Glass-ceramics and glasses

Abstract

The present application relates to glass-ceramics and glasses. The glass-ceramics comprise: a silicate glass and a crystalline phase, wherein the crystalline phase includes non-stoichiometric sub-valent oxides of tungsten and / or molybdenum (or titanium) forming a 'bronze' type solid state defect structure in which vacancies are occupied by dopant cations.

Description

[0001] Cross-reference

[0002] This application claims priority to U.S. Application No. 62 / 575,763, filed October 23, 2017, and is a continuation-in-part of U.S. Application No. 15 / 840,040, filed December 13, 2017, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure generally relates to articles comprising glass and / or glass-ceramics, and more specifically, to compositions and methods for forming such articles. Background Technology

[0004] Alkali metal silicate glass-ceramics with ultraviolet (“UV”) and near-infrared (“NIR”) absorption properties are a class of glass-ceramics that exhibit optical properties depending on the wavelength of light incident on them. Conventional UV / IR blocking glasses (with low or high visible light transmittance) are formed by introducing certain cationic substances (e.g., Fe²⁺ to absorb NIR wavelengths, Fe³⁺ to absorb UV wavelengths, and other dopants (e.g., Co, Ni, and Se) to modify visible light transmittance) that are incorporated into a glass network. Typically, these glass-ceramics are produced by melting the components together to form a glass, followed by in-situ formation of submicron precipitates through post-forming heat treatment. These submicron precipitates (e.g., tungstate and molybdate crystals) are absorbent for specific wavelength bands, giving the glass-ceramic inherent optical properties. Such conventional glass-ceramics can be produced in transparent or milky forms.

[0005] It is believed that in order to produce glasses and glass-ceramics that are transparent at visible wavelengths, conventional tungsten- and molybdenum-containing alkali silicate glasses are limited to a specific and narrow compositional range. The believed compositional range is based on the perceived solubility limit of tungsten oxide within the peralkaline glass. For example, when batched and melted in a conventional manner, at low temperatures during the initial stages of the melt immediately after charging into the furnace, the tungsten oxide reacts with the alkali metal oxides in the batch to form a dense alkali tungstate liquid (e.g., the reaction occurs at about 500°C). Because of this high density phase, it quickly separates at the bottom of the crucible. At significantly higher temperatures (e.g., above about 1000°C), the silicate components begin to melt and, because of their lower density, they remain on top of the alkali tungstate liquid. The difference in density of the components results in the layering of the different liquids, which leads those skilled in the art to believe that they are immiscible with one another. This effect is observed particularly when R2O (e.g., Li20, Na20, K20, Rb20, Cs20) minus Al203is about 0 mole% or greater. The resulting apparent liquid immiscibility at the melting temperature results in the tungsten-rich phase to separate and crystallize when it cools, which manifests itself as opaque crystals that are milky in color. Molybdenum-containing melts also suffer from this problem.

[0006] Those skilled in the art observe the separation of the tungsten-rich and / or molybdenum-rich phase from the silicate-rich phase and believe that the solubility limit of tungsten and / or molybdenum in the silicate-rich phase (e.g., about 2.5 mole%). The believed solubility limit prevents the glass from becoming supersaturated with tungsten oxide or molybdenum oxide, thereby preventing the formation of glass-ceramics with crystalline phases containing these elements by controlled precipitation of components upon heat treatment for shaping. Thus, the believed solubility limit prevents the development of glass-ceramic compositions that achieve sufficient amounts of dissolvable tungsten and / or molybdenum to enable the formation of wavelength-dependent submicron-sized crystals containing tungsten and / or molybdenum by subsequent heat treatment.

[0007] In view of these limitations, new compositions and methods are needed that would facilitate improved near-infrared and ultraviolet blocking (e.g., by higher tungsten and molybdenum solubility). SUMMARY

[0008] It has been discovered that a homogeneous single phase super-alkaline melt containing W or Mo can be obtained by using a "bound" alkaline material as described herein. Exemplary bound alkaline materials can include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspar, alkaline containing aluminosilicates and / or other naturally occurring or man-made alkaline containing materials and one or more minerals containing aluminum and / or silicon atoms. By introducing the alkaline material in a bound form, the alkaline material can not react with the W or Mo present in the melt to form a dense alkaline tungstate and / or molybdate liquid. In addition, variations in such batch materials can enable melting of strong super-alkaline compositions (e.g., R2O-Al2O3= about 2.0 mole% or greater) without forming any alkaline tungstate and / or molybdate second phase. This also enables varying the melting temperature and mixing method and still produce a single phase homogeneous glass.

[0009] According to aspects of the disclosure, the glass-ceramic comprises: a silicate-containing glass and a crystalline phase, wherein the crystalline phase includes a non-stoichiometric sub-valent oxide of tungsten and / or molybdenum (or titanium) forming a 'bronze' type solid state defect structure in which vacancies are occupied by dopant cations.

[0010] In some embodiments, the glass-ceramic comprises an amorphous phase and a crystalline phase, the crystalline phase comprising a plurality of precipitates of the formula M x WO3and / or M x MoO3, where 0 < x < 1 and M is a dopant cation. In some such embodiments, the precipitates have a length of about 1 nm to about 200 nm as measured by electron microscopy. The precipitates of the crystalline phase can be substantially uniformly distributed throughout the glass-ceramic.

[0011] In addition, the glass-ceramic can comprise an amorphous phase and a crystalline phase, the crystalline phase comprising a plurality of precipitates of the formula M x TiO2, where 0 < x < 1 and M is a dopant cation. In some embodiments, the precipitates have a length of about 1 nm to about 200 nm, or 1 nm to about 300 nm, or 1 nm to about 500 nm as measured by electron microscopy. The precipitates of the crystalline phase can be substantially uniformly distributed throughout the glass-ceramic.

[0012] In some embodiments, the glass-ceramic comprises a silicate-containing glass and crystals of a non-stoichiometric low-valence oxide of tungsten and / or molybdenum intercalated with dopant cations uniformly distributed in the silicate-containing glass. The glass-ceramic can have a transmittance of about 5% or more per mm over at least one 50 nm wide band of wavelengths in the range from about 400 nm to about 700 nm. The dopant cations can be: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and / or Ce. In some such embodiments, at least some of the crystals are located at a depth greater than about 10 μιη from an outer surface of the glass-ceramic. The crystals can have a rod-like morphology.

[0013] In some embodiments, the glass-ceramic comprises a silicate-containing glass and crystals of a non-stoichiometric low-valence oxide of tungsten and / or molybdenum intercalated with dopant cations uniformly distributed in the silicate-containing glass. The glass-ceramic can have a transmittance of about 5% or more per mm over at least one 50 nm wide band of wavelengths in the range from about 400 nm to about 700 nm. The dopant cations can be: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and / or Ce. In some such embodiments, at least some of the crystals are located at a depth greater than about 10 μιη from an outer surface of the glass-ceramic. The crystals can have a rod-like morphology.

[0014] In other embodiments, the glass-ceramic comprises a silicate-containing glass and crystals of a non-stoichiometric low-valence oxide of titanium intercalated with dopant cations uniformly distributed in the silicate-containing glass; and / or a silicate-containing glass phase and a crystalline phase comprising a non-stoichiometric low-valence oxide of titanium forming a solid-state defect structure having vacancies occupied by dopant cations.

[0015] In some embodiments, an article comprises at least one amorphous phase and one crystalline phase, the article comprising from about 1 mol% to about 95 mol% Si02as a batch component. The crystalline phase comprises oxides of at least one of: (i) W, (ii) Mo, (iii) V and an alkali cation, and (iv) Ti and an alkali cation (from about 0.1 mol% to about 100 mol% of the crystalline phase). The article can be substantially free of Cd and Se.

