₂O present in amounts from about 0 mol% to about 45 mol%; wherein R'₂O comprises Li₂O, Na₂O, K₂O, Ag₂O, Cu₂O, CuO, or combinations thereof, wherein the composition comprises a host crystalline phase comprising a β-spodumene phase and optionally a spodumene phase. In some respects, such glass-ceramic compositions may be defined as ion-exchanged glass-ceramic compositions.

[0073] In a further aspect, when R'2O contains Li2O, the composition may contain a subcrystalline phase comprising a lithium silicate phase.

[0074] In a further aspect, in such ion-exchange compositions, SiO2 may be present in any amount from about 48 mol% to about 80 mol%, including exemplary values ​​of about 50 mol%, about 51 mol%, about 52 mol%, about 53 mol%, about 54 mol%, about 55 mol%, about 56 mol%, about 57 mol%, about 58 mol%, about 59 mol%, about 60 mol%, about 61 mol%, about 62 mol%, about 63 mol%, about 64 mol%, about 65 mol%, about 66 mol%, about 67 mol%, about 68 mol%, about 69 mol%, about 70 mol%, about 71 mol%, about 72 mol%, about 73 mol%, about 74 mol%, about 75 mol%, about 76 mol%, about 77 mol%, about 78 mol%, and about 79 mol%. It should be understood that SiO2 can exist in any amount between any two of the aforementioned values, for example, about 45 mol% to about 75 mol%, or about 55 mol% to about 80 mol%, or about 65 mol% to about 80 mol%, or about 65 mol% to about 75 mol%.

[0075] In other respects, in such ion-exchange compositions, Al₂O₃ may be present in any amount from about 2 mol% to about 20 mol%, including exemplary values ​​of about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, and about 19 mol%. It should be understood that Al₂O₃ may be present in any amount between any two of the foregoing values, for example, about 3 mol% to about 12 mol%, or about 5 mol% to about 15 mol%, or about 6 mol% to about 14 mol%.

[0076] In other respects, in such ion-exchange compositions, R'₂O can be in any amount from 0 mol% to about 45 mol%, including about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, about 20 mol%, about 21 mol%, about 22 mol%, about 23 mol%, about 24 mol%, about 25 mol%, about 26 mol%, about 27 mol%, about 28 mol%, about 29 mol%, about 30 mol%, about 31 mol%, about 32 mol%, about 33 mol%, about 34 mol%, about 35 mol%, about 36 mol%. Exemplary values ​​of approximately 37 mol%, approximately 38 mol%, approximately 39 mol%, approximately 40 mol%, approximately 41 mol%, approximately 42 mol%, approximately 43 mol%, and approximately 44 mol% are present. It should be understood that R'2O may be present in any amount between any two of the foregoing values, for example, approximately 13 mol% to approximately 45 mol%, or approximately 5 mol% to approximately 15 mol%, or approximately 8 mol% to approximately 12 mol%.

[0077] Similar to the disclosed compositions described above, wherein Al₂O₃ is present in an amount of about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a petalite phase. In other aspects, when Al₂O₃ is present in an amount of about 5 mol% to about 7.5 mol% and Li₂O is present in an amount of 20 mol% to about 25 mol%, the glass-ceramic composition comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase and about 20% to about 80% of a petalite phase; and a secondary phase comprising up to 10 mol% of a lithium silicate phase. In a further aspect, if the glass-ceramic composition comprises a main crystalline phase comprising about 60% to about 90% of a β-spodumene phase when Al2O3 is present at about 7 mol% to about 12 mol%, and a secondary crystalline phase (if R'2O comprises Li2O) comprising up to about 10% of a lithium silicate phase.

[0078] Furthermore, the amount of R'2O can be adjusted to provide a glass composition exhibiting the desired melting temperature and / or liquidus temperature. Without being bound by theory, for example, the addition of alkali metal oxides can increase the coefficient of thermal expansion (CTE) of the glass and / or glass-ceramic comprising such precursor glass compositions and / or decrease the chemical durability of said glass and / or glass-ceramic. The amount of excess alkali in the glass composition can also determine the ceramization or heat treatment temperature used to form the glass-ceramic.

[0079] In a further aspect, such ion-exchange glass-ceramic compositions may also comprise: a) 0 mol% to about 8 mol% of B₂O₃, b) 0 mol% to about 8 mol% of ZrO₂, c) 0 mol% to about 5 mol% of P₂O₅, and d) 0 mol% to about 5 mol% of Na₂O. In other aspects, the glass-ceramic compositions disclosed herein may also comprise a) 0 mol% to about 5 mol% of B₂O₃, b) 0 mol% to about 3 mol% of ZrO₂, c) 0 mol% to about 3 mol% of P₂O₅, and d) 0 mol% to about 3 mol% of Na₂O.

[0080] In such exemplary aspects, B2O3 may be present in any amount from about 0 mol% to about 8 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, and about 7 mol%. It should be understood that B2O3 may be present in any amount between any two of the foregoing values, for example, from about 0.1 mol% to about 5 mol%, from about 0.1 mol% to about 3 mol%, or from about 0.1 mol% to about 2 mol%.

[0081] In a further aspect, ZrO2 may be present in any amount from 0 mol% to about 8 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, and about 7 mol%. It should be understood that ZrO2 may be present in any amount having values ​​between any two of the foregoing values, for example, from 0 mol% to about 3 mol%, or from about 0.1 mol% to about 6 mol%, or from about 2 mol% to about 6 mol%.

[0082] In a further aspect, P2O5 may be present in any amount from 0 mol% to about 5 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, and about 4 mol%. It should be understood that P2O5 may be present in any amount having any value between any two of the foregoing values, for example, from 0 mol% to about 3 mol%, or from about 0.1 mol% to about 5 mol%, or from about 1 mol% to about 5 mol%.

[0083] In a further aspect, Na₂O may be present in any amount from 0 mol% to about 5 mol%, including exemplary values ​​of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 2 mol%, about 3 mol%, and about 4 mol%. It should be understood that Na₂O may be present in any amount having values ​​between any two of the foregoing values, for example, from 0 mol% to about 3 mol%, or from about 0.1 mol% to about 2 mol%, or from about 1 mol% to about 5 mol%.

[0084] Furthermore, any glass-ceramic composition disclosed herein (both glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit a density of about 2.00 g / cm³. 3 Approximately 2.6 g / cm 3 Including approximately 2.01 g / cm³ 3 Approximately 2.02 g / cm³ 3 Approximately 2.03 g / cm³ 3 Approximately 2.04 g / cm³ 3 Approximately 2.05 g / cm³ 3 Approximately 2.06 g / cm³ 3 Approximately 2.07 g / cm³ 3 Approximately 2.08 g / cm³ 3 Approximately 2.09 g / cm³ 3 Approximately 2.1 g / cm³ 3 Approximately 2.11 g / cm³ 3 Approximately 2.12 g / cm³ 3 Approximately 2.13 g / cm³ 3 Approximately 2.14 g / cm³ 3 Approximately 2.15 g / cm³ 3 Approximately 2.16 g / cm³ 3 Approximately 2.17 g / cm³ 3 Approximately 2.18 g / cm³ 3 Approximately 2.19 g / cm³3 Approximately 2.20 g / cm³ 3 Approximately 2.21 g / cm³ 3 Approximately 2.22 g / cm³ 3 Approximately 2.23 g / cm³ 3 and approximately 2.24 g / cm 3 Approximately 2.25 g / cm³ 3 Approximately 2.26 g / cm³ 3 Approximately 2.27 g / cm³ 3 Approximately 2.28 g / cm³ 3 Approximately 2.29 g / cm³ 3 Approximately 2.30 g / cm³ 3 Approximately 2.31 g / cm³ 3 Approximately 2.32 g / cm³ 3 Approximately 2.33 g / cm³ 3 and approximately 2.34 g / cm 3 Approximately 2.35 g / cm³ 3 Approximately 2.36 g / cm³ 3 Approximately 2.37 g / cm³ 3 Approximately 2.38 g / cm³ 3 Approximately 2.39 g / cm³ 3 Approximately 2.4 g / cm³ 3 Approximately 2.41 g / cm³ 3 Approximately 2.42 g / cm³ 3 Approximately 2.43 g / cm³ 3 Approximately 2.44 g / cm³ 3 Approximately 2.45 g / cm³ 3 Approximately 2.46 g / cm³ 3 Approximately 2.47 g / cm³ 3 Approximately 2.48 g / cm³ 3 Approximately 2.49 g / cm³ 3 Approximately 2.5 g / cm³ 3 Approximately 2.51 g / cm³ 3 Approximately 2.52 g / cm³ 3 Approximately 2.53 g / cm³ 3 Approximately 2.54 g / cm³ 3 Approximately 2.55 g / cm³ 3 Approximately 2.56 g / cm³ 3 Approximately 2.57 g / cm³ 3 Approximately 2.58 g / cm³ 3 and approximately 2.59 g / cm 3 Example values.

[0085] In a further aspect, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit an average transmittance greater than about 80% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm. In such exemplary aspects, the average transmittance may be greater than about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 99.5%, and about 99.99%. In a further aspect, the average transmittance is measured at wavelengths in the range of about 390 nm to about 700 nm (including exemplary values ​​of about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, and about 650 nm). It should be understood that, in such exemplary aspects, the glass-ceramic composition is substantially transparent. In other exemplary aspects, the glass-ceramic composition is transparent. In other exemplary aspects, the glass-ceramic composition comprises a plurality of grains, wherein the median size of the grains is from about 20 nm to about 80 nm, including exemplary values ​​of about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, and about 75 nm.

[0086] In other aspects, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit an average transmittance between 20% and 80% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm. In such exemplary aspects, the average transmittance is about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, and about 80%. In a further aspect, the average transmittance is measured at wavelengths in the range of about 390 nm to about 700 nm (including exemplary values ​​of about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, and about 650 nm). It should be understood that in such exemplary aspects, the glass-ceramic composition is substantially translucent. In other aspects, the glass-ceramic composition is translucent. In a further exemplary aspect, the glass-ceramic composition comprises a plurality of grains, wherein the median size of the grains is from about 80 nm to about 500 nm, including exemplary values ​​of about 100 nm, about 120 nm, about 150 nm, about 170 nm, about 200 nm, about 220 nm, about 250 nm, about 270 nm, about 300 nm, about 320 nm, about 350 nm, about 370 nm, about 400 nm, about 420 nm, about 450 nm, and about 470 nm.

[0087] In other respects, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit an average transmittance of less than 20% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm. In such exemplary respects, the average transmittance is about 20%, about 19%, about 18%, about 17%, about 16%, about 15%, about 14%, about 13%, about 12%, about 11%, about 10%, about 9%, about 8%, about 7%, about 6%, about 5%, about 4%, about 3%, about 2%, and about 1%. In a further respect, the average transmittance is measured at wavelengths in the range of about 390 nm to about 700 nm (including exemplary values ​​of about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, and about 650 nm). It should be understood that in such exemplary respects, the glass-ceramic composition is substantially opaque. In other respects, the glass-ceramic composition is opaque. In a further exemplary aspect, the glass-ceramic composition comprises a plurality of grains, wherein the median size of the grains is greater than about 500 nm, greater than about 550 nm, greater than about 600 nm, greater than about 650 nm, greater than about 700 nm, greater than about 750 nm, greater than about 800 nm, greater than about 850 nm, greater than about 900 nm, greater than about 950 nm, or greater than about 1,000 nm.

[0088] In other respects, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit a Vickers hardness equal to or greater than about 6.0 GPa, or greater than about 7 GPa, or greater than about 8 GPa, or greater than about 9 GPa or greater than about 10 GPa.

[0089] In a further aspect, any glass-ceramic composition (glass-ceramic composition and ion-exchanged glass-ceramic composition) disclosed herein may exhibit a Vickers hardness that is at least about 5% greater than that of standard soda-lime silicate glass, or at least about 7%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, or at least about 50% greater than that of standard soda-lime silicate glass.

[0090] In other respects, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit crack resistance greater than about 0.2 kgf, about 0.4 kgf, about 0.6 kgf, about 0.8 kgf, or greater than about 1 kgf, or greater than about 1.5 kgf, greater than about 2 kgf, greater than about 5 kgf, or greater than about 10 kgf. In a further exemplary aspect, the glass-ceramic compositions disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may exhibit crack resistance at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, or at least 10 times higher than standard soda-lime silicate glass.