[0016] In other embodiments, a glass (e.g., a glass precursor to a glass-ceramic) comprises a batch composition of: S1O2 about 25 mole percent to about 99 mole percent, AI2O3 about 0 mole percent to about 50 mole percent, WO3 plus M0O3 about 0.35 mole percent to about 30 mole percent, R2O about 0.1 mole percent to about 50 mole percent, where R2O is one or more of Li2O, Na2O, K2O, Rb2O, and Cs2O, and where R2O minus AI2O3 is about -35 mole percent to about 7 mole percent. In some such embodiments, at least one of (i) RO ranges from about 0.02 mole percent to about 50 mole percent, and (ii) Sn02 is about 0.01 mole percent to about 5 mole percent, where RO is one or more of MgO, CaO, SrO, BaO, and ZnO. In some such embodiments, if WO3 is about 1 mole percent to about 30 mole percent, then the glass further comprises about 0.9 mole percent or less Fe203, or S1O2 is about 60 mole percent to about 99 mole percent. If WO3 is about 0.35 mole percent to about 1 mole percent, then the glass can comprise about 0.01 mole percent to about 5.0 mole percent Sn02. If M0O3 is about 1 mole percent to about 30 mole percent, then S1O2 can range from about 61 mole percent to about 99 mole percent, or then Fe203 can be about 0.4 mole percent or less and R2O is greater than RO. If M0O3 is about 0.9 mole percent to about 30 percent and S1O2 is about 30 mole percent to about 99 mole percent, then the glass can further comprise about 0.01 mole percent to about 5 mole percent Sn02.

[0017] In some embodiments, a method of forming a glass-ceramic comprises: melting together (1) a bound alkali species, (2) silica, and (3) tungsten and / or molybdenum to form a glass melt; solidifying the glass melt into a glass; and precipitating a crystalline phase within the glass to form a glass-ceramic article. The glass can be a single, homogeneous solid phase. The crystalline phase can comprise tungsten and / or molybdenum. Further, in some such embodiments, the bound alkali species comprises: (A) a feldspar, (B) a nepheline, (C) sodium borate, (D) spodumene, (E) albite, (F) potassium feldspar, (G) an alkali aluminosilicate-containing species, (H) an alkali silicate-containing species, and / or (I): (I-i) an alkali species bound to alumina, (I-ii) an alkali species bound to boron oxide, and / or (I-iii) an alkali species bound to silica.

[0018] In other embodiments, a method of forming a glass-ceramic includes the steps of melting silica together with tungsten and / or molybdenum to form a glass melt; solidifying the glass melt to form a glass; and precipitating bronze-type crystals comprising tungsten and / or molybdenum in the glass. The precipitation of the crystalline phase can include heat-treating the glass. In at least some such embodiments, the method further includes the step of growing the precipitates of the crystalline phase to a length of at least about 1 nm and no more than about 500 nm.

[0019] In other embodiments, a glass-ceramic includes a silicate-containing glass phase; and a crystalline phase comprising a low valence oxide of titanium, the low valence oxide of titanium including a solid state defect structure in which a vacancy is occupied by a dopant cation.

[0020] In other embodiments, a glass-ceramic includes an amorphous phase; and a crystalline phase comprising a low valence oxide of titanium of the formula M x TiO2, where 0 < x < 1 and M is a dopant cation.

[0021] In other embodiments, a glass-ceramic includes a silicate-containing glass; and a plurality of crystals uniformly distributed in the silicate-containing glass, where the crystals include a non-stoichiometric low valence oxide of titanium, and where the crystals incorporate a dopant cation.

[0022] In other embodiments, a glass-ceramic article includes at least one amorphous phase and a crystalline phase; and about 1 mol% to about 95 mol% SiO2; where the crystalline phase includes about 0.1 mol% to about 100 mol% of a non-stoichiometric low valence oxide of titanium of the crystalline phase, the oxide including at least one of: (i) Ti, (ii) V, and an alkali cation.

[0023] In other embodiments, a method of forming a glass-ceramic includes melting components including silica and titanium together to form a glass melt; solidifying the glass melt to form a glass, where the glass includes a first average near-infrared absorbance; and precipitating a crystalline phase in the glass to form a glass-ceramic, the glass-ceramic including: (a) a second average near-infrared absorbance, where a ratio of the second average near-infrared absorbance to the first average near-infrared absorbance is about 1.5 or greater, and (b) an average optical density per mm of about 1.69 or less.

[0024] In other embodiments, in the batch components, the glass comprises: S1O2 from about 1 mol% to about 90 mol%; AI2O3 from about 0 mol% to about 30 mol%; Ti02 from about 0.25 mol% to about 30 mol%; metal sulfide from about 0.25 mol% to about 30 mol%; R2O from about 0 mol% to about 50 mol%, wherein R2O is one or more of L12O, Na20, K2O, Rb20, and Cs20; and RO from about 0 mol% to about 50 mol%, wherein RO is one or more of BeO, MgO, CaO, SrO, BaO, and ZnO, wherein the glass is substantially free of Cd.

[0025] These and other features, aspects, and advantages of the present disclosure will become better understood with reference to the following description and appended claims, taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments and together with the description serve to explain principles and operation of the various embodiments. Thus, the disclosure will be better understood with reference to the following description and drawings, of which:

[0027] Figure 1 is a cross-sectional view of an article according to at least one example of the present disclosure, the article comprising a substrate comprising a glass-ceramic composition.

[0028] Figure 2A is a plot of transmittance versus wavelength for a comparative CdSe glass and a heat treated glass-ceramic according to at least one example of the present disclosure.

[0029] Figure 2B is a plot of transmittance versus wavelength for a comparative CdSe glass and a heat treated glass-ceramic according to at least one example of the present disclosure. Figure 2A is an image of

[0030] Figure 3A is a plot of transmittance versus wavelength for a comparative CdSe glass and a heat treated glass-ceramic according to at least one example of the present disclosure.

[0031] Figure 3B is a plot of transmittance versus wavelength for a comparative CdSe glass and a heat treated glass-ceramic according to at least one example of the present disclosure. Figure 3A is an image of

[0032] Figure 4Ais a plot of transmittance versus wavelength for comparative CdSe glass and glass-ceramic samples heat treated at 700 °C and 800 °C according to various conditions according to examples of the disclosure.

[0033] Figure 4B is a plot of transmittance versus wavelength for comparative CdSe glass and glass-ceramic samples heat treated at 700 °C and 800 °C according to various conditions according to examples of the disclosure. Figure 4A is a plot of transmittance versus wavelength for comparative CdSe glass and glass-ceramic samples heat treated at 700 °C and 800 °C according to various conditions according to examples of the disclosure.

[0034] Figure 4C is a plot of transmittance versus wavelength for comparative CdSe glass and glass-ceramic samples heat treated at 700 °C and 800 °C according to various conditions according to examples of the disclosure. Figure 4A is a plot of transmittance versus wavelength for comparative CdSe glass and glass-ceramic samples heat treated at 700 °C and 800 °C according to various conditions according to examples of the disclosure.

[0035] Figure 5 is an X-ray diffraction ("XRD") plot of a heat treated glass-ceramic according to at least one example of the disclosure.

[0036] Figures 6A-6C is a representative Raman spectrum of a glass-ceramic sample heat treated at 650 °C and 700 °C according to various conditions according to examples of the disclosure and a glass-ceramic sample that was splat-quenched.

[0037] Figure 7A is a Raman spectrum of a glass-ceramic sample heat treated at 650 °C and 700 °C according to various conditions according to examples of the disclosure and a glass-ceramic sample that was splat-quenched.

[0038] Figure 8 is a plot of residual stress versus substrate depth for two glass-ceramic samples having compressive stress regions derived from two representative ion exchange processing conditions according to examples of the disclosure.

[0039] Figure 9 is a scanning electron microscope (SEM) micrograph of a glass-ceramic according to an example embodiment.

[0040] Figure 10A and 10B are SEM and transmission electron microscope (TEM) micrographs, respectively, of a glass-ceramic according to another example embodiment.

[0041] Figure 11A and 11B are SEM and TEM micrographs, respectively, of a glass-ceramic according to another example embodiment.

[0042] Figure 12Aand 12B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FLZ in the as-fabricated unannealed state and heat treated state (600°C 1 h) collected as OD / mm.