[0091] Furthermore, any glass-ceramic composition disclosed herein (both glass-ceramic compositions and ion-exchanged glass-ceramic compositions) can exhibit a coefficient of thermal expansion of approximately 40 x 10⁻⁶. -7 ℃ to approximately 90x10 -7 / ℃, including approximately 41x10 -7 / ℃, approximately 42x10 -7 / ℃, approximately 43x10 -7 / ℃, approximately 44x10 -7 / ℃, approximately 45x10 -7 / ℃, approximately 46x10 -7 / ℃, approximately 47x10 -7 / ℃, approximately 48x10 -7 / ℃, approximately 49x10 -7 / ℃, approximately 50x10 -7 / ℃, approximately 51x10 -7 / ℃, approximately 52x10 -7 / ℃, approximately 53x10 -7 / ℃, approximately 54x10 -7 / ℃, approximately 55x10 -7 / ℃, approximately 56x10 -7 / ℃, approximately 57x10 -7 / ℃, approximately 58x10 -7 / ℃, approximately 59x10 -7 / ℃, approximately 60x10 -7 / ℃, approximately 61x10 -7 / ℃, approximately 62x10 -7 / ℃, approximately 63x10 -7 / ℃, approximately 64x10 -7 / ℃, approximately 65x10 -7 / ℃, approximately 66x10 -7 / ℃, approximately 67x10 -7 / ℃, approximately 68x10 -7 / ℃, approximately 69x10 -7 / ℃, approximately 70x10 -7 / ℃, approximately 71x10 -7 / ℃, approximately 72x10 -7 / ℃, approximately 73x10 -7 / ℃, approximately 74x10 -7 / ℃, approximately 75x10 -7 / ℃, approximately 76x10 -7 / ℃, approximately 77x10 -7 / ℃, approximately 78x10 -7 / ℃, approximately 79x10 -7 / ℃, approximately 80x10 -7 / ℃, approximately 81x10 -7 / ℃, approximately 82x10 -7 / ℃, approximately 83x10 -7 / ℃, approximately 84x10 -7 / ℃, approximately 85x10 -7 / ℃, approximately 86x10 -7 / ℃, approximately 87x10 -7 / ℃, approximately 88x10 -7 / ℃ and approximately 89x10 -7 Exemplary values ​​for °C. It should be understood that, in such respects, °C is averaged over a range of about 25 °C to about 300 °C. It should be understood that the glass-ceramic composition may contain any value of thermal expansion between any two of the foregoing values.

[0092] In a further aspect, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) includes a glass transition temperature (T0) of about 450°C to about 600°C (including exemplary values ​​of about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, and about 590°C). g ).

[0093] In a further aspect, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may contain one or more clarifying agents. In some aspects, the composition may contain a clarifying agent in amounts greater than 0 mol% to about 1 mol% (including exemplary values ​​of about 0.1 mol%, about 0.2 mol%, about 0.3 mol%, about 0.4 mol%, about 0.5 mol%, about 0.6 mol%, about 0.7 mol%, about 0.8 mol%, and about 0.9 mol%). It should be understood that the clarifying agent may be present in any amount having values ​​between any two of the foregoing values.

[0094] In a further aspect, the clarifying agent may include any clarifying agent known in the art. In some aspects, the clarifying agent may comprise a salt, a metal oxide, or any combination thereof. In some aspects, when the clarifying agent comprises a salt, such salt may comprise a sulfate, chloride, iodide, bromide, or a combination thereof. In a further aspect, when the clarifying agent comprises a metal oxide, the metal oxide may comprise CeO2, SnO2, Fe2O3, As2O3, Sb2O3, MnO2, or a combination thereof. However, in other aspects, the glass composition does not contain any heavy metals. In such aspects, the glass composition is substantially free of heavy metals.

[0095] In some respects, adding clarifying agents can reduce bubble formation in the glass melt, thereby reducing the number of bubbles in glass-ceramics.

[0096] It should be understood that, in some respects, any glass-ceramic composition disclosed herein (glass-ceramic compositions and ion-exchanged glass-ceramic compositions) may also contain other components. For example, but not limited to, the disclosed compositions may contain one or more coloring components. In such respects, said one or more coloring components are selected from transition metal oxides and / or rare earth metal oxides. For example, but not limited to, said one or more coloring components may include V₂O₅, Cr₂O₃, TiO₂, MnO₂, NiO, ZnO, CuO, Co₃O₄, and combinations thereof. In the presence of coloring components, these components are present in a total amount equal to or less than about 1 mol%, less than about 0.9 mol%, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol%, less than about 0.5 mol%, less than about 0.4 mol%, less than about 0.3 mol%, less than about 0.2 mol%, and less than about 0.1 mol%. It should be understood that coloring components may be present in any amount having values ​​between any two of the foregoing values.

[0097] In a further aspect, to avoid potentially undesirable coloring effects on the glass-ceramic compositions disclosed herein, trace amounts of a decolorizing agent may be added. In this regard, the decolorizing agent may include one or more of sodium sulfate, selenium compounds, erbium oxide, cerium oxide, cobalt oxide, manganese oxide, and other multivalent elements. In a further aspect, these decolorizing agents may reduce coloring through any mechanism known in the art, including chemical and / or physical mechanisms. In a further aspect, these agents may be present in a total amount equal to or less than about 1 mol%, less than about 0.9 mol%, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol%, less than about 0.5 mol%, less than about 0.4 mol%, less than about 0.3 mol%, less than about 0.2 mol%, less than about 0.1 mol%, less than about 0.05 mol%, or less than about 0.01 mol%. It should be understood that the decolorizing agent may be present in any amount having a value between any two of the foregoing values.

[0098] Furthermore, any glass-ceramic composition disclosed herein may be ion-exchangeable.

[0099] Furthermore, such ion-exchanged glass-ceramic compositions can also be substantially transparent. In other respects, such ion-exchanged glass-ceramic compositions are substantially translucent. And in yet another respect, such ion-exchanged glass-ceramic compositions are substantially opaque.

[0100] Furthermore, these ion-exchanged glass-ceramic compositions may include a compressive stress layer. It should be understood that this layer is formed through an ion-exchange process.

[0101] Furthermore, when the glass-ceramic composition contains R'2O, and when R'2O includes Ag2O and / or Cu2O and / or CuO, such compositions may also exhibit antimicrobial, antiviral, antibacterial, and / or antifungal properties.

[0102] In a further aspect, the glass composition described herein may be substantially transparent at wavelengths in the range of about 400 nm to about 800 nm. In some exemplary and non-limiting aspects, the glass composition exhibits percentage transmittance greater than about 87%, greater than about 88%, greater than about 89%, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, and greater than about 99% at wavelengths in the range of about 400 nm to about 800 nm (including exemplary values ​​of about 430 nm, about 450 nm, about 470 nm, about 500 nm, about 530 nm, about 550 nm, about 570 nm, about 600 nm, about 630 nm, about 650 nm, about 670 nm, about 700 nm, about 730 nm, about 750 nm, and about 770 nm).

[0103] Products

[0104] In some aspects, this document discloses articles comprising any of the compositions disclosed above. For example, but not limited to, articles comprising: a) about 2 mol% to about 20 mol% Al₂O₃; b) about 2 mol% to about 45 mol% Li₂O; and about 48 mol% to about 80 mol% SiO₂; having a β-spodumene phase and a lithium silicate crystalline phase, and optionally a petrified feldspar phase. In other aspects, articles comprising: a) about 3 mol% to about 12 mol% Al₂O₃; b) about 13 mol% to about 45 mol% Li₂O; and about 48 mol% to about 75 mol% SiO₂; having a β-spodumene phase and a lithium silicate crystalline phase, and optionally a petrified feldspar phase.

[0105] In other respects, this document discloses an article comprising: a) about 2 mol% to about 20 mol% of Al2O3, b) SiO2 present in about 48 mol% to about 80 mol%; and R'2O present in greater than 0 mol% to about 45 mol%; wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase. In other respects, this document discloses an article comprising: a) about 3 mol% to about 12 mol% of Al2O3, b) SiO2 present in about 48 mol% to about 75 mol%; and R'2O present in greater than 0 mol% to about 45 mol%; wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase.

[0106] In some aspects, glass-ceramic articles comprising a composition having a compression layer are also disclosed. In such exemplary aspects, the compression layer may extend from the surface of the article to a depth of the compression layer, wherein the depth is from about 1 μm to about 100 μm, including exemplary values ​​of about 2 μm, about 5 μm, about 10 μm, about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, and about 95 μm. In a further aspect, the depth of the compression layer may be up to about 25% of the thickness of the glass-ceramic article, including exemplary values ​​of about 1%, about 5%, about 10%, about 15%, and about 20% of the thickness of the glass-ceramic article.

[0107] In a further aspect, the compressive stress layer may exhibit compressive stress of at least about 10 MPa, at least about 20 MPa, at least about 50 MPa, at least about 80 MPa, at least about 100 MPa, at least about 120 MPa, at least about 150 MPa, at least about 180 MPa, at least about 200 MPa, at least about 210 MPa, or at least about 250 MPa.

[0108] In a further aspect, the articles disclosed herein exhibit ring-to-ring strength that is at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 45%, or at least 50% higher than that of standard soda-lime silicate glass tested under similar conditions.

[0109] In a further aspect, the article may be substantially transparent. In other aspects, the article may be substantially translucent. In still other aspects, the article may be substantially opaque. In a further aspect, the article may comprise a composition containing a coloring component. In such exemplary aspects, the article may have color.

[0110] In a further aspect, the articles may include any articles known in the art that require the mechanical and optical properties disclosed herein. In other aspects, the articles disclosed herein may include hollow vessels, tableware, containers, plates, plates (including plates prepared by the float glass process), cookware, powders, fibers, cones, spheres, blades, or any combination thereof. In a further aspect, the articles disclosed herein may be formed by any process. For example, the articles may be formed by float glass or flatbed pressing, press blowing, blow blowing, or any combination thereof. In a further aspect, the articles disclosed herein may also be used in various electronic devices or portable computing devices, light diffusers, automotive, electrical appliances, medical industry, food industry, and even construction applications. In a further aspect, the articles disclosed herein may have shapes or structures known in the art.

[0111] This document also discloses a tableware comprising any of the glass-ceramic compositions disclosed above. In some aspects, but not limited to, the tableware may include blown and / or pressed products. In a further exemplary aspect, the tableware may be formed by a pressing process, a press-blown process, a blow-blown process, or any combination thereof. In other aspects, this document discloses a hollow vessel comprising any of the glass-ceramic compositions disclosed above. In some aspects, but not limited to, the hollow vessel may be formed by a press-blown process, a blow-blown process, or a combination thereof. This document also discloses a cookware comprising any of the glass-ceramic compositions disclosed above. In a further aspect, this document discloses a powder comprising any of the glass-ceramic compositions disclosed above. In some aspects, but not limited to, the cookware may be formed by a pressing process, a press-blown process, a blow-blown process, or any combination thereof. In other aspects, this document discloses a fiber comprising any of the glass-ceramic compositions disclosed above. In some aspects, but not limited to, the fiber may include continuous or discontinuous fiber products or glass fiber reinforced composites.

[0112] method

[0113] This document also discloses methods for preparing the disclosed compositions and articles. In some aspects, this document discloses a method comprising the steps of: a) forming a mixture comprising about 2 mol% to about 20 mol% Al2O3, about 2 mol% to about 45 mol% Li2O, and about 48 mol% to about 80 mol% SiO2; b) forming a homogeneous composition; and c) ceramizing the homogeneous composition to form a glass-ceramic composition.

[0114] In other respects, this document discloses a method comprising the following steps: a) forming a mixture comprising about 3 mol% to about 12 mol% Al2O3, about 13 mol% to about 45 mol% Li2O, and about 48 mol% to about 75 mol% SiO2; b) forming a homogeneous composition; and c) ceramizing the homogeneous composition to form a glass-ceramic composition.

[0115] It should be understood that Al2O3, Li2O and SiO2 may be present in any amount as disclosed in the above compositions.

[0116] In a further aspect, the mixture formed by the methods disclosed herein may also contain 0 mol% to about 8 mol% of ZrO2, or 0 mol% to about 5 mol% of P2O5, or combinations thereof. In other aspects, the mixture formed by the methods disclosed herein may also contain 0 mol% to about 3 mol% of ZrO2, or 0 mol% to about 3 mol% of P2O5, or combinations thereof. It should be understood that ZrO2 and P2O5 may be present in any amounts disclosed in the above compositions.

[0117] In a further aspect, the step of forming a homogeneous composition includes melting the mixture in a furnace at a temperature of about 1300°C to about 1700°C for a first predetermined time. At such a temperature, the temperature in the furnace can be any temperature in the range of about 1300°C to about 1700°C, including about 1310°C, about 1320°C, about 1330°C, about 1340°C, about 1350°C, about 1360°C, about 1370°C, about 1380°C, about 1390°C, about 1400°C, about 1410°C, about 1420°C, about 1430°C, about 1440°C, about 1450°C, about 1460°C, about 1470°C, and about 1700°C. Exemplary values ​​of approximately 480°C, 1,490°C, 1,500°C, 1,510°C, 1,520°C, 1,530°C, 1,540°C, 1,550°C, 1,560°C, 1,570°C, 1,580°C, 1,590°C, 1,600°C, 1,610°C, 1,620°C, 1,630°C, 1,640°C, 1,650°C, 1,660°C, 1,670°C, 1,680°C, and 1,690°C.

[0118] In a further aspect, the method disclosed herein also includes an annealing step at a temperature of about 450°C to about 700°C, said temperature including exemplary values ​​of about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, about 590°C, about 600°C, about 610°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, and about 690°C.

[0119] In a further aspect, the ceramization step includes heating the homogeneous composition at a nucleation temperature for a second predetermined time. In such an exemplary aspect, the nucleation temperature is from 450°C to about 700°C, including exemplary values ​​of about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, about 590°C, about 600°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, and about 690°C.

[0120] In a further aspect, the ceramization step in the methods disclosed herein further includes heating the composition to a crystallization temperature at a rate of about 5°C / min to about 15°C / min and holding the composition at the crystallization temperature for a third predetermined time. In such exemplary aspects, heating is performed at a rate of about 5°C / min to about 15°C / min, including exemplary aspects of about 6°C / min, about 7°C / min, about 8°C / min, about 9°C / min, about 10°C / min, about 11°C / min, about 12°C / min, about 13°C / min, and about 14°C / min.

[0121] In a further aspect, the crystallization temperature is from about 580°C to about 800°C, including exemplary values ​​of about 590°C, about 600°C, about 610°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, about 690°C, about 700°C, about 710°C, about 720°C, about 730°C, about 740°C, about 750°C, about 760°C, about 770°C, about 780°C, and about 790°C.

[0122] It should be understood that those skilled in the art can adjust the nucleation and crystallization temperatures to suit different glass compositions within the above range.

[0123] In other respects, the first scheduled time is from about 0.5 hours to about 20 hours, including exemplary values ​​of about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, about 8 hours, about 9.5 hours, about 10 hours, about 10.5 hours, about 11 hours, about 11.5 hours, about 12 hours, about 12.5 hours, about 13 hours, about 13.5 hours, about 14 hours, about 14.5 hours, about 15 hours, about 15.5 hours, about 16 hours, about 16.5 hours, about 17 hours, about 17.5 hours, about 18 hours, about 18.5 hours, about 19 hours, and about 19.5 hours.

[0124] In other respects, the first scheduled time is from about 3 hours to about 5 hours, including exemplary values ​​of about 3.1 hours, about 3.2 hours, about 3.3 hours, about 3.4 hours, about 3.5 hours, about 3.6 hours, about 3.7 hours, about 3.8 hours, about 3.9 hours, about 4.0 hours, about 4.1 hours, about 4.2 hours, about 4.3 hours, about 4.4 hours, about 4.5 hours, about 4.6 hours, about 4.7 hours, about 4.8 hours and about 4.9 hours.

[0125] In other respects, the second scheduled time is from about 0.5 hours to about 20 hours, including exemplary values ​​of about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, about 8 hours, about 9.5 hours, about 10 hours, about 10.5 hours, about 11 hours, about 11.5 hours, about 12 hours, about 12.5 hours, about 13 hours, about 13.5 hours, about 14 hours, about 14.5 hours, about 15 hours, about 15.5 hours, about 16 hours, about 16.5 hours, about 17 hours, about 17.5 hours, about 18 hours, about 18.5 hours, about 19 hours, and about 19.5 hours.

[0126] In other respects, the second scheduled time is from about 3 hours to about 5 hours, including exemplary values ​​of about 3.1 hours, about 3.2 hours, about 3.3 hours, about 3.4 hours, about 3.5 hours, about 3.6 hours, about 3.7 hours, about 3.8 hours, about 3.9 hours, about 4.0 hours, about 4.1 hours, about 4.2 hours, about 4.3 hours, about 4.4 hours, about 4.5 hours, about 4.6 hours, about 4.7 hours, about 4.8 hours and about 4.9 hours.

[0127] In other respects, the third scheduled time is from about 0.5 hours to about 20 hours, including exemplary values ​​of about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, about 8 hours, about 9.5 hours, about 10 hours, about 10.5 hours, about 11 hours, about 11.5 hours, about 12 hours, about 12.5 hours, about 13 hours, about 13.5 hours, about 14 hours, about 14.5 hours, about 15 hours, about 15.5 hours, about 16 hours, about 16.5 hours, about 17 hours, about 17.5 hours, about 18 hours, about 18.5 hours, about 19 hours, and about 19.5 hours.

[0128] In other respects, the third scheduled time is approximately 3 hours to approximately 5 hours, including exemplary values ​​of approximately 3.1 hours, approximately 3.2 hours, approximately 3.3 hours, approximately 3.4 hours, approximately 3.5 hours, approximately 3.6 hours, approximately 3.7 hours, approximately 3.8 hours, approximately 3.9 hours, approximately 4.0 hours, approximately 4.1 hours, approximately 4.2 hours, approximately 4.3 hours, approximately 4.4 hours, approximately 4.5 hours, approximately 4.6 hours, approximately 4.7 hours, approximately 4.8 hours, and approximately 4.9 hours.

[0129] In other respects, the first, second, and / or third scheduled times may be the same or different.

[0130] In some aspects, P2O5 can be used as a nucleating agent in the methods disclosed herein. As used herein, the term "nucleating agent" refers to a component in a glass-ceramic (and / or precursor glass composition and / or glass comprising such composition) that serves as the starting point for the nucleus itself (i.e., a discontinuity or defect in a homogeneous or amorphous phase that produces a crystalline phase), and no other component is required to promote nucleation. It should be understood that in other exemplary aspects, TiO2 and / or ZrO2 can also be used as nucleating agents.

[0131] In other respects, ZrO2 can be a crystal size growth limiting agent.

[0132] This document also discloses aspects in which the glass-ceramic composition formed by the methods disclosed herein may comprise a β-spodumene phase, optionally a lepidolite phase, and a lithium silicate crystalline phase.

[0133] In a further aspect, the glass-ceramic composition formed by the disclosed method may contain about 5 mol% to about 7.5 mol% of Al2O3, said amount including exemplary values ​​of about 5.1 mol%, about 5.2 mol%, about 5.3 mol%, about 5.4 mol%, about 5.5 mol%, about 5.6 mol%, about 5.7 mol%, about 5.8 mol%, about 5.9 mol%, about 6.0 mol%, about 6.1 mol%, about 6.2 mol%, about 6.3 mol%, about 6.4 mol%, about 6.5 mol%, about 6.6 mol%, about 6.7 mol%, about 6.8 mol%, about 6.9 mol%, about 6.9 mol%, about 7.0 mol%, about 7.1 mol%, about 7.2 mol%, about 7.3 mol%, and about 7.4 mol%. In such exemplary values, the glass-ceramic article comprises a main crystalline phase comprising about 20% to about 80% of a β-spodumene phase, including exemplary values ​​of 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, and about 75% of the β-spodumene phase. In a further aspect, the main phase may comprise about 20% to about 80% of a lithite phase, including 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, and about 75% of the β-spodumene phase. In a further aspect, such compositions may comprise a subcrystalline phase comprising up to about 10% (including exemplary values ​​of about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 9.5%, and about 9.99%) of a lithium silicate phase.

[0134] In a further exemplary aspect, when Al2O3 is present at about 5 mol% to about 7.5 mol%, Li2O may be present at about 20 mol% to about 25 mol%, including exemplary values ​​of about 21 mol%, about 21.5 mol%, about 22 mol%, about 22.5 mol%, about 23 mol%, about 23.5 mol%, about 24 mol%, and about 24.5 mol%.

[0135] In a further aspect, the glass-ceramic composition formed by the disclosed method may contain about 7 mol% to about 12 mol% of Al2O3, said amount comprising about 7.1 mol%, about 7.2 mol%, about 7.3 mol%, about 7.4 mol%, about 7.5 mol%, about 7.6 mol%, about 7.7 mol%, about 7.8 mol%, about 7.9 mol%, about 8.0 mol%, about 8.1 mol%, about 8.2 mol%, about 8.3 mol%, about 8.4 mol%, about 8.5 mol%, about 8.6 mol%, about 8.7 mol%, about 8.8 mol%, about 8.9 mol%, about 9.0 mol%, about 9.1 mol%, about 9.2 mol%, about 9.3 mol%, and about 9.4 mol%, about 9.5 mol%, about 9.6 mol%, about 9.7 mol%, about 9.8 mol%, about 9.9 mol%, and about 10.0 mol%. Exemplary values ​​for mol%, about 10.1 mol%, about 10.2 mol%, about 10.3 mol%, about 10.4 mol%, about 10.5 mol%, about 10.6 mol%, about 10.7 mol%, about 10.8 mol%, about 10.9 mol%, about 11.00 mol%, about 11.1 mol%, about 11.2 mol%, about 11.3 mol%, about 11.4 mol%, about 11.5 mol%, about 11.6 mol%, about 11.7 mol%, about 11.8 mol%, and about 11.9 mol%. In such exemplary aspects, the glass-ceramic composition comprises a main crystalline phase comprising about 60% to about 90% of a β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of a lithium silicate phase. In such respects, the primary crystalline phase may comprise about 60% to about 90% of a β-spodumene phase, including exemplary values ​​of about 65%, about 70%, about 75%, about 80%, and about 85% of the β-spodumene phase. In other respects, the secondary crystalline phase comprises up to about 10% (including exemplary values ​​greater than 0%, about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 9.5%, about 9.9%, and about 9.99%) of a lithium silicate phase. In a further respect, when a lithium silicate crystalline phase is present, the phase may include a lithium metasilicate crystalline phase.

[0136] In a further aspect, the mixture formed from the compositions disclosed herein may further comprise about 0 mol% to about 8 mol% of B₂O₃ and 0 mol% to about 8 mol% of Na₂O. In an even further aspect, the mixture formed from the compositions disclosed herein may further comprise about 0 mol% to about 5 mol% of B₂O₃ and 0 mol% to about 3 mol% of Na₂O. It should be understood that B₂O₃ and Na₂O may be present in any amounts as disclosed in the above compositions.

[0137] In a further aspect, the methods disclosed herein may include an ion exchange treatment step comprising placing the glass-ceramic composition in a molten salt bath. In this respect, the molten salt bath may contain any ions suitable for ion exchange of the glass-ceramic composition. In some aspects, the molten bath may contain sodium, potassium, silver, or copper (I) ions, or combinations thereof. In other aspects, the ion exchange treatment may be carried out under conditions that effectively provide a glass-ceramic composition for ion exchange.

[0138] In a further aspect, the molten bath may contain any disclosed ions or mixtures thereof. In some aspects, conditions for effectively providing ion-exchange glass-ceramic compositions include exposing the glass-ceramic composition to a molten salt at a temperature of about 380°C to about 500°C, said temperature including exemplary values ​​of about 390°C, about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, and about 490°C, for a period of about 4 hours to about 20 hours, including exemplary values ​​of about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, and about 19 hours.

[0139] In some further exemplary and non-limiting aspects, the ion exchange treatment step may be performed after the ceramization step.