[0043] Figure 13A and 13B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FMB in the as-fabricated unannealed state and heat treated state (700°C 1 h) collected as OD / mm.

[0044] Figure 14A and 14B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FMC in the as-fabricated unannealed state and heat treated state (500°C 1 h and 600°C 1 h) collected as OD / mm.

[0045] Figure 15A and 15B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FMD in the as-fabricated unannealed state and heat treated state (500°C 1 h and 600°C 1 h) collected as OD / mm.

[0046] Figure 16A and 16B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FME in the as-fabricated unannealed state and heat treated state (600°C 1 h and 700°C 1 h) collected as OD / mm.

[0047] Figure 17A and 17B are the transmission and absorption spectra of a 0.5 mm polished plate of composition 889FMG in the as-fabricated unannealed state and heat treated state (700°C 1 h and 700°C 2 h) collected as OD / mm.

[0048] Figures 18A-18D are TEM micrographs of titanium containing crystals within a sample of heat treated composition 889FMC heat treated at 700°C for 1 hour.

[0049] Figure 19A is a TEM micrograph of titanium containing crystals within a sample of heat treated composition 889FMC heat treated at 700°C for 1 hour.

[0050] Figure 19B is Figure 19A a TEM micrograph of titanium containing crystals within a sample of heat treated composition 889FMC heat treated at 700°C for 1 hour. DETAILED DESCRIPTION

[0051] Before the present technology is disclosed and described, it is to be understood that this technology is not limited to the details of construction or to the methods described herein below and in the drawings. Those skilled in the art will understand that many modifications of the details of the devices and methods described can be made without departing from the scope of the technology. For example, although the technology is described in terms of a specific embodiment, those skilled in the art will understand that features and attributes related to one embodiment described in the text or shown in one of the drawings can be applied to other embodiments described in the text or shown in other drawings.

[0052] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

[0053] In this document, relational terms, such as first and second, top and bottom, and the like, are used solely to distinguish one entity or action from another entity or action, without necessarily requiring or implying any actual such relationship or order between such entities or actions.

[0054] Modifications of the technology will occur to those skilled in the art upon reading this disclosure. Therefore, it is understood that the embodiments shown and described herein are merely illustrative applications of the principles of the technology and are not intended to limit the scope of the technology as defined by the claims, which follow, as interpreted according to the principles of patent law including the home of equivalents.

[0055] Those skilled in the art will appreciate that the disclosure and other components described herein are not limited to any particular material. Unless otherwise stated herein, other exemplary embodiments of the technology disclosed herein can be formed from a wide range of various materials.

[0056] For the purposes of this disclosure, the term "connected" (or "coupled") generally means the joining of two components (electrical or mechanical) directly or indirectly to one another. Such joining can be stationary in nature or movable in nature. Such joining can be achieved with the two components and any additional intermediate member(s) (electrical or mechanical) that are integrally connected to the two components or with the two components and any additional intermediate member(s) that can be removably connected to the two components. Such

[0057] As used herein, the term "about" means amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximated and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and other factors that are expected to be within the scope of those skilled in the art. When used in a context to refer to a range of values or endpoints, the term "about" should be understood that the disclosure includes the specific values or endpoints referred to. Whether or not the term "about" is used to describe a value or range of values, the endpoints of the ranges are not to be included as being modified by "about" unless the term "about" is specifically used to refer to the endpoint(s). It is also to be understood that the endpoints of the ranges are significant, and that the scope of any range is in fact bounded by the numerical values which are the endpoints of that range.

[0058] The terms "substantial," "substantially," and variations thereof as used herein are intended to note that a described feature is equal or approximately equal to a value or description. For example, a "substantially planar" surface is intended to denote a surface that is planar or approximately planar. Moreover, "substantially" is intended to denote that two values are equal or approximately equal. In some embodiments, "substantially" can denote that the numerical values of a value or values are within about 10%, for example within about 5%, or within about 2% of each other.

[0059] Directional terms, such as "upper," "lower," "left," "right," "front," "back," "top," and "bottom," are used to assist in describing the disclosed embodiments. These terms are not intended to limit the scope of the disclosure.

[0060] As used herein, the terms "the," "a," or "an," mean "at least one," and should not be limited to only one unless explicitly indicated to the contrary. Thus, for example, reference to "an element" includes embodiments having two or more such elements, unless the context clearly indicates otherwise.

[0061] Unless otherwise indicated, all compositional expressions are in mole percent (mol%) of ingredients. Those skilled in the art will appreciate that various melt components (e.g., fluorine, alkali metals, boron, etc.) can be subject to different levels of volatilization during the melting of the components (e.g., as a function of vapor pressure, melt time, and / or melt temperature). As such, the term "about" in connection with such components is intended to include values that differ from the as-ingredient composition provided herein by about 0.2 mol% when measured in the final article. In view of the foregoing, substantial compositional identity between the final article and the ingredient composition is contemplated.

[0062] For purposes of the present disclosure, the terms "bulk," "bulk composition," and / or "overall composition" are intended to include the overall composition of the entire article, which can differ from the "local" or "localized" composition, which can differ from the bulk composition due to the formation of crystalline and / or ceramic phases.

[0063] Further, as used herein, the terms "article," "glass article," "ceramic article," "glass-ceramic," "glass element," "glass-ceramic article," and "glass-ceramic article" can be used interchangeably and encompass, in their broadest sense, any object fabricated wholly or partially of glass and / or glass-ceramic material.

[0064] As used herein, "glass state" refers to the inorganic amorphous phase material in the articles of the disclosure that is a fusion product that cools to a rigid state without crystallizing. As used herein, "glass-ceramic state" refers to the inorganic material in the articles of the disclosure that includes both the glass state as well as "crystalline phase" and / or "crystalline precipitates" as described herein.

[0065] The coefficient of thermal expansion (CTE) is in units of 10 -7 / °C, measured over a temperature range of about 0°C to about 300°C, unless otherwise specified.

[0066] As used herein, "transmission" and "transmittance" refer to external transmission or transmittance, taking into account absorption, scattering, and reflection. In the transmission and transmittance values reported herein, Fresnel reflections are not excluded.

[0067] As used herein in the disclosure, "optical density units," "OD," and "OD units" are used interchangeably to mean optical density units, which are generally understood to be a measure of the absorbance of a test material, measured with a spectrometer to give OD = -log(I / I0), where I0is the intensity of light incident on the sample and I is the intensity of light transmitted through the sample. Further, the term "OD / mm" or "OD / cm" as used in the disclosure is a normalized absorbance measurement, determined by dividing the optical density units (i.e., as measured by optical spectrometer) by the sample thickness (e.g., in millimeters or centimeters). Further, any optical density units referred to over a specific wavelength range (e.g., 3.3 OD / mm to 24.0 OD / mm in UV wavelengths from 280 nm to 380 nm) give the average value of the optical density units over that specific wavelength range.

[0068] As used herein, the term "haze" means the percentage of transmitted light that is scattered outside an angular cone of about ±2.5° as measured in a sample having a thickness of about 1 mm in accordance with ASTM Method D 1003.

[0069] Further, as used herein, the term “[glass or glass-ceramic] free of [component]” (e.g., glass-ceramic free of cadmium and free of selenium) means that the glass or glass-ceramic is completely free of or substantially free of (i.e., < 500 ppm) the listed component(s), and that its preparation did not involve the intentional, deliberate, or purposeful addition or batching of the listed component(s) into the glass or glass-ceramic.

[0070] When referring to the glass-ceramics and glass-ceramic materials and articles of the present disclosure, the compressive stress and depth of compression (“DOC”) are measured by employing a commercial instrument, such as the Scattered Light Polarimeter SCALP 220 manufactured by Glas Stress, Ltd. (Tallinn, Estonia) with the accompanying software version 5; or the FSM-6000 manufactured by Orihara Co., Ltd. (Tokyo, Japan), unless otherwise specified. Both of these instruments measure optical retardation, which must be converted to stress by the stress optical coefficient (“SOC”) of the material being measured. Thus, the stress measurement relies on an accurate measurement of the SOC, which is related to the birefringence of the glass. In turn, the SOC is measured according to a modified version of Procedure C described in ASTM Standard C770-98 (2013), entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” which is incorporated herein by reference in its entirety. The modified Procedure C involves the use of a glass or glass-ceramic disc as the test specimen, having a thickness of 5 to 10 mm and a diameter of 12.7 mm. The disc is isotropic and homogeneous, and is core drilled, with both sides polished and parallel. The modified Procedure C also involves calculating the maximum force F 最大值 to be applied to the disc 最大值 :

[0071] F 最大值 = 7.854 * D * h

[0072] where F 最大值 is the maximum force (N), D is the diameter of the disc (mm), and h is the thickness of the light path (mm). For each application of force, the stress is calculated using the equation:

[0073] σ (MPa) = 8F / (π * D * h)

[0074] where F is the force (N), D is the diameter of the disc (mm), and h is the thickness of the light path (mm).

[0075] Further, as used herein, the terms "sharp cut-off wavelength" and "cut-off wavelength" are used interchangeably and mean a cut-off wavelength in the range of about 350 nm to 800 nm, where the glass-ceramic has a substantially higher transmittance above the cut-off wavelength (λc) than below the cut-off wavelength (λc). The cut-off wavelength (λc) is the wavelength at the midpoint between the "absorption limit wavelength" and the "high transmittance limit wavelength" in a given spectrum of the glass-ceramic. The "absorption limit wavelength" is defined as the wavelength at which the transmittance is 5%; and in the "high transmittance wavelength" is defined as the wavelength at which the transmittance is 72%. It will be appreciated that "sharp UV cut-off" as used herein can be a sharp cut-off wavelength as described above that occurs in the ultraviolet band of the electromagnetic spectrum.

[0076] The articles of the present disclosure include glasses and / or glass-ceramics having one or more of the compositions listed herein. The articles can be used in any number of applications. For example, in any number of optical-related applications and / or aesthetic applications, the articles can be used in the form of substrates, elements, lenses, coverings, and / or other elements.

[0077] The articles are formed from a batch composition and cast in a glass state. The articles can subsequently be annealed and / or heat treated (e.g., thermally processed) to form a glass-ceramic state having a plurality of ceramic or crystalline particles. It will be appreciated that depending on the casting technique employed, the articles can readily crystallize and become glass-ceramic (e.g., substantially cast in a glass-ceramic state) without additional thermal processing. In examples where post-shaping thermal processing is employed, a portion of the article, a majority of the article, substantially all of the article, or the entire article can be transformed from a glass state to a glass-ceramic state. As such, while the composition of the article can be described in connection with a glass state and / or a glass-ceramic state, the bulk composition of the article can remain substantially unchanged when transformed between the glass state and the glass-ceramic state, although localized portions of the article can have different compositions (i.e., due to the formation of ceramic or crystalline precipitates).

[0078] According to various examples, the articles can include: AI2O3; SiO2; B2O3; WO3; MO3; R2O, where R2O is one or more of Li2O, Na2O, K2O, Rb2O, and Cs2O; RO, where RO is one or more of MgO, CaO, SrO, BaO, and ZnO; and a plurality of dopants. It will be appreciated that a plurality of other components (e.g., F, As, Sb, Ti, P, Ce, Eu, La, Cl, Br, etc.) do not depart from the teachings provided herein.

[0079] According to a first example, an article can comprise: S1O2 about 58.8 mole% to about 77.58 mole%, AI2O3 about 0.66 mole% to about 13.69 mole%, B2O3 about 4.42 mole% to about 27 mole%, R2O about 0 mole% to about 13.84 mole%, RO about 0 mole% to about 0.98 mole%, WO3 about 1.0 mole% to about 13.24 mole%, and Sn02 about 0 mole% to about 0.4 mole%. Such examples of articles can relate generally to Examples 1-109 of Table 1.

[0080] According to a second example, an article can comprise: S1O2 about 65.43 mole% to about 66.7 mole%, AI2O3 about 9.6 mole% to about 9.98 mole%, B2O3 about 9.41 mole% to about 10.56 mole%, R2O about 6.47 mole% to about 9.51 mole%, RO about 0.96 mole% to about 3.85 mole%, WO3 about 1.92 mole% to about 3.85 mole%, Mo03 about 0 mole% to about 1.92 mole%, and Sn02 about 0 mole% to about 0.1 mole%. Such examples of articles can relate generally to Examples 110-122 of Table 2.

[0081] According to a third example, an article can comprise: S1O2 about 60.15 mole% to about 67.29 mole%, AI2O3 about 9.0 mole% to about 13.96 mole%, B2O3 about 4.69 mole% to about 20 mole%, R2O about 2.99 mole% to about 12.15 mole%, RO about 0.00 mole% to about 0.14 mole%, WO3 about 0 mole% to about 7.03 mole%, Mo03 about 0 mole% to about 8.18 mole%, Sn02 about 0.05 mole% to about 0.15 mole%, and V2O5 about 0 mole% to about 0.34 mole%. Such examples of articles can relate generally to Examples 123-157 of Table 3.

[0082] According to a fourth example, an article can comprise: S1O2 about 54.01 mole% to about 67.66 mole%, AI2O3 about 9.55 mole% to about 11.42 mole%, B2O3 about 9.36 mole% to about 15.34 mole%, R2O about 9.79 mole% to about 13.72 mole%, RO about 0.00 mole% to about 0.22 mole%, WO3 about 1.74 mole% to about 4.48 mole%, Mo03 about 0 mole% to about 1.91 mole%, Sn02 about 0.0 mole% to about 0.21 mole%, V2O5 about 0 mole% to about 0.03 mole%, Ag about 0 mole% to about 0.48 mole%, and Au about 0 mole% to about 0.01 mole%. Such examples of articles can relate generally to Examples 158-311 of Table 4.

[0083] According to a 5th example, an article can comprise: S1O2 from about 60.01 mol% to about 77.94 mol%, AI2O3 from about 0.3 mol% to about 10.00 mol%, B2O3 from about 10 mol% to about 20 mol%, R2O from about 0.66 mol% to about 10 mol%, WO3 from about 1.0 mol% to about 6.6 mol%, and Sn02 from about 0.0 mol% to about 0.1 mol%. Such examples of articles can relate generally to Examples 312-328 of Table 5.

[0084] The article can have: from about 1 mol% to about 99 mol% S1O2, or from about 1 mol% to about 95 mol% S1O2, or from about 45 mol% to about 80 mol% S1O2, or from about 60 mol% to about 99 mol% S1O2, or from about 61 mol% to about 99 mol% S1O2, or from about 30 mol% to about 99 mol% S1O2, or from about 58 mol% to about 78 mol% S1O2, or from about 55 mol% to about 75 mol% S1O2, or from about 50 mol% to about 75 mol% S1O2, or from about 54 mol% to about 68 mol% S1O2, or from about 60 mol% to about 78 mol% S1O2, or from about 65 mol% to about 67 mol% S1O2, or from about 60 mol% to about 68 mol% S1O2, or from about 56 mol% to about 72 mol% S1O2, or from about 60 mol% to about 70 mol% S1O2. It will be appreciated that any and all values and ranges between the recited S1O2 ranges are contemplated. S1O2 can be the primary glass-forming oxide and affect the stability, devitrification resistance, and / or viscosity of the article.