[0140] It should also be understood that, in the aspects disclosed herein, the ion exchange treatment step may include placing the composition disclosed herein in a first melt bath containing one or more molten oxides and forming a first ion-exchange composition. In other aspects, the method may further include placing the first ion-exchange composition in a second bath containing one or more molten oxides and forming a second ion-exchange composition, and so on, until the desired ion-exchange composition is formed. It should be understood that, in these exemplary and non-limiting aspects, the first melt bath composition and the second melt bath composition may contain the same or different molten oxides. In other aspects, the desired ion-exchange composition may be formed in one step. In some exemplary aspects, a melt bath containing potassium (K) ions (or silver (Ag) or copper (Cu) (I)) or Cu (II) may replace sodium (Na) ions or lithium (Li) ions in the glass-ceramic composition, depending on the temperature conditions. In yet another exemplary aspect, a melt bath containing sodium (Na) ions may further replace lithium (Li) ions in the glass-ceramic composition, depending on the temperature conditions. In a further aspect, other alkali metal ions, such as cesium or rubidium, may also be present. In other exemplary and non-limiting aspects, ion exchange with divalent metal ions such as calcium, barium, or magnesium may be used if desired. It should also be understood that the melt bath may contain salts of any desired metal ions known in the art, for example, said salts may include nitrates, sulfates, halides, etc.

[0141] It should also be understood that any ion exchange mechanism known in the art may be considered. In some aspects, larger ions in the composition may be replaced by smaller ions in the bath. However, in further aspects, smaller ions in the composition may be replaced by larger ions in the bath. Such ion exchange processes can be controlled by adjusting the temperature and exposure time.

[0142] Furthermore, when the bath contains silver or copper ions, the resulting ion exchange composition can exhibit antimicrobial, antibacterial, antifungal, or antiviral properties in the material.

[0143] In a further aspect, the ion-exchanged glass-ceramic composition comprises: a) Al2O3 present in about 2 mol% to about 20 mol%; b) SiO2 present in about 48 mol% to about 80 mol%; c) R'2O present in greater than 0 mol% to about 45 mol%; and wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a host crystalline phase comprising a β-spodumene phase and optionally a spodumene phase. In other respects, the ion-exchanged glass-ceramic composition comprises: a) Al₂O₃ present in amounts from about 3 mol% to about 12 mol%; b) SiO₂ present in amounts from about 48 mol% to about 75 mol%; c) R'₂O present in amounts greater than 0 mol% to about 45 mol%; and wherein R'₂O comprises Li₂O, Na₂O, K₂O, Ag₂O, Cu₂O, CuO, or combinations thereof, wherein the composition comprises a host crystalline phase comprising a β-spodumene phase and optionally a spodumene phase. It should be understood that any component disclosed herein may comprise any amount disclosed in the compositions described above.

[0144] In a further aspect, the methods disclosed herein provide ion-exchanged glass-ceramic compositions comprising a compressive stress layer. It should be understood that the compressive stress layer formed by the disclosed methods can exhibit any of the properties described above and have any thickness or depth as described above. In a further aspect, the properties of the compressive stress layer can be adjusted by various ion exchange processing steps, such as a single ion exchange step or multiple ion exchange procedures, as described above.

[0145] It should also be understood that, in some respects, the amount and type of ions added via ion exchange can affect the transparency of the composition. However, in other respects, the amount and type of ions added via ion exchange can affect the coefficient of thermal expansion (CTE) of the composition. Without being bound by theory, for example, the addition of alkali metal oxides can increase the CTE of the glass and / or glass-ceramic and / or decrease the chemical durability of said glass and / or glass-ceramic.

[0146] In a further aspect, the glass-ceramic compositions and ion-exchanged glass-ceramic compositions may exhibit any of the properties and characteristics disclosed above. In such exemplary aspects, these compositions may be transparent, translucent, or opaque, and have any of the medium particle sizes disclosed above.

[0147] In a further aspect, the methods disclosed herein include steps for forming glass-ceramic articles. Any method known in the art for forming or shaping articles can be used. For example, but not limited to, methods for forming glass-ceramic articles may include drawing glass (by slot drawing or fusion drawing processes), float glass processing, or thin rolling. In other aspects, the methods may include shaping glass or glass-ceramic into any desired shape. Various forming methods may also be used, such as casting, molding, pressing, rolling, float glass, etc. In a further aspect, the articles disclosed herein may be formed by float / flat glass pressing, press blowing, blow blowing, or any combination thereof.

[0148] In a further aspect, articles formed by the methods disclosed herein may include hollow vessels, tableware, containers, plates, plates, float plates / flat plates, cookware, powders, fibers, cones, spheres, blades, or any combination thereof.

[0149] Example

[0150] Example 1

[0151] The following embodiments are provided to provide a complete disclosure and description to those skilled in the art of how to manufacture and evaluate the compounds, compositions, articles, apparatus, and / or methods claimed herein, and are intended to be illustrative only and not to limit this disclosure. Efforts have been made to ensure the accuracy of figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be taken into account.

[0152] LAS glass-ceramic samples were prepared using powders of Li₂CO₃ (Alfa Aesar, USA, 99%), SiO₂ (Alfa Aesar, USA, 99.5%), Al₂O₃ (Alfa Aesar, USA, 99.5%), H₃BO₃ (Acros Organics, USA, 99+%), Na₂CO₃ (JTBaker, USA), Al(PO₃)₃ (Alfa Aesar, USA), and ZrO₂ (Fisher Chemical, USA). The compositions of Li₂CO₃, SiO₂, and Al₂O₃ were primarily based on the SiO₂-Al₂O₃-Li₂O phase diagram (e.g., ...). Figure 1As shown in M. KrishnaMurthy et al., Phase equilibria in the system lithium metasilicate–β‐eucryptite, J. Am. Ceram. Soc. 37 (1) (1954) 14-17). Since the composition of the residual glass differs from that of the crystals, the gradients of Li₂O and Al₂O₃ were investigated to maximize the percentage of spodumene and β-spodumene crystals in the final glass-ceramic. P₂O₅ was used as a nucleating agent to introduce bulk nucleation and accelerate the nucleation rate of the crystalline phases, and ZrO₂ was used to limit crystal size to obtain transparency. Different amounts of P₂O₅ and ZrO₂ were investigated to change the number and size of crystals to optimize transparency and improve mechanical strength. B₂O₃ and Na₂O were used to promote glass-forming ability. The compositions of the various glass-ceramic samples prepared in this paper are shown in Table 1.

[0153] In this embodiment, a mixture of 200 g of powder was double-melted in a platinum crucible at 1,550 °C and held for 3 h and 5 h for homogenization and clarification. The molten glass was poured onto a stainless steel plate, annealed at 520 °C for more than 8 h, and slowly cooled to room temperature in a furnace to release thermal stress. Homogenization was verified using a Polariscope to avoid unwanted nucleation and crystal growth in the glass-ceramic.

[0154] Glass samples were cut into small pieces and prepared for ceramization. Different temperatures were selected as nucleation temperatures, and the glass transition temperature (Tg) was measured by differential scanning calorimetry (DSC). g Within a small range above ) . Different crystal growth methods are selected based on the crystallization temperature measured by DSC. The small glass slide is held at the nucleation temperature for 4 hours, then increased to the crystal growth temperature at 10℃ / min, held for 4 hours to allow crystal growth, and then slowly cooled to room temperature in the furnace.

[0155] Glass samples were ground into powder and measured using inductively coupled plasma atomic emission spectrometry (ICP-AES) to investigate compositional differences between the glass samples and the batch. DSC measurements were performed using a TA SDT 600 at a rate of 10 °C / min in a heat-cool-heat cycle to determine the glass transition temperature and crystallization temperature. The cooling process provided the known thermal history, and T... g Recorded as the onset temperature in the glass transition region. Using a rotational viscometer (VIS 403, TA Instruments) at 10... 0.7 -10 6.6Viscosity-temperature parameters were measured in the Pa·s range at a cooling rate of 20 K / min. The observed high cooling rate is attributed to the crystallization of the supercooled liquid in the lithium aluminosilicate glass.

[0156] The densities of both glass and glass-ceramics were measured at room temperature using the Archimedes method with distilled water as the liquid medium. A Cu K... α The PANalytical Empryean X-ray diffractometer obtained X-ray diffraction (XRD) patterns (2θ, 10) from radiation sources (40 kV and 40 mA). Up to 70 To identify the crystal phase and calculate the percentage of different crystals.

[0157] Ultraviolet-visible (UV-VIS) transmission spectra in the range of 250 nm to 800 nm were obtained using a Perkin-Elmer Lambda 950 UV-VIS-NIR spectrophotometer. The glass-ceramic samples used for UV-VIS spectroscopy were optically polished to a uniform thickness (2.0 ± 0.1 mm).

[0158] Table 1. Composition of LAS glass-ceramic batch materials.

[0159]

[0160] Vickers hardness and toughness were determined using a Mitutoyo HM-200 microhardness tester. At 136... o At least 10 indentations were measured on the polished surface of each sample under a diamond indenter. The hardness was measured at 0.1 kgf (1 kgf = 9.8 N) and calculated according to the following equation (1):

[0161] (1);

[0162] Where HV is Vickers hardness in GPa, F is load in kgf, and d1 and d2 are the lengths of the two diagonals left by the indenter in mm. Vickers toughness was measured at 0.8 kgf and calculated using equation (2):

[0163] (2);

[0164] Where K IC It is the indentation fracture toughness, measured in MPa·m. 0.5E is the elastic Young's modulus in GPa, H is the hardness in GPa, P is the load in N, and c0 is half the diagonal crack length in meters. The elastic modulus was measured using nanoindentation. For fracture toughness, indentation testing was used instead of the three-point bending test used in current studies due to lower dimensional requirements and smaller sample size.

[0165] The number of cracks in the indentation test was found to increase with increasing load, exhibiting an S-shaped pattern. Yoshida et al. fitted the curves of sodium aluminosilicate glasses using the Weibull equation, and Pönitzsch et al. fitted the curves of calcium aluminosilicate glasses using the Weibull equation (Yoshida, A. et al., Crack initiation behavior of sodiumaluminosilicate glasses. J. of Non-Cryst. Solids 344 (1-2) (2004) 37-43; A. Pönitzsch et al., Bulk elastic properties, hardness, and fatigue of calciumaluminosilicate glasses in the intermediate-silica range. J. of Non-Cryst. Solids 434 (2016) 1-12).

[0166] The Weibull equation is shown in equation (3):

[0167] (3)

[0168] Where F(P) is the crack probability (ideal number of cracks divided by four), P is the load, β is the scale parameter, and m is the Weibull modulus. Crack resistance is defined as F(P) = 0.5, which is the load required to produce two-quarters of the cracks.

[0169] The linear coefficient of thermal expansion (CTE) of the glass-ceramic sample was obtained using a Thermomechanical Analyzer (TMA) Q400 from TA Instruments under a force of 0.0500 N. The sample was ground to 6... 20 mm, and heated from room temperature to 300°C at a heating rate of 5°C / min.

[0170] Example 2

[0171] Glass composition

[0172] The composition from the ICP data was found to be very close to that of the batch, with errors of less than 0.5 mol% for the major oxides and less than 0.2 mol% for the minor oxides. Due to evaporation losses, the amounts of P₂O₅, Li₂O, and B₂O₃ were found to be lower than in the batch, leading to an increase in the percentage of SiO₂ and Al₂O₃ in the glass composition. Due to the large atomic mass and high melting point, the amount of ZrO₂ in the glass was found to be slightly lower than in the batch.

[0173] Crystal phase

[0174] Further investigation revealed that when Li₂O was maintained in excess, the crystal phase types derived from the XRD patterns varied primarily with the amounts of Al₂O₃ and SiO₂. When the molar percentages of Al₂O₃:Li₂O:SiO₂ were 5.4:22.5:68.3 to 7.4:20.5:68.3, the main crystal phases were petalite and LiAlSi₃O₈, with Li₂SiO₃ being the minor phase. Figure 2A ).

[0175] Without being bound by any theory, based on the XRD pattern, LiAlSi3O8 is considered to be a solid solution of β-spodumene due to similar peak positions. When the amount of Al2O3 is greater than 7.4 mol%, XRD shows only the presence of β-spodumene solid solution because no petalite phase appears in the XRD pattern. Figure 2B Again, not wanting to be bound by any theory, let's assume that LiAlSi3O8 is more transparent than lithium feldspar (LiAlSi4O). 10 It is preferable to crystallize because the LiAlO2:SiO2 ratio in LiAlSi3O8 is higher.