[0085] The article can comprise: from about 0 mol% to about 50 mol% AI2O3, or from about 0.5 mol% to about 20 mol% AI2O3, or from about 0.5 mol% to about 15 mol% AI2O3, or from about 7 mol% to about 15 mol% AI2O3, or from about 0.6 mol% to about 17 mol% AI2O3, or from about 0.6 mol% to about 14 mol% AI2O3, or from about 7 mol% to about 14 mol% AI2O3, or from about 9.5 mol% to about 10 mol% AI2O3, or from about 9 mol% to about 14 mol% AI2O3, from about 9.5 mol% to about 11.5 mol% AI2O3, or from about 0.3 mol% to about 10 mol% AI2O3, or from about 0.3 mol% to about 15 mol% AI2O3, or from about 2 mol% to about 16 mol% AI2O3, or from about 5 mol% to about 12 mol% AI2O3, or from about 8 mol% to about 12 mol% AI2O3, or from about 5 mol% to about 10 mol% AI2O3. It will be appreciated that any and all values and ranges between the recited ranges of AI2O3 are contemplated. AI2O3 can be used as an adjustable network former and contribute to stable articles with low CTE, article rigidity, and facilitate melting and / or shaping.

[0086] The article can include WO3and / or MoO3. For example, WO3plus MoO3may be about 0.35 mole percent to about 30 mole percent. MoO3may be about 0 mole percent and WO3is about 1.0 mole percent to about 20 mole percent, or MoO3may be about 0 mole percent and WO3is about 1.0 mole percent to about 14 mole percent, or MoO3is about 0 mole percent to about 8.2 mole percent and WO3is about 0 mole percent to about 16 mole percent, or MoO3is about 0 mole percent to about 8.2 mole percent and WO3is about 0 mole percent to about 9 mole percent, or MoO3is about 1.9 mole percent to about 12.1 mole percent and WO3is about 1.7 mole percent to about 12 mole percent, or MoO3is about 0 mole percent to about 8.2 mole percent and WO3is about 0 mole percent to about 7.1 mole percent, or MoO3is about 1.9 mole percent to about 12.1 mole percent and WO3is about 1.7 mole percent to about 4.5 mole percent, or MoO3is about 0 mole percent and WO3is about 1.0 mole percent to about 7.0 mole percent. For MoO3, the glass composition can have: about 0.35 mole percent to about 30 mole percent MoO3, or about 1 mole percent to about 30 mole percent MoO3, or about 0.9 mole percent to about 30 percent MoO3, or about 0.9 mole percent to about 20 percent MoO3, or about 0 mole percent to about 1.0 mole percent MoO3, or about 0 mole percent to about 0.2 mole percent MoO3. For WO3, the glass composition can have: about 0.35 mole percent to about 30 mole percent WO3, or about 1 mole percent to about 30 mole percent WO3, or about 1 mole percent to about 17 mole percent WO3, or about 1.9 mole percent to about 10 mole percent WO3, or about 0.35 mole percent to about 1 mole percent WO3, or about 1.9 mole percent to about 3.9 mole percent WO3, or about 2 mole percent to about 15 mole percent WO3, or about 4 mole percent to about 10 mole percent of WO3, or about 5 mole percent to about 7 mole percent WO3. It will be understood that any and all values and ranges between the recited WO3and / or MoO3ranges above are contemplated.

[0087] The article can comprise: about 2 mol% to about 40 mol% B2O3, or about 4 mol% to about 40 mol% B2O3, or about 4.0 mol% to about 35 mol% B2O3, or about 4.0 mol% to about 27 mol% B2O3, or about 5.0 mol% to about 25 mol% B2O3, or about 9.4 mol% to about 10.6 mol% B2O3, or about 5 mol% to about 20 mol% B2O3, or about 4.6 mol% to about 20 mol% B2O3, or about 9.3 mol% to about 15.5 mol% B2O3, or about 10 mol% to about 20 mol% B2O3, or about 10 mol% to about 25 mol% B2O3. It will be appreciated that any and all values and ranges between the recited ranges for B2O3 are contemplated. B2O3 can be a glass-forming oxide that serves to lower the CTE, density, and viscosity, making the article easier to melt and shape at low temperatures.

[0088] The article can comprise at least one alkali metal oxide. The alkali metal oxide can be represented by the chemical formula R2O, where R2O is one or more of Li2O, Na2O, K2O, Rb2O, Cs2O, and / or combinations thereof. The article can have an alkali metal oxide composition of about 0.1 mol% to about 50 mol% R2O, or about 0 mol% to about 14 mol% R2O, or about 3 mol% to about 14 mol% R2O, or about 5 mol% to about 14 mol% R2O, or about 6.4 mol% to about 9.6 mol% R2O, or about 2.9 mol% to about 12.2 mol% R2O, or about 9.7 mol% to about 12.8 mol% R2O, or about 0.6 mol% to about 10 mol% R2O, or about 0 mol% to about 15 mol% R2O, or about 3 mol% to about 12 mol% R2O, or about 7 mol% to about 10 mol% R2O. It will be appreciated that any and all values and ranges between the recited ranges for R2O are contemplated. Alkali oxides (e.g., Li2O, Na2O, K2O, Rb2O, and Cs2O) can be incorporated in the article for a variety of reasons, including (i) to lower the melting temperature, (ii) to increase formability, (iii) to allow for chemical strengthening by ion exchange, and / or (iv) as a means of partitioning certain crystallites.

[0089] According to various examples, the range of R2O minus Al2O3 is about -35 mol% to about 7 mol%, or about -12 mol% to about 2.5 mol%, or about -6% to about 0.25%, or about -3.0 mol% to about 0 mol%. It will be appreciated that any and all values and ranges between the recited ranges for R2O minus Al2O3 are contemplated.

[0090] The article can include at least one alkaline earth oxide. The alkaline earth oxide can be represented by the chemical formula RO, where RO is one or more of MgO, CaO, SrO, BaO, and ZnO. The article can include RO in the following amounts: from about 0.02 mole percent to about 50 mole percent RO, or from about 0.01 mole percent to about 5 mole percent RO, or from about 0.02 mole percent to about 5 mole percent RO, or from about 0.05 mole percent to about 10 mole percent RO, or from about 0.10 mole percent to about 5 mole percent RO, or from about 0.15 mole percent to about 5 mole percent RO, or from about 0.05 mole percent to about 1 mole percent RO, or from about 0.5 mole percent to about 4.5 mole percent RO, or from about 0 mole percent to about 1 mole percent RO, or from about 0.96 mole percent to about 3.9 mole percent RO, or from about 0.2 mole percent to about 2 mole percent RO, or from about 0.01 mole percent to about 0.5 mole percent RO, or from about 0.02 mole percent to about 0.22 mole percent RO. It will be understood that any and all values and ranges between the recited RO ranges are contemplated. According to various examples, R2O can be greater than RO. In addition, the article can be free of RO. Alkaline earth oxides (e.g., MgO, CaO, SrO, and BaO) and other divalent oxides (e.g., ZnO) can improve the melting behavior of the article and can also serve to increase the CTE, Young's modulus, and shear modulus of the article.

[0091] The article can include: from about 0.01 mole percent to about 5 mole percent Sn02, or from about 0.01 mole percent to about 0.5 mole percent Sn02, or from about 0.05 mole percent to about 0.5 mole percent Sn02, or from about 0.05 mole percent to about 2 mole percent Sn02, or from about 0.04 mole percent to about 0.4 mole percent Sn02, or from about 0.01 mole percent to about 0.4 mole percent Sn02, or from about 0.04 mole percent to about 0.16 mole percent Sn02, or from about 0.01 mole percent to about 0.21 mole percent Sn02, or from about 0 mole percent to about 0.2 mole percent Sn02, or from about 0 mole percent to about 0.1 mole percent Sn02. It will be understood that any and all values and ranges between the recited Sn02ranges are contemplated. The article can also include a low concentration of Sn02as a fining agent (e.g., other fining agents can include Ce02, As203, Sb205, CI - or F - and / or other elements) to help eliminate gaseous inclusions during melting. Certain fining agents can also act as redox couples, color centers, and / or species that nucleate or intercalate into the crystallites formed in the article.

[0092] The composition of certain components of the article can depend on the presence and / or composition of other components. For example, if WO3 is about 1 mole % to about 30 mole %, the article further comprises about 0.9 mole % or less Fe2O3, or SiO2 is about 60 mole % to about 99 mole %. In another example, if WO3 is about 0.35 mole % to about 1 mole %, the article comprises about 0.01 mole % to about 5.0 mole % SnO2. In another example, if MoO3 is about 1 mole % to about 30 mole %, SiO2 is about 61 mole % to about 99 mole %, or Fe2O3 is about 0.4 mole % or less and R2O is greater than RO. In another example, if MoO3 is about 0.9 mole % to about 30 % and SiO2 is about 30 mole % to about 99 mole %, the article comprises about 0.01 mole % to about 5 mole % SnO2.

[0093] The articles can be substantially free of cadmium and substantially free of selenium. According to various examples, the articles can also include at least one dopant selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, Se, Ta, Bi, Ag, Ce, Pr, Nd, and Er for adjusting ultraviolet, visible, color, and / or near infrared absorption. The dopant concentration in the articles can be from about 0.0001 mole percent to about 1.0 mole percent. For example, the articles can include at least one of the following: Ag from about 0.01 mole percent to about 0.48 mole percent, Au from about 0.01 mole percent to about 0.13 mole percent, V2O5 from about 0.01 mole percent to about 0.03 mole percent, Fe2O3 from about 0 mole percent to about 0.2 mole percent, Fe2O3 from about 0 mole percent to about 0.2 mole percent, and CuO from about 0.01 mole percent to about 0.48 mole percent. According to another example, the articles can include at least one of the following: Ag from about 0.01 mole percent to about 0.75 mole percent, Au from about 0.01 mole percent to about 0.5 mole percent, V2O5 from about 0.01 mole percent to about 0.03 mole percent, and CuO from about 0.01 mole percent to about 0.75 mole percent. The articles can include from about 0 mole percent to about 5 mole percent fluorine to soften the glass. The articles can include from about 0 mole percent to about 5 mole percent phosphorus to further adjust the physical properties of the articles and to regulate crystal growth. The articles can include Ga2O3, In2O3, and / or GeO2 to further adjust the physical and optical properties (e.g., refractive index) of the articles. From about 0.001 mole percent to about 0.5 mole percent of the following trace impurities can be present to further adjust the absorption of ultraviolet, visible (e.g., from about 390 nm to about 700 nm), and near infrared (e.g., from about 700 nm to about 2500 nm) light and / or to make the articles fluorescent: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Te, Ta, Re, Os, Ir, Pt, Au, Ti, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In addition, small amounts of P2O5 can be added to certain compositions to further adjust the physical properties and viscosity of the articles.

[0094] It will be appreciated that each of the compositions and composition ranges for SiO2, Al2O3, WO3, MoO3, WO3 plus MoO3, B2O3, R2O, RO, V2O5, Ag, Au, CuO, SnO2, and dopants noted above can be used with any other composition and / or composition range for the other components of the articles listed herein.

[0095] As explained above, conventional forming of tungsten-containing, molybdenum- containing, or mixed tungsten-molybdenum-containing alkali glasses is hindered by the segregation of melt components during the melting process. Segregation of glass components during the melting process results in perceived solubility limits of alkali tungstate in the molten glass and, by extension, in articles cast from such melts. Generally, when tungsten melts, molybdenum melts, or mixed tungsten-molybdenum melts are even slightly over-alkaline (e.g., R2O-Al2O3= about 0.25 mole percent or greater), the molten borosilicate glass simultaneously forms a glass and a dense liquid second phase. While the concentration of the alkali tungstate second phase can be reduced by thorough mixing, high temperature melting, and use of small batch sizes (about 1000 g), it cannot be completely eliminated resulting in the formation of a deleterious second crystalline phase. It is believed that the formation of this alkali tungstate phase occurs in the initial stages of melting where tungsten and / or molybdenum oxides react with "free" or "unbound" alkali carbonates. Due to the high density of the alkali tungstate and / or alkali molybdate phase relative to the forming borosilicate glass, it rapidly segregates and / or layers, pooling at the bottom of the crucible and, due to the significant density difference, cannot quickly dissolve in the glass. Since R2O can provide advantageous properties to the glass composition, simply reducing the R2O component present in the melt can be undesirable.

[0096] The inventors of the present disclosure have discovered that a homogeneous single phase over-alkaline W- or Mo-containing melt can be obtained by using "bound" alkali species. For the purposes of the present disclosure, "bound" alkali species are alkali elements that are bound to alumina, boron oxide, and / or silica, and "free" or "unbound" alkali species are alkali carbonates, alkali nitrates, and / or alkali sulfates in which the alkali species are not bound to silica, boron oxide, and / or alumina. Exemplary bound alkali species can include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspar, alkali aluminosilicate-containing, alkali silicate-containing, and / or other naturally occurring or man-made alkali-containing species and minerals of one or more aluminum, boron, and / or silicon atoms. By introducing the alkali species in a bound form, the alkali species can not react with the W or Mo present in the melt to form a dense alkali tungstate and / or alkali molybdate liquid. Furthermore, variations in such a batch can enable the melting of strongly over-alkaline compositions (e.g., R2O-Al2O3= about 2.0 mole percent or greater) without the formation of any alkali tungstate and / or alkali molybdate second phase. This also enables variations in the melting temperature and mixing method and still results in a single phase homogeneous glass. It will be appreciated that, since the alkali tungstate phase is not completely immiscible with the borosilicate glass, extended agitation can also enable mixing of the two phases to cast a single phase article.

[0097] Once the glass melt is cast and solidified to form a glassy article, the article can be annealed, heat treated, or otherwise thermally processed to form a crystalline phase in the article. Thus, the article can be transformed from a glassy state to a glass-ceramic state. The crystalline phase of the glass-ceramic state can have various morphologies. According to various examples, the crystalline phase forms as a plurality of precipitates in regions of the article that are heat treated. As such, the precipitates can have a generally crystalline structure.

[0098] As used herein, "crystalline phase" refers to an inorganic material in an article of the present disclosure that is a solid composed of atoms, ions, or molecules arranged in a pattern that is three- dimensionally periodic. Further, unless otherwise specified, the following methods are employed to determine the presence of a "crystalline phase" as referred to in the present disclosure. First, powder X-ray diffraction ("XRD") is employed to detect the presence of crystalline precipitates. Then, in cases where XRD is unsuccessful (e.g., due to the size, mass, and / or chemistry of the precipitates), Raman spectroscopy ("Raman") is employed to detect the presence of crystalline precipitates. Optionally, transmission electron microscopy ("TEM") is employed to visually verify or otherwise confirm the determination of crystalline precipitates by XRD and / or Raman techniques. In certain cases, the mass and / or size of the precipitates can be sufficiently low that visual verification of the precipitates is particularly difficult. As such, XRD and Raman of larger material samples can advantageously have larger sample sizes to determine the presence of precipitates.

[0099] The crystalline precipitates can have a generally rod-like or needle-like morphology. The precipitates can have a longest length dimension of about 1 nm to about 500 nm, or about 1 nm to about 400 nm, or about 1 nm to about 300 nm, or about 1 nm to about 250 nm, or about 1 nm to about 200 nm, or about 1 nm to about 100 nm, or about 1 nm to about 75 nm, or about 1 nm to about 50 nm, or about 1 nm to about 25 nm, or about 1 nm to about 20 nm, or about 1 nm to about 10 nm. Electron microscopy can be employed to measure the dimensions of the precipitates. For purposes of the present disclosure, the term "electron microscopy" means a visual measurement of the longest length of the precipitates by scanning electron microscopy first, and transmission electron microscopy if the precipitates cannot be resolved. Since the crystalline precipitates can generally have a rod-like or needle-like morphology, the width of the precipitates can be about 2 nm to about 30 nm, or about 2 nm to about 10 nm, or about 2 nm to about 7 nm. It will be appreciated that the dimensions and / or morphology of the precipitates can be uniform, substantially uniform, or can vary. Generally, the peraluminous nature of the article can produce needle-like shaped precipitates having a length of about 100 nm to about 250 nm and a width of about 5 nm to about 30 nm. The peralkaline nature of the article can produce needle-like precipitates having a length of about 10 nm to about 30 nm and a width of about 2 nm to about 7 nm. Ag-, Au- and / or Cu-containing examples of the article can produce rod-like precipitates having a length of about 2 nm to about 20 nm and a width or diameter of about 2 nm to about 10 nm. The volume fraction of the crystalline phase in the article can be about 0.001% to about 20%, or about 0.001% to about 15%, or about 0.001% to about 10%, or about 0.001% to about 5%, or about 0.001% to about 1%.