[0176] It was also found that when Al2O3 was below 5.4 mol%, the crystal peak at 2θ38.4 became stronger. Figure 2B When the amount of Al2O3 is reduced to 3.4 mol%, this peak is several times higher than the other peaks. Again, without being bound by any theory, this strong peak (the plane (002) of Li2SiO3) is considered to be due to the anisotropic growth of lithium metasilicate crystals in the glass-ceramic. When the amount of SiO2 is too high compared to Al2O3, SiO2 crystals may exist in the XRD pattern ( Figure 2B Furthermore, without being bound by any theory, it was found that nucleation and crystal growth temperatures do not affect the type of crystal phase, but they do affect the ratio of different crystals. The peaks of β-spodumene solid solutions were found to be more intense, while the lithium metasilicate peaks disappeared at high temperatures.

[0177] Because the crystal growth rate of transparent glass-ceramics is much lower than the maximum growth rate, the crystalline to amorphous ratio increases with increasing crystal growth temperature. This ratio can also be affected by the amounts of P₂O₅, B₂O₃, and ZrO₂. Again, without being bound by any theory, it is assumed that large Zr atoms increase the activation barrier, thus reducing the frequency of successful transitions from the liquid to the crystal. As a result, the crystalline to amorphous ratio decreases significantly with increasing ZrO₂ content. P₂O₅, as a nucleating agent, lowers the nucleation temperature and increases the nucleation rate, thus leading to an increase in the crystalline to amorphous ratio. B₂O₃ has a smaller effect on the ratio than ZrO₂ and P₂O₅. However, a large amount of B₂O₃ leads to a decrease in viscosity at the crystal growth temperature, which slightly lowers the activation barrier for atomic migration from the liquid to the crystal, thus increasing the crystalline to amorphous ratio.

[0178] Example 3

[0179] DSC pattern and viscosity

[0180] The glass transition temperature and melting point (T) were studied. m ) and the change in crystallization temperature with the amount of Li2O and Al2O3 ( Figures 3A-3B ). Discover T g It increases linearly with increasing Al2O3 content and decreasing Li2O content. Figure 3B It was found that for sample 12, which had 3.4 mol% Al₂O₃ and 24.5 mol% Li₂O, T g The temperature was 484 °C. For sample 13, which had 11.4 mol% Al₂O₃ and 16.5 mol% Li₂O, the temperature Tg increased by approximately 60 °C. Further findings revealed that T... m The decrease is due to the increase in Al2O3 and the decrease in Li2O.

[0181] Not wanting to be bound by any theory, based on the LiAlO2-SiO2 phase diagram, the crystallization peak near 750℃ is considered to be the peak of the β-spodumene solid solution. Figure 4The depth of this peak decreases with decreasing Al2O3 content, indicating that β-spodumene solid solutions are less preferred at low Al2O3 concentrations. Further analysis revealed a negative peak at 723 °C in sample LAS12 with 3.4 mol% Al2O3, which likely corresponds to the melting point of Li2SiO3. Analysis of this sample also showed another crystallization peak at approximately 860 °C. Hopefully, without being bound by any theory, this peak is attributed to β-spodumene based on the phase diagram. No petalite peak was observed in the DSC pattern. Again, without being bound by any theory, it is hypothesized that this phenomenon is due to the potentially slow growth of petalite compared to the heating rate of 10 °C / min in the DSC. Again, without being bound by any theory, it is further hypothesized that this slow growth is the reason why the glass-ceramic sample remained transparent for several hours in the furnace.

[0182] like Figures 5A-5B As shown, the viscosity-temperature curves of LAS10 and LAS11 were also compared with those of standard soda-lime silicate glass (SG80(a)). It was found that LAS10 and LAS11 crystallized at approximately 950 °C with a cooling rate of 20 K / min. It was also found that the viscosity of lithium aluminum silicate glass was lower than that of SG80 at high temperatures. The data for LAS11 were then fitted using the Yue-Ellison-Gupta-Allan (MYEGA) equation, for log... 10 η ∞ Using -2.93. The T-value fitted in the MYEGA equation. g It is 451℃, which is higher than the T from DSC. g The temperature was 61°C lower. Not wanting to be bound by any theory, it is assumed that this error may be due to the limited range of viscosity data at high temperatures. Brittleness (m) is a parameter used to understand liquid dynamics and glass transition behavior, and can also be predicted from the MYEGA equations. The brittleness of LAS11 was found to be 27.

[0183] Example 4

[0184] Density of glass samples and glass-ceramic samples

[0185] The density of the glass sample was measured and found to be 2.38 g / cm³. 3 Up to 2.47 g / cm 3 Within a certain range, it is mainly affected by the amount of ZrO2. Figure 6 The results show that the density of the glass increases with the amount of ZrO2. A multiple linear regression equation was used to predict the effect of different oxides on the glass density (Equation 4):

[0186] ρ(g / cm 3)=2.37745+0.00027[Al2O3]+0.00003[Li2O]+0.00078[B2O3]+0.00000[Na2O]+0.02481[ZrO2]+0.00000[P2O5] (4)

[0187] Where ρ is density, 2.37745 g / cm³ 3 The density of pure silicate glass is predicted from a multiple linear regression equation, which is consistent with experimental data (2.20 g / cm³). 3 Compared to the previous model, the percentage error is 8.1%. Again, not wanting to be bound by any theory, it is assumed that this percentage error is mainly due to the simplified linear model. The R-squared value of the fitted model is found to be... 2 The value was 0.92, indicating that 92% of the variability could be explained by linear regression of different oxides. According to the fitted data, the density of the glass samples increased primarily with the amount of ZrO2.

[0188] The results show that the density of the glass-ceramic sample is slightly higher than that of its parent glass. Without being bound by any theory, it is assumed that this is due to the ordered structure and fewer open spaces in the crystals of the glass-ceramic. However, it was also found that the density of the glass-ceramic is less than about 2% higher than that of its parent glass.

[0189] Example 5

[0190] transmittance

[0191] Figure 7 The transmittance of different glass-ceramic samples prepared in this paper is shown. For example... Figure 7 As shown, the first number in the glass-ceramic designation refers to the nucleation temperature and nucleation time, and the second number refers to the crystal growth temperature and crystal growth time. It was found that, except for sample LAS 26, most samples had an average transmittance higher than approximately 80% in the visible light region (390–700 nm) (Table 2).

[0192] Table 2. Transmittance of exemplary glass-ceramic samples.

[0193]

[0194] Further investigation revealed that most of the studied samples were transparent at low crystal growth temperatures, and tended to be translucent and opaque at higher crystal growth temperatures. Additionally, samples containing a large amount of lithium metasilicate were found to tend to be translucent or opaque at low crystal growth temperatures. Without being bound by any theory, it is assumed that the transparency of the glass-ceramic composition is related to the anisotropic growth of lithium metasilicate, corresponding to strong peaks in the XRD pattern.

[0195] Furthermore, samples containing a large amount of β-spodumene solid solution were found to be transparent at high crystal growth temperatures. As shown in the DSC patterns, although β-spodumene crystallized at higher temperatures, the crystals were smaller than those of petalite and lithium metasilicate at the same crystal growth temperature.

[0196] Example 6

[0197] microstructure

[0198] Figures 8A-8C Secondary electron images of the microstructure of opaque, translucent, and transparent LAS glass-ceramics obtained from SEM are shown. Crystals were observed under an electron microscope due to the different chemical durability of crystals and glass to hydrofluoric acid. The results show that the crystal size increases with crystal growth temperature and exposure time. The crystal size of the transparent glass-ceramics, directly measured under SEM, is between 20 nm and 40 nm. Small pits were observed on the crystal surface due to etching of dislocations by hydrofluoric acid.

[0199] Example 7

[0200] Vickers hardness and crack resistance

[0201] The indentation hardness and toughness of the exemplary samples disclosed herein are shown in Table 3. PPG, a standard soda-lime silicate glass containing 74 mol% SiO2, 13.3 mol% Na2O, 8.3 mol% CaO, 0.06 mol% Al2O3 and 3.7 mol% MgO

[43] , was measured under the same conditions. The indentation hardness of the glass-ceramic sample increased with increasing crystal growth temperature and was much higher than that of PPG. The indentation toughness of the glass-ceramic sample was higher than that of soda-lime silicate glass (0.75 MPa·m). 1 / 2 ) and Pyrex (0.70 MPa·m 1 / 2 Samples with higher Al2O3 content were found to have higher indentation hardness and toughness.

[0202] Figures 9A-9B The crack probability of glass-ceramic samples with different indenter loads compared to PPG is shown. The R-values ​​of the Weibull distribution for different samples are also presented. 2 Greater than 0.87. The average crack resistance of the samples was found to be 0.56 kgf, or 4 times higher than that of PPG. Without wishing to be bound by any theory, it is assumed that this high crack resistance is a result of the ceramization process. The interlocking microstructure formed by the grains in the glass-ceramic composite promotes crack bridging and deflection, thereby leading to increased crack resistance.

[0203] Example 8

[0204] coefficient of thermal expansion

[0205] Figure 10 The linear coefficient of thermal expansion (CTE) obtained by TMA in the range of 25°C to 300°C for LAS10 and LAS11 glasses and glass-ceramics is shown. The CTE of glass-ceramics was found to be between 40 and 90. 10 -7 Within the range of / ℃, its coefficient of thermal expansion is significantly higher than that of SiO2 glass (5.5). 10 -7 / ℃). The CTE of the glass-ceramic was found to be lower than that of the corresponding glass, indicating that the CTE of the lithium feldspar and β-spodumene crystals was lower than that of the glass matrix. The samples with higher Li2O content had higher CTE.

[0206] The claims are not intended to include, and should not be construed as including, a limitation of means plus function or steps plus function, unless such limitation is explicitly described in the given claim using the phrases “means for…” or “steps for…” respectively.

[0207] In view of the described processes and compositions, certain more specific aspects of the invention are described below. However, these specifically enumerated aspects should not be construed as limiting any different claims containing different or more general teachings as set forth herein, or as limiting a "specific" aspect in any way, rather than in the inherent meaning of the language and the formulas used literally therein.

[0208] Table 3. Indentation hardness and toughness of LAS glass-ceramics

[0209]

[0210] aspect:

[0211] Aspect 1: A glass-ceramic composition comprising: about 2 mol% to about 20 mol% of Al2O3; about 2 mol% to about 45 mol% of Li2O; and about 48 mol% to about 80 mol% of SiO2; having a β-spodumene phase and a lithium silicate crystal phase, and optionally a lithite phase.

[0212] Aspect 2: A glass-ceramic composition as described in Aspect 1, wherein Al2O3 is present in the form of about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 20% to about 80% of the β-spodumene phase and about 20% to about 80% of the lepidolite phase; and a secondary crystalline phase comprising up to about 10% of the lithium silicate phase.

[0213] Aspect 3: The glass-ceramic composition as described in aspect 2, wherein Li2O is present in an amount of about 20 mol% to about 25 mol%.

[0214] Aspect 4: A glass-ceramic composition as described in aspect 1, wherein Al2O3 is present in an amount of about 7 mol% to about 12 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 60% to about 90% of the β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of the lithium silicate phase.

[0215] Aspect 5: A glass-ceramic composition as described in any one of Aspects 1-4, wherein the lithium silicate crystalline phase comprises a lithium metasilicate crystalline phase.

[0216] Aspect 6: The glass-ceramic composition as described in any one of Aspects 1-5 further comprises 0 mol% to about 8 mol% of B2O3, 0 mol% to about 8 mol% of ZrO2, 0 mol% to about 5 mol% of P2O5, and 0 mol% to about 5 mol% of Na2O.

[0217] Aspect 7: A glass-ceramic composition as described in any one of Aspects 1-6, wherein the composition exhibits about 2.00 g / cm³. 3 Approximately 2.6 g / cm 3 The density.

[0218] Aspect 8: A glass-ceramic composition as described in any one of Aspects 1-7, exhibiting an average transmittance of more than about 80% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm.