[0100] The smaller size of the precipitates can be advantageous for reducing the amount of light scattering by the precipitates, resulting in high optical clarity of the glass article when in the glass-ceramic state. As explained in more detail below, the size and / or mass of the precipitates in the article can vary, such that different portions of the article can have different optical properties. For example, portions of the article in which precipitates are present can result in changes in the absorption, color, reflectance and / or transmission, and refractive index of light compared to portions of the article having different (e.g., size and / or mass) precipitates and / or portions of the article in which precipitates are not present.

[0101] The precipitates can include oxides of tungsten and / or molybdenum. The crystalline phase includes oxides of at least one of (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation (about 0.1 mole percent to about 100 mole percent of the crystalline phase). Without being bound by theory, it is believed that during thermal processing (e.g., heat treatment) of the article, tungsten and / or molybdenum cations aggregate to form crystalline precipitates, thereby transitioning from a glassy state to a glass-ceramic state. The molybdenum and / or tungsten present in the precipitates can be reduced or partially reduced. For example, the molybdenum and / or tungsten in the precipitates can have an oxidation state of 0 to about +6. According to various examples, the molybdenum and / or tungsten can have a +6 oxidation state. For example, the precipitates can have a chemical structure of approximately WO3and / or MoO3. However, it is also possible that a significant portion of the tungsten and or molybdenum is in a +5 oxidation state, and the precipitates can be referred to as non-stoichiometric tungsten suboxides, non-stoichiometric molybdenum suboxides, "molybdenum bronze," and / or "tungsten bronze." One or more of the above alkali metals and / or dopants can be present in the precipitates to compensate for the +5 charge of the W or Mo. Tungsten bronze and / or molybdenum bronze are M x WO3or M x MoO3in the chemical formula form, where M = one or more of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and / or U, and where 0 < x < 1. M x WO3and M x The WO3and MoO3structures are believed to be solid state defect structures, where the holes (i.e., vacancies and / or channels in the lattice) in the network of reduced WO3or MoO3are randomly occupied by M atoms, which dissociate into M + cations and free electrons. Depending on the concentration of "M," the material properties can range from metallic to semiconducting, thereby enabling tuning of various optical absorption and electrical properties. The more W or Mo in the +5 state, the more M+cations are needed to compensate and the greater the value of x.

[0102] Tungsten bronze is of the general formula M xNon-stoichiometric compounds of W03, where M is a cationic dopant, such as some other metal, most commonly an alkali metal, and x is a variable less than 1. For clarity, although referred to as 'bronze', these compounds are not structurally or chemically related to metallic bronze, which is an alloy of copper and tin. Tungsten bronze is a solid phase spectrum with homogeneity varying with x. Depending on the dopant M and corresponding concentration x, the material properties of tungsten bronze can range from metallic to semiconducting, and exhibit tunable optical absorption. The structure of these bronzes is a solid state defect structure, where M' cations are intercalated into the pores or channels of the binary oxide matrix and decompose into M+ cations and free electrons.

[0103] For clarity, M x WO3 is a nomenclature convention for a complex system of non-stoichiometric or'sub-stoichiometric' compounds, with varying crystal structures, which can be hexagonal, tetragonal, cubic or pyrochlore, where M can be one or a combination of certain elements of the periodic table, where x varies from 0 < x < 1, where the oxidation state of the bronze-forming element (in this case, W) is a mixture of its highest oxidation state (W 6+ ) and a lower oxidation state (e.g., W 5+ ), and where the number three ("3") in W03 indicates that the number of oxygen anions can be between 2 and 3. Thus, as an alternative, M x WO3 can be expressed as M x WO Z in chemical form, where 0 < x < 1 and 2 < z < 3, or can be expressed as M x WO 3-z , where 0 < x < 1 and 0 < z < 1. However, for convenience, M x WO3 is used for such non-stoichiometric crystals. Similarly, 'bronze' is generally applicable to ternary metal oxides of the form M' x M" y O z , where (i) M" is a transition metal, (ii) M" y O z is its highest binary oxide, (iii) M' is some other metal, and (iv) x is a variable falling in the range 0 < x < 1.

[0104] A portion of the article, a majority of the article, substantially the entire article, or the entire article can be heat processed to form the precipitates. Heat processing techniques can include, but are not limited to, furnaces (e.g., heat treatment furnaces), microwaves, lasers, and / or other techniques of local and / or bulk heating of the article. When heat processing is performed, the crystalline precipitates nucleate internally in a homogeneous manner within the article, where the article is transformed from a glassy state to a glass-ceramic state by the heat processing. As such, in some examples, the article can include both a glassy state and a glass-ceramic state. In examples where the bulk of the article is heat processed (e.g., the entire article is placed in a furnace), the precipitates can be formed uniformly throughout the article. In other words, the precipitates can be present throughout the bulk of the article (i.e., more than about 10 μιη from the surface) starting from the outer surface of the article. In examples where the article is locally heat processed (e.g., by a laser), the precipitates can only be present where the heat processing reaches a sufficient temperature (e.g., at the surface and into the bulk of the article near the heat source). It will be appreciated that the article can be subjected to more than one heat processing to produce the precipitates. Additionally or alternatively, heat processing can be employed to remove and / or alter precipitates that have already formed (e.g., as a result of a prior heat processing). For example, heat processing can result in the decomposition of the precipitates.

[0105] According to various examples, the article can be optically transparent to the visible light region of the electromagnetic spectrum (i.e., from about 400 nm to about 700 nm) for both regions where the precipitates are present and where the precipitates are not present (i.e., in portions that are in a glassy state or a glass-ceramic state). As used herein, the term "optically transparent" means having a transmittance (e.g., in % / mm) of greater than about 1% over a 1 mm path length for at least one 50 nm wide band of wavelengths in the range from about 400 nm to about 700 nm. In some examples, the article has a transmittance of about 5% mm or greater, about 10% mm or greater, about 15% mm or greater, about 20% mm or greater, about 25% mm or greater, about 30% mm or greater, about 40% mm or greater, about 50% mm or greater, about 60% mm or greater, about 70% mm or greater, about 80% mm or greater, and greater than all lower values between these values for at least one 50 nm wide band of wavelengths in the visible light spectrum.

[0106] According to various examples, the glass-ceramic state of the article absorbs light in the ultraviolet ("UV") region (i.e., wavelengths less than about 400 nm) based on the presence of precipitates without the use of additional coatings or films. In some implementations, the glass-ceramic state of the article is characterized by a transmittance of less than 10% / mm, less than 9% / mm, less than 8% / mm, less than 7% / mm, less than 6% / mm, less than 5% / mm, less than 4% / mm, less than 3% / mm, less than 2% / mm, and even less than 1% / mm for light in at least one 50 nm wide wavelength band of light in the UV spectral region (e.g., about 200 nm to about 400 nm). In some examples, the glass-ceramic state absorbs or has an absorption of at least 90% / mm, at least 91% / mm, at least 92% / mm, at least 93% / mm, at least 94% / mm, at least 95% / mm, at least 96% / mm, at least 97% / mm, at least 98% / mm, or even at least 99% / mm for light in at least one 50 nm wide wavelength band of light in the UV spectral region. The glass-ceramic state can have a sharp UV cutoff wavelength of about 320 nm to about 420 nm. For example, the glass-ceramic state can have a sharp UV cutoff of about 320 nm, about 330 nm, about 340 nm, about 350 nm, about 360 nm, about 370 nm, about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm, or any value therebetween.