[0219] Aspect 9: A glass-ceramic composition as described in any one of Aspects 1-7, exhibiting an average transmittance between 20% and 80% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm.

[0220] Aspect 10: A glass-ceramic composition as described in any one of Aspects 1-7, exhibiting an average transmittance of less than 20% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample prepared from said composition and having a thickness of about 2.00 mm.

[0221] Aspect 11: The glass-ceramic composition as described in aspect 8, comprising a plurality of grains, wherein the median size of the grains is about 20 nm to about 80 nm.

[0222] Aspect 12: The glass-ceramic composition as described in aspect 9, comprising a plurality of grains, wherein the median size of the grains is greater than about 80 nm to about 500 nm.

[0223] Aspect 13: The glass-ceramic composition as described in aspect 10, comprising a plurality of grains, wherein the median size of the grains is greater than about 500 nm.

[0224] Aspect 14: The glass-ceramic composition as described in any one of Aspects 1-13 exhibits a Vickers hardness equal to or greater than about 6.0 GPa.

[0225] Aspect 15: The glass-ceramic composition as described in any one of Aspects 1-14 exhibits a Vickers hardness that is at least about 5% greater than that of standard soda-lime silicate glass.

[0226] Aspect 16: The glass-ceramic composition as described in any one of Aspects 1-15 exhibits crack resistance greater than about 0.2 kgf.

[0227] Aspect 17: The glass-ceramic composition as described in any one of Aspects 1-16 exhibits crack resistance greater than about 0.4 kgf.

[0228] Aspect 18: A glass-ceramic composition as described in any of Aspects 1-17, exhibiting at least 4 times greater crack resistance than standard soda-lime silicate glass.

[0229] Aspect 19: The glass-ceramic composition as described in any one of Aspects 1-18, exhibiting about 40 x 10 -7 / ℃ to approximately 90x10 -7 The coefficient of thermal expansion at / ℃.

[0230] Aspect 20: A glass-ceramic composition as described in any one of Aspects 1-19, wherein the composition exhibits a glass transition temperature (T0) of about 450°C to about 600°C. g ).

[0231] Aspect 21: A glass-ceramic composition as described in any one of Aspects 1-20, wherein the composition further comprises one or more clarifying agents selected from CeO2, SnO2, Fe2O3, As2O3, Sb2O3, MnO2 or combinations thereof, and wherein the one or more clarifying agents are present in a total amount equal to or less than about 1 mol%.

[0232] Aspect 22: The glass-ceramic composition of any one of aspects 1-21 further comprises one or more coloring components selected from transition metal oxides and / or rare earth metal oxides, wherein said one or more coloring components are present in a total amount equal to or less than about 1 mol%.

[0233] Aspect 23: The glass-ceramic composition of any one of Aspects 1-22 further comprises a decolorizing agent, said decolorizing agent comprising sodium sulfate, selenium compounds, erbium oxide, cerium oxide, cobalt oxide, manganese oxide, or any combination thereof.

[0234] Aspect 24: A glass-ceramic composition as described in any one of Aspects 1-23, wherein the composition is ion-exchangeable.

[0235] Aspect 25: A glass-ceramic composition comprising: Al2O3 present in about 2 mol% to about 20 mol%; SiO2 present in about 48 mol% to about 80 mol%; R'2O present in greater than 0 mol% to about 45 mol%; and wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase.

[0236] Aspect 26: The glass-ceramic composition as described in aspect 25, wherein when R'2O comprises Li2O, the composition comprises a subcrystalline phase comprising a lithium silicate phase.

[0237] Aspect 27: A glass-ceramic composition as described in aspect 25 or 26, wherein Al2O3 is present in an amount of about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 20% to about 80% of the β-spodumene phase and about 20% to about 80% of the lepidolite phase.

[0238] Aspect 28: A glass-ceramic composition as described in aspect 26, wherein Al2O3 is present in the form of about 5 mol% to about 7.5 mol% and Li2O is present in the form of about 20 mol% to about 25 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 20% to about 80% of the β-spodumene phase and about 20% to about 80% of the lepidolite phase; and a secondary phase comprising up to 10 mol% of the lithium silicate phase.

[0239] Aspect 29: A glass-ceramic composition as described in aspect 25 or 26, wherein Al2O3 is present in an amount of about 7 mol% to about 12 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 60% to about 90% of the β-spodumene phase.

[0240] Aspect 30: A glass-ceramic composition as described in aspect 26, wherein Al2O3 is present in an amount of about 7 mol% to about 12 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 60% to about 90% of the β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of the lithium silicate phase.

[0241] Aspect 31: A glass-ceramic composition as described in any one of Aspects 25-30, wherein the composition further comprises: B2O3 present in 0 mol% to about 8 mol%, ZrO2 present in 0 mol% to about 8 mol%, and P2O5 present in 0 mol% to about 5 mol%.

[0242] Aspect 32: A glass-ceramic composition as described in any one of Aspects 25-31, wherein the composition is transparent, translucent or opaque.

[0243] Aspect 33: The glass-ceramic composition as described in any one of Aspects 25-32 further comprises a compression layer.

[0244] Aspect 34: A glass-ceramic composition as described in any one of Aspects 25-33, wherein the composition exhibits about 2.00 g / cm³. 3 Approximately 2.6 g / cm 3 The density.

[0245] Aspect 35: A glass-ceramic composition as described in any one of Aspects 32-34, wherein the composition is transparent and comprises a plurality of grains, wherein the median size of the grains is about 20 nm to about 80 nm.

[0246] Aspect 36: A glass-ceramic composition as described in any one of Aspects 32-34, wherein the composition is translucent and comprises a plurality of grains, wherein the median size of the grains is greater than about 80 nm to about 500 nm.

[0247] Aspect 37: A glass-ceramic composition as described in any one of Aspects 32-34, wherein the composition is opaque and comprises a plurality of grains, wherein the median size of the grains is about greater than 500 nm.

[0248] Aspect 38: The glass-ceramic composition as described in any one of Aspects 25-37 exhibits a Vickers hardness equal to or greater than about 6.0 GPa.

[0249] Aspect 39: The glass-ceramic composition as described in any one of Aspects 25-38 exhibits a Vickers hardness that is at least about 5% greater than that of standard soda-lime silicate glass.

[0250] Aspect 40: The glass-ceramic composition as described in any one of Aspects 25-39 exhibits crack resistance greater than about 0.2 kgf.

[0251] Aspect 41: The glass-ceramic composition as described in any one of Aspects 25-40 exhibits crack resistance greater than about 0.4 kgf.

[0252] Aspect 42: A glass-ceramic composition as described in any of Aspects 25-41, which exhibits at least 4 times greater crack resistance than standard soda-lime silicate glass.

[0253] Aspect 43: The glass-ceramic composition as described in any one of aspects 25-42, exhibiting about 40 x 10 -7 / ℃ to approximately 90x10 -7 The coefficient of thermal expansion at / ℃.

[0254] Aspect 44: A glass-ceramic composition as described in any one of Aspects 25-43, wherein the composition exhibits a glass transition temperature (T0) of about 450°C to about 600°C. g ).

[0255] Aspect 45: A glass-ceramic composition as described in any one of Aspects 25-44, wherein the composition further comprises one or more clarifying agents selected from CeO2, SnO2, Fe2O3, As2O3, Sb2O3, MnO2 or combinations thereof, and wherein the one or more clarifying agents are present in a total amount equal to or less than about 1 mol%.

[0256] Aspect 46: A glass-ceramic composition as described in any one of Aspects 25-45, wherein the composition further comprises a decolorizing agent comprising sodium sulfate, a selenium compound, erbium oxide, cerium oxide, cobalt oxide, manganese oxide, or any combination thereof.

[0257] Aspect 47: A glass-ceramic composition as described in any one of Aspects 25-46, further comprising one or more coloring components selected from transition metal oxides and / or rare earth metal oxides, wherein said one or more coloring components are present in a total amount equal to or less than about 1 mol%.

[0258] Aspect 48: A glass-ceramic composition as described in any one of Aspects 25-47, wherein Ag2O and / or Cu2O and / or CuO are present, and wherein the glass-ceramic composition exhibits antimicrobial, antiviral, antibacterial and / or antifungal properties.

[0259] Aspect 49: A glass-ceramic article comprising any one of aspects 1-48.

[0260] Aspect 50: A glass-ceramic article comprising a composition as described in any one of Aspects 33-48, wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is about 1 μm to about 100 μm.

[0261] Aspect 51: A glass-ceramic article comprising a composition as described in any one of Aspects 33-48, wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is at most about 25% of the thickness of the glass-ceramic article.

[0262] Aspect 52: A glass-ceramic article comprising: about 2 mol% to about 20 mol% of Al2O3; about 2 mol% to about 45 mol% of Li2O; and about 48 mol% to about 80 mol% of SiO2; having a β-spodumene phase and a lithium silicate phase and optionally a lithite phase.

[0263] Aspect 53: A glass-ceramic article comprising: Al2O3 present in about 2 mol% to about 20 mol%; SiO2 present in about 48 mol% to about 80 mol%; and R'2O present in greater than 0 mol% to about 45 mol%; wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase.

[0264] Aspect 54: Articles as described in any one of Aspects 49-53, wherein the articles include hollow vessels, tableware, containers, plates, plates, float plates, cookware, powders, fibers, cones, spheres, blades, or any combination thereof.

[0265] Aspect 55: Articles as described in any one of Aspects 49-54, wherein the articles are formed by a float / flat glass pressing process, a press-blown process, a blow-blown process, or any combination thereof.

[0266] Aspect 56: A tableware comprising any one of aspects 1-48.

[0267] Aspect 57: The tableware as described in aspect 56, wherein the tableware is formed by glass pressing, press blowing and / or blow blowing processes.

[0268] Aspect 58: A hollow vessel comprising any one of aspects 1-48.

[0269] Aspect 59: Hollow vessel as described in aspect 57, wherein the hollow vessel is formed by glass pressing, press blowing and / or blow blowing processes.

[0270] Aspect 60: A powder comprising any one of the compositions described in aspects 1-48.

[0271] Aspect 61: A cookware comprising any one of aspects 1-48.

[0272] Aspect 62: Cookware as described in aspect 61, wherein the cookware is formed by glass pressing, press blowing and / or blow blowing processes.

[0273] Aspect 63: A fiber comprising the composition as described in any one of aspects 1-48.

[0274] Aspect 64: Fibers as described in aspect 63, wherein the fibers are formed by continuous or discontinuous fiber drawing or spinning processes.

[0275] Aspect 65: A float or flat glass pressing product comprising any one of aspects 1-48.

[0276] Aspect 66: A pressure blow process product comprising the composition as described in any one of Aspects 1-48.

[0277] Aspect 67: A blow-dry product comprising any one of aspects 1-48.

[0278] Aspect 68: A method comprising: a) forming a mixture comprising: about 2 mol% to about 20 mol% of Al2O3; about 2 mol% to about 45 mol% of Li2O; and about 48 mol% to about 80 mol% of SiO2; b) forming a homogeneous composition; and c) ceramizing the homogeneous composition to form a glass-ceramic composition.

[0279] Aspect 69: The method of aspect 68, wherein the mixture further comprises 0 mol% to about 8 mol% of ZrO2, or 0 mol% to about 5 mol% of P2O5 or a combination thereof.

[0280] Aspect 70: The method as described in aspect 68 or 69, wherein the step of forming the homogeneous composition comprises melting the mixture in a furnace at a temperature of about 1,300°C to about 1,700°C for a first predetermined time.

[0281] Aspect 71: The method of aspect 70 further includes an annealing step at a temperature of about 450°C to about 700°C.

[0282] Aspect 72: The method of any one of Aspects 68-71, wherein the ceramization step comprises heating the homogeneous composition at a nucleation temperature for a second predetermined time.

[0283] Aspect 73: The method as described in aspect 72, wherein the nucleation temperature is about 450°C to about 650°C.

[0284] Aspect 74: The method as described in aspect 71 or 72, wherein the ceramization step further comprises heating the composition to a crystallization temperature at a rate of about 5°C / min to about 15°C / min and holding the composition at the crystallization temperature for a third predetermined time.

[0285] Aspect 75: The method as described in aspect 74, wherein the crystallization temperature is about 580°C to about 800°C.

[0286] Aspect 76: The method of any one of Aspects 74-75, wherein the first, second, and / or the third predetermined time is about 3 to 5 hours.

[0287] Aspect 77: The method of any one of Aspects 72-76, wherein P2O5 is a nucleating agent.

[0288] Aspect 78: The method of any one of Aspects 74-77, wherein ZrO2 is a crystal size growth limiting agent.

[0289] Aspect 79: The method of any one of Aspects 68-78, wherein the glass-ceramic composition comprises a β-spodumene phase, optionally a lepidolite phase and a lithium silicate crystalline phase.

[0290] Aspect 80: The method of aspect 79, wherein Al2O3 is present in the form of about 5 mol% to about 7.5 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 20% to about 80% of the β-spodumene phase and about 20% to about 80% of the lepidolite phase; and a secondary crystalline phase comprising up to about 10% of the lithium silicate phase.

[0291] Aspect 81: The method as described in aspect 80, wherein Li2O is present in the composition at about 20 mol% to about 25 mol%.

[0292] Aspect 82: The method of aspect 81, wherein Al2O3 is present in the form of about 7 mol% to about 12 mol%, the glass-ceramic composition comprising a main crystalline phase comprising about 60% to about 90% of the β-spodumene phase; and a secondary crystalline phase comprising up to about 10% of the lithium silicate phase.

[0293] Aspect 83: The method of any one of aspects 80-82, wherein the lithium silicate crystalline phase comprises the lithium metasilicate crystalline phase.

[0294] Aspect 84: The method of any one of claims 68-83, wherein the mixture further comprises 0 mol% to about 8 mol% of B2O3 and 0 mol% to about 8 mol% of Na2O.

[0295] Aspect 85: The method of any one of aspects 68-84 further includes an ion exchange treatment step, said step comprising exposure to a salt bath, spray, paste, steam-assisted ion exchange, plasma-assisted ion exchange, or any combination thereof.

[0296] Aspect 86: The method as described in aspect 85, wherein the ion exchange process is electrically accelerated.

[0297] Aspect 87: The method as described in Aspect 85 or 86, wherein the ion exchange treatment step comprises placing the glass-ceramic composition in a molten salt bath containing sodium, potassium, silver, or copper (I) ions or combinations thereof, under conditions that effectively provide ion exchange of the glass-ceramic composition.

[0298] Aspect 88: The method of aspect 87, wherein the ion-exchanged glass-ceramic composition comprises: Al2O3 present in about 2 mol% to about 20 mol%; SiO2 present in about 48 mol% to about 80 mol%; R'2O present in greater than 0 mol% to about 45 mol%; and wherein R'2O comprises Li2O, Na2O, K2O, Ag2O, Cu2O, CuO or combinations thereof, wherein the composition comprises a main crystalline phase comprising a β-spodumene phase and optionally a spodumene phase.

[0299] Aspect 89: The method as described in Aspect 87 or 88, wherein the conditions for effectively providing the ion-exchange glass-ceramic composition include exposing the glass-ceramic composition to molten salt at a temperature of about 380°C to about 500°C for a period of about 4 hours to about 20 hours.

[0300] Aspect 90: The method of any one of aspects 87-89, wherein the ion-exchanged glass-ceramic composition comprises a compressive stress layer.

[0301] Aspect 91: The method of any one of aspects 68-90, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits about 2.00 g / cm³. 3 Approximately 2.6 g / cm 3 The density.

[0302] Aspect 92: The method of any one of Aspects 68-91, wherein for a sample formed of the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition and having a thickness of about 2.00 mm, the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits an average transmittance of more than about 80% at wavelengths in the range of about 390 nm to about 700 nm.

[0303] Aspect 93: The method of any one of Aspects 68-92, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits an average transmittance between 20% and 80% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample formed of the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition and having a thickness of about 2.00 mm.

[0304] Aspect 94: The method of any one of Aspects 68-93, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits an average transmittance of less than 20% at wavelengths in the range of about 390 nm to about 700 nm, as measured for a sample formed of the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition and having a thickness of about 2.00 mm.

[0305] Aspect 95: The method of aspect 94, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition comprises a plurality of grains, wherein the size of the grains is from about 20 nm to about 80 nm.

[0306] Aspect 96: The method of aspect 95, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition comprises a plurality of grains, wherein the median size of the grains is greater than about 80 nm to about 500 nm.

[0307] Aspect 97: The method of aspect 96, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition comprises a plurality of grains, wherein the median size of the grains is greater than about 500 nm.

[0308] Aspect 98: The method of any one of Aspects 68-97, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits a Vickers hardness equal to or greater than about 6.0 GPa.

[0309] Aspect 99: The method of any one of Aspects 68-98, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits a Vickers hardness at least about 5% greater than that of a composition comprising standard soda-lime silicate glass.

[0310] Aspect 100: The method of any one of Aspects 68-99, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits crack resistance greater than about 0.2 kgf.

[0311] Aspect 101: The method of any one of aspects 68-100, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits crack resistance greater than about 0.4 kgf.

[0312] Aspect 102: The method of any one of aspects 68-101, wherein the glass-ceramic composition exhibits at least 4 times higher crack resistance than a composition comprising standard soda-lime silicate glass.

[0313] Aspect 103: The method of any one of aspects 68-102, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits about 40 x 10⁻⁶. -7 / ℃ to approximately 90x10 -7 The coefficient of thermal expansion at / ℃.

[0314] Aspect 104: The method of any one of Aspects 68-103, wherein the glass-ceramic composition and / or the ion-exchanged glass-ceramic composition exhibits a glass transition temperature T of about 450°C to about 600°C. g .

[0315] Aspect 105: The method of any one of aspects 68-104 further includes the step of forming a glass-ceramic article.

[0316] Aspect 106: The method of aspect 105, wherein the step of forming the glass-ceramic article includes float or flat pressing, pressure blowing, blow blowing, or any combination thereof.

[0317] Aspect 107: The method as described in Aspect 105 or 106, wherein the glass-ceramic article comprises the ion-exchange composition, and wherein the compression layer extends from the surface of the article to a depth of the compression layer, wherein the depth is about 1 μm to about 100 μm.

[0318] Aspect 108: The method of any one of Aspects 105-107, wherein the glass-ceramic article comprises the ion-exchange composition, and wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is at most about 25% of the thickness of the glass-ceramic article.

[0319] Aspect 109: The method of any one of Aspects 105-108, wherein the articles comprise hollow vessels, tableware, containers, plates, plates, float plates, cookware, powders, fibers, cones, spheres, blades, or any combination thereof.

[0320] Aspect 110: A method of forming an article comprising forming a composition as described in any one of Aspects 1-48; and subsequently forming the article, wherein the article comprises a hollow vessel, tableware, container, plate, plate, float / flat plate, cookware, powder, fiber, cone, sphere, blade, or any combination thereof.

[0321] Aspect 111: The method of aspect 110, wherein the forming step comprises a float / flat plate pressing process, a pressure blowing process, a blow blowing process, or any combination thereof.

[0322] Aspect 112: The method as described in aspect 110 or 111, wherein the step of forming the composition comprises the method as described in any one of aspects 68-104.

[0323] References

[0324]

[0325]

[0326]

[0327]

Claims

1. A glass-ceramic article comprising: a) 5 mol% to 7.5 mol% Al2O3; b) 20 mol% to 25 mol% Li₂O; c) 48 mol% to 80 mol% SiO2; and d) 0.01 mol% to 1 mol% of P2O5; It has a main crystalline phase comprising 20% ​​to 80% β-spodumene phase and 20% to 80% lepidolite phase, and a secondary crystalline phase comprising up to 10% lithium silicate phase.

2. The glass-ceramic article of claim 1, wherein the lithium silicate crystalline phase includes the lithium metasilicate crystalline phase.

3. The glass-ceramic article as described in claim 1 or 2, further comprising: a) 0.01 mol% to 8 mol% of B2O3, b) 0.01 mol% to 8 mol% ZrO2, and c) 0.01 mol% to 5 mol% Na2O.

4. The glass-ceramic article of claim 1 or 2, wherein the article exhibits a density of 2.00 g / cm 3 to 2.6 g / cm 3 .

5. The glass-ceramic article as claimed in claim 1 or 2, wherein for a sample prepared from the glass-ceramic article and having a thickness of 2.00 mm, the glass-ceramic article exhibits an average transmittance of greater than 80% in the wavelength range of 390 nm to 700 nm.

6. The glass-ceramic article as claimed in claim 1 or 2, wherein for a sample prepared from the glass-ceramic article and having a thickness of 2.00 mm, the glass-ceramic article exhibits an average transmittance between 20% and 80% in the wavelength range of 390 nm to 700 nm.

7. The glass-ceramic article of claim 1 or 2, wherein for a sample prepared from the glass-ceramic article and having a thickness of 2.00 mm, the glass-ceramic article exhibits an average transmittance of less than 20% in the wavelength range of 390 nm to 700 nm.

8. The glass-ceramic article of claim 5, comprising a plurality of grains, wherein the median size of the grains is 20 nm to 80 nm.

9. The glass-ceramic article of claim 6, comprising a plurality of grains, wherein the median size of the grains is greater than 80 nm to 500 nm.

10. The glass-ceramic article of claim 7, comprising a plurality of grains, wherein the median size of the grains is greater than 500 nm.

11. The glass-ceramic article as claimed in claim 1 or 2, exhibiting a Vickers hardness equal to or greater than 6.0 GPa.

12. The glass-ceramic article as claimed in claim 1 or 2, which exhibits a Vickers hardness at least 5% greater than that of standard soda-lime silicate glass.

13. The glass-ceramic article as claimed in claim 1 or 2, exhibiting crack resistance greater than 0.2 kgf.

14. The glass-ceramic article as claimed in claim 1 or 2, exhibiting crack resistance greater than 0.4 kgf.

15. The glass-ceramic article as claimed in claim 1 or 2, which exhibits at least 4 times higher crack resistance than standard soda-lime silicate glass.

16. The glass-ceramic article of claim 1 or 2, exhibiting a coefficient of thermal expansion of 40 x 10 -7 / °C to 90 x 10 -7 / °C.

17. The glass-ceramic article of claim 1 or 2, wherein the article exhibits a glass transition temperature (Tg) of 450 °C to 600 °C. g ).

18. The glass-ceramic article of claim 1 or 2, wherein the article further comprises one or more clarifying agents selected from CeO2, SnO2, Fe2O3, As2O3, Sb2O3, or MnO2, and wherein the one or more clarifying agents are present in a total amount equal to or less than 1 mol%.

19. The glass-ceramic article of claim 1 or 2, further comprising one or more coloring components selected from transition metal oxides and / or rare earth metal oxides, wherein said one or more coloring components are present in a total amount equal to or less than 1 mol%.

20. The glass-ceramic article as claimed in claim 1 or 2, further comprising a decolorizing agent, said decolorizing agent comprising sodium sulfate, selenium compound, erbium oxide, cerium oxide, cobalt oxide, or manganese oxide.

21. The glass-ceramic article as claimed in claim 1 or 2, wherein the article is ion-exchangeable.

22. A glass-ceramic article comprising: a) Al₂O₃ present in quantities ranging from 5 mol% to 7.5 mol%, b) SiO2 present in a concentration of 48 mol% to 80 mol%; c) R2 present in amounts greater than 20 mol% to 25 mol%; and d) P₂O₅ present in quantities ranging from 0.01 mol% to 1 mol%; and R2 comprises Li2O, Na2O, K2O, Ag2O, Cu2O, or CuO, wherein the article comprises a main crystalline phase comprising 20% ​​to 80% β-spodumene phase and 20% to 80% lepidolite phase, and a secondary crystalline phase comprising up to 10% lithium silicate phase.

23. The glass-ceramic article of claim 22, wherein R2 comprises Li2O.

24. The glass-ceramic article of claim 22 or 23, wherein the article further comprises: a) B₂O₃ present in quantities ranging from 0.01 mol% to 8 mol%, b) 0.01 mol% to 8 mol% ZrO2.

25. The glass-ceramic article as claimed in claim 22 or 23, wherein the article is transparent, translucent, or opaque.

26. The glass-ceramic article as claimed in claim 22 or 23, further comprising a compression layer.

27. The glass-ceramic article of claim 22 or 23, wherein the article exhibits a density of 2.00 g / cm3 3 to 2.6 g / cm3 3 .

28. The glass-ceramic article of claim 22 or 23, wherein the article is transparent and comprises a plurality of grains, wherein the median size of the grains is 20 nm to 80 nm.

29. The glass-ceramic article of claim 22 or 23, wherein the article is translucent and comprises a plurality of grains, wherein the median size of the grains is greater than 80 nm to 500 nm.

30. The glass-ceramic article of claim 22 or 23, wherein the article is opaque and comprises a plurality of grains, wherein the median size of the grains is greater than 500 nm.

31. The glass-ceramic article as claimed in claim 22 or 23, exhibiting a Vickers hardness equal to or greater than 6.0 GPa.

32. The glass-ceramic article as claimed in claim 22 or 23, which exhibits a Vickers hardness at least 5% greater than that of standard soda-lime silicate glass.

33. The glass-ceramic article as claimed in claim 22 or 23, exhibiting crack resistance greater than 0.2 kgf.

34. The glass-ceramic article as claimed in claim 22 or 23, exhibiting crack resistance greater than 0.4 kgf.

35. The glass-ceramic article as claimed in claim 22 or 23, which exhibits at least 4 times greater crack resistance than standard soda-lime silicate glass.

36. The glass-ceramic article as claimed in claim 22 or 23, exhibiting a size of 40 x 10. -7 / ℃ to 90x10 -7 The coefficient of thermal expansion at / ℃.

37. The glass-ceramic article of claim 22 or 23, wherein the article exhibits a glass transition temperature (T0) of 450°C to 600°C. g ).

38. The glass-ceramic article of claim 22 or 23, wherein the article further comprises one or more clarifying agents selected from CeO2, SnO2, Fe2O3, As2O3, Sb2O3, or MnO2, and wherein the one or more clarifying agents are present in a total amount equal to or less than 1 mol%.

39. The glass-ceramic article of claim 22 or 23, wherein the article further comprises a decolorizing agent, the decolorizing agent comprising sodium sulfate, selenium compounds, erbium oxide, cerium oxide, cobalt oxide, or manganese oxide.

40. The glass-ceramic article of claim 22 or 23, further comprising one or more coloring components selected from transition metal oxides and / or rare earth metal oxides, wherein said one or more coloring components are present in a total amount equal to or less than 1 mol%.

41. The glass-ceramic article of claim 22 or 23, wherein Ag2O and / or Cu2O and / or CuO are present, and wherein the glass-ceramic article exhibits antimicrobial, antiviral, antibacterial and / or antifungal properties.

42. The glass-ceramic article of claim 26, wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is from 1 μm to 100 μm.

43. The glass-ceramic article of claim 26, wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is at most 25% of the thickness of the glass-ceramic article.

44. The article of claim 22, wherein the article comprises a hollow vessel, tableware, board, cookware, powder, fiber, cone, sphere, or blade.

45. The article of claim 22, wherein the article is formed by a float glass or flat glass pressing process, a press-blown process, or a blow-blown process.

46. ​​A tableware comprising the article of any one of claims 1-41.

47. The tableware as claimed in claim 46, wherein the tableware is formed by a pressing process, a press-blowing process, and / or a blow-blowing process.

48. A hollow vessel comprising the article of any one of claims 1-41.

49. The hollow vessel of claim 48, wherein the hollow vessel is formed by a pressing process, a press-blowing process, and / or a blow-blowing process.

50. A powder comprising the article as claimed in any one of claims 1-41.

51. A cookware comprising the article of any one of claims 1-41.

52. The cookware of claim 51, wherein the cookware is formed by a pressing process, a press-blowing process, and / or a blow-blowing process.

53. A fiber comprising the article as claimed in any one of claims 1-41.

54. The fiber of claim 53, wherein the fiber is formed by a continuous or discontinuous fiber drawing or spinning process.

55. A float / flat glass pressing product comprising the article of any one of claims 1-41.

56. A pressure blown product comprising the article of any one of claims 1-41.

57. A blow-dry product comprising an article of any one of claims 1-41.

58. A method for preparing glass-ceramic articles, comprising: a) Forming a mixture comprising the following: 5 mol% to 7.5 mol% Al2O3; 20 mol% to 25 mol% Li₂O; 48 mol% to 80 mol% SiO2; and 0.01 mol% to 1 mol% of P2O5; b) Formation of a homogeneous composition; as well as c) Ceramizing the homogeneous composition to form a glass-ceramic article having a main crystalline phase comprising 20% ​​to 80% β-spodumene phase and 20% to 80% lepidolite phase, and a secondary crystalline phase comprising up to 10% lithium silicate phase.

59. The method of claim 58, wherein the mixture further comprises 0.01 mol% to 8 mol% ZrO2.

60. The method of claim 58 or 59, wherein the step of forming the homogeneous composition comprises melting the mixture in a furnace at a temperature of 1,300°C to 1,700°C for a first predetermined time.

61. The method of claim 60, further comprising the step of annealing at a temperature of 450°C to 700°C.

62. The method of claim 60, wherein the ceramization step comprises heating the homogeneous composition at a nucleation temperature for a second predetermined time.

63. The method of claim 62, wherein the nucleation temperature is 450°C to 650°C.

64. The method of claim 62, wherein the ceramization step further comprises heating the homogeneous composition to a crystallization temperature at a rate of 5°C / min to 15°C / min and holding the homogeneous composition at the crystallization temperature for a third predetermined time.

65. The method of claim 64, wherein the crystallization temperature is 580°C to 800°C.

66. The method of claim 64, wherein the first predetermined time, the second predetermined time, and / or the third predetermined time are 3 to 5 hours.

67. The method of claim 62, wherein P2O5 is a nucleating agent.

68. The method of claim 64, wherein ZrO2 is a crystal size growth limiting agent.

69. The method of claim 58, wherein the lithium silicate crystalline phase comprises lithium metasilicate crystalline phase.

70. The method of claim 58, wherein the mixture further comprises a) 0.01 mol% to 8 mol% of B2O3, and b) 0.01 mol% to 8 mol% Na2O.

71. The method of claim 58, wherein the glass-ceramic article exhibits 2.00 g / cm³. 3 Up to 2.6 g / cm 3 The density.

72. The method of claim 58, wherein for a sample formed from the glass-ceramic article and having a thickness of 2.00 mm, the glass-ceramic article exhibits an average transmittance of greater than 80% in the wavelength range of 390 nm to 700 nm.

73. The method of claim 58, wherein the glass-ceramic article exhibits an average transmittance between 20% and 80% in the wavelength range of 390 nm to 700 nm, as measured for a sample formed from the glass-ceramic article and having a thickness of 2.00 mm.

74. The method of claim 58, wherein the glass-ceramic article exhibits an average transmittance of less than 20% in the wavelength range of 390 nm to 700 nm, as measured for a sample formed from the glass-ceramic article and having a thickness of 2.00 mm.

75. The method of claim 74, wherein the glass-ceramic article comprises a plurality of grains, wherein the size of the grains is from 20 nm to 80 nm.

76. The method of claim 75, wherein the glass-ceramic article comprises a plurality of grains, wherein the median size of the grains is greater than 80 nm to 500 nm.

77. The method of claim 76, wherein the glass-ceramic article comprises a plurality of grains, wherein the median size of the grains is greater than 500 nm.

78. The method of claim 58, wherein the glass-ceramic article exhibits a Vickers hardness equal to or greater than 6.0 GPa.

79. The method of claim 58, wherein the glass-ceramic article exhibits a Vickers hardness at least 5% greater than that of articles comprising standard soda-lime silicate glass.

80. The method of claim 58, wherein the glass-ceramic article exhibits crack resistance greater than 0.2 kgf.

81. The method of claim 58, wherein the glass-ceramic article exhibits crack resistance greater than 0.4 kgf.

82. The method of claim 58, wherein the glass-ceramic article exhibits at least four times greater crack resistance than articles comprising standard soda-lime silicate glass.

83. The method of claim 58, wherein the glass-ceramic article exhibits a size of 40 x 10. -7 / ℃ to 90x10 -7 The coefficient of thermal expansion at / ℃.

84. The method of claim 58, wherein the glass-ceramic article exhibits a glass transition temperature T of 450°C to 600°C. g .

85. The method of claim 58, further comprising an ion exchange treatment step, the step comprising exposure to a salt bath, spray, paste, steam-assisted ion exchange, or plasma-assisted ion exchange.

86. The method of claim 85, wherein the ion exchange process is electrically accelerated.

87. The method of claim 85 or 86, wherein the ion exchange treatment step comprises placing the glass-ceramic article in a molten salt bath containing sodium, potassium, silver, or copper (I) ions, provided that ion exchange is effectively provided.

88. The method of claim 87, wherein the ion-exchanged glass-ceramic article comprises: a) Al2O3 present in quantities ranging from 5 mol% to 7.5 mol%; b) SiO2 present in a concentration of 48 mol% to 80 mol%; c) R2 present in amounts greater than 20 mol% to 25 mol%; and d) 0.01 mol% to 1 mol% of P2O5; R2 comprises Li2O, Na2O, K2O, Ag2O, Cu2O, or CuO, wherein the article comprises a main crystalline phase comprising 20% ​​to 80% β-spodumene phase and 20% to 80% lepidolite phase, and a secondary crystalline phase comprising up to 10% lithium silicate phase.

89. The method of claim 87, wherein the conditions for effectively providing the ion-exchanged glass-ceramic article include exposing the glass-ceramic article to molten salt at a temperature of 380°C to 500°C for 4 to 20 hours.

90. The method of claim 87, wherein the ion-exchanged glass-ceramic article comprises a compression layer.

91. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits 2.00 g / cm³. 3 Up to 2.6 g / cm 3 The density.

92. The method of claim 87, wherein for a sample formed from the ion-exchanged glass-ceramic article having a thickness of 2.00 mm, the ion-exchanged glass-ceramic article exhibits an average transmittance of greater than 80% in the wavelength range of 390 nm to 700 nm.

93. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits an average transmittance between 20% and 80% in the wavelength range of 390 nm to 700 nm, as measured for a sample formed from the ion-exchanged glass-ceramic article and having a thickness of 2.00 mm.

94. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits an average transmittance of less than 20% in the wavelength range of 390 nm to 700 nm, as measured for a sample formed from the ion-exchanged glass-ceramic article and having a thickness of 2.00 mm.

95. The method of claim 94, wherein the ion-exchanged glass-ceramic article comprises a plurality of grains, wherein the size of the grains is from 20 nm to 80 nm.

96. The method of claim 95, wherein the ion-exchanged glass-ceramic article comprises a plurality of grains, wherein the median size of the grains is greater than 80 nm to 500 nm.

97. The method of claim 96, wherein the ion-exchanged glass-ceramic article comprises a plurality of grains, wherein the median size of the grains is greater than 500 nm.

98. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits a Vickers hardness equal to or greater than 6.0 GPa.

99. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits a Vickers hardness at least 5% greater than that of articles comprising standard soda-lime silicate glass.

100. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits a crack resistance greater than 0.2 kgf.

101. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits crack resistance greater than 0.4 kgf.

102. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits a 40x10⁻⁶ Ω·cm². -7 / ℃ to 90x10 -7 The coefficient of thermal expansion at / ℃.

103. The method of claim 87, wherein the ion-exchanged glass-ceramic article exhibits a glass transition temperature T of 450°C to 600°C. g .

104. The method of claim 90, further comprising the step of forming a glass-ceramic article.

105. The method of claim 104, wherein the step of forming the glass-ceramic article includes a float glass or flat sheet pressing process, a pressure blowing process, or a blow blowing process.

106. The method of claim 104, wherein the glass-ceramic article comprises the ion-exchanged article, and wherein the compression layer extends from the surface of the article to a depth of the compression layer, wherein the depth is from 1 μm to 100 μm.

107. The method of claim 104, wherein the glass-ceramic article comprises the ion-exchanged article, and wherein the compression layer extends from the surface of the article to a depth of the compression layer, and wherein the depth is at most 25% of the thickness of the glass-ceramic article.

108. The method of claim 104, wherein the article comprises a hollow vessel, tableware, board, cookware, powder, fiber, cone, sphere, or blade.

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