[0107] In some examples, the glass-ceramic state of the article has a transmittance of greater than about 5% / mm, greater than about 10% / mm, greater than about 15% / mm, greater than about 20% / mm, greater than about 25% / mm, greater than about 30% / mm, greater than about 40% / mm, greater than about 50% / mm, greater than about 60% / mm, greater than about 70% / mm, greater than about 80% / mm, greater than about 90% / mm, and greater than all lower values between these values, for at least one 50 nm wide wavelength band of light in the near infrared (NIR) spectral region (e.g., about 700 nm to about 2700 nm). In other examples, the glass-ceramic state of the article has a transmittance of less than about 90% / mm, less than about 80% / mm, less than about 70% / mm, less than about 60% / mm, less than about 50% / mm, less than about 40% / mm, less than about 30% / mm, less than about 25% / mm, less than about 20% / mm, less than about 15% / mm, less than about 10% / mm, less than about 5% / mm, less than 4% / mm, less than 3% / mm, less than 2% / mm, less than 1% / mm, and even less than 0.1% / mm, and less than all upper values between these values, for at least one 50 nm wide wavelength band of light in the NIR spectral region. In other examples, the glass-ceramic state of the article absorbs or has an absorption of at least 90% / mm, at least 91% / mm, at least 92% / mm, at least 93% / mm, at least 94% / mm, at least 95% / mm, at least 96% / mm, at least 97% / mm, at least 98% / mm, or at least 99% / mm, or even at least 99.9% / mm, for at least one 50 nm wide wavelength band of light in the NIR spectral region.

[0108] Various examples of the disclosure can provide various properties and advantages. It will be appreciated that while certain properties and advantages can be disclosed in connection with certain compositions, the various properties and advantages disclosed can be equally applicable to other compositions.

[0109] For the compositions of Tables 1 and 5 below, the articles made from the disclosed compositions can exhibit low coefficients of thermal expansion ("CTE"). For example, over a temperature range of about 0°C to about 300°C, the articles can have a CTE of about 10 x 10 -7 ℃ -1 to about 60 x 10 -7 ℃ -1of the product can exhibit a transmittance of less than 1% at about 368 nm or less, optical transparency in the visible region (e.g., about 500 nm to about 700 nm), and strong attenuation (e.g., blocking) of NIR wavelengths (e.g., about 700 nm to about 1700 nm). Such products can be advantageous over conventional NIR management solutions because the product does not employ a coating or film (e.g., which can be mechanically brittle, or sensitive to UV light and moisture). Because the product is impervious to oxygen, moisture, and ultraviolet wavelengths (i.e., by virtue of its glass or glass-ceramic nature), NIR-absorbing precipitates can be protected from harsh environmental conditions (e.g., moisture, caustic acids, bases, and gases) and rapid temperature changes. Furthermore, the UV cutoff wavelength and refractive index changes of the glass-ceramic state of the product can be adjusted by post-shaping heat treatment. The glass-ceramic state of the product can exhibit a UV cutoff or refractive index change as a result of its crystalline precipitates. The glass state of the product can have a refractive index of about 1.505 to about 1.508, while the glass-ceramic state of the product can have a refractive index of about 1.520 to about 1.522. The UV cutoff and refractive index that can be adjusted thermally can enable compliance with multiple UV cutoff glass specifications with one pot of glass, by varying the post-shaping heat processing conditions of the product. The thermally adjusted refractive index can result in a large refractive index delta (10 -2 ) of about 0.012. Because the heat treatment required to adjust the UV absorption is done at high viscosity (e.g., 10 8 to 10 12 poise), the final product can be heat processed without damaging the surface or causing distortion.

[0110] For the compositions of Tables 1 and 2, products made from these compositions can provide a new class of non-toxic, cadmium- and selenium-free products that exhibit optical extinction with sharp and adjustable cutoff wavelengths. Unlike Cd-free alternatives that are Se-containing CdSe filter glasses, these products do not contain Resource Conservation and Recovery Act ("RCRA") metals or other hazardous agents. Furthermore, unlike Cd-free alternatives that contain indium and or gallium, the products can be constructed from lower cost elements. For optical properties, products made from these compositions can provide high transparency (e.g., greater than about 90%) over NIR for out to 2.7 microns. Furthermore, the products can exhibit sharp visible cutoff wavelengths of about 320 nm to about 525 nm, which can be adjusted by heat processing conditions (e.g., time and temperature) and by composition.

[0111] For the compositions of Table 3, articles of these exemplary compositions can use molybdenum in place of tungsten, which can be advantageous since molybdenum is generally less expensive than tungsten. Further, articles made from these compositions can be heat processed into a glass-ceramic state, which provides various optical properties. For example, for a thickness of about 0.5 mm, articles of such compositions can have a transmittance of about 4% to about 30% in the visible spectrum (e.g., about 400 nm to about 700 nm), about 5% to about 15% in the NIR (e.g., about 700 nm to about 1500 nm), and about 1% or less in the UV for wavelengths less than about 370 nm or about 5% or less in the UV for wavelengths from 370 nm to about 390 nm. According to some examples, mixed molybdenum-tungsten examples of the articles can absorb 92.3% of the solar spectrum. Such optical properties can be perceived visually as a color of the article. Similar to other compositions, the optical properties arise from growth of precipitates, and as such, the color can change across the article based on heat processing. This color that can be thermally adjusted can be used to create a color gradient within the article, such as a shaded edge or boarder in a windshield or sunroof of the article. Such features can be advantageous to eliminate fritting onto conventional windshield and sunroof surfaces. This color that can be thermally adjusted can be used to create a gradient absorption across the article. Further, articles produced from these compositions can be bleached and patterned by laser (e.g., operating at 355 nm, 810 nm, and 10.6 pm wavelengths). After exposure to these wavelengths of laser, the exposed portions of the article change from a blue or gray color (e.g., due to the color of the precipitates) to a clear water white or yellowish color due to thermal decomposition of the UV and NIR absorbing precipitates. By rastering the laser along the surface of the article to selectively bleach the desired areas, a pattern can be created in the article. When the article is bleached, the resulting glass state is not absorbing for NIR, so the bleaching process is self-limiting (i.e., because the NIR absorbing precipitates have been decomposed). Further, selective laser exposure can not only create a pattern, but also a variable UV & NIR absorption across the article. According to other examples, the articles can be milled to a small enough size and functionalized for use as a photothermal susceptible agent for cancer treatment (i.e., due to its NIR absorbing optical properties).

[0112] For the compositions of Table 4, articles made from these compositions can be capable of being heat treated (e.g., to form a glass-ceramic state) after shaping, thereby simultaneously adjusting optical absorption and producing a wide range of colors from a single composition. Further, such examples can be fusion formable and / or ion exchangeable. Conventional colored glass compositions employing Ag, Au, and / or Cu generally rely on the formation of nanoscale metal precipitates to produce color. The inventors of the present disclosure have discovered that Ag 1+Cations can intercalate into tungsten and molybdenum oxides to form silver tungsten bronzes and / or silver molybdenum bronzes, which can provide multi-color properties to the article. Unexpectedly, the addition of M x WO3or M x MoO3to the composition of the article can produce a variety of colors (e.g., red, orange, yellow, green, blue, various browns, and / or combinations thereof) by heat processing the article for different times and temperatures. It will be appreciated that Au and / or Cu can be used in a similar manner. Analysis confirms that the color tunability is not a result of the ensemble of metal nanoparticles templated on the crystalline phase (e.g., M x WO3or M x MoO3) as a whole. Rather, it is believed that the color tunability in these multi-color articles arises from changes in the band gap energy of the doped tungsten and / or molybdenum oxide precipitates, from the intercalation of the basic ions into the precipitates, and from the concentration of Ag 1+ , Au and / or Cu cations forming pure basic, pure metal, and / or mixed alkali metal, tungsten and / or molybdenum bronzes of different stoichiometry. The band gap energy change of the precipitates is due to its stoichiometry, which is largely independent of the precipitate size and / or shape. Thus, the doped M x WO3or M x MoO3precipitates can remain the same size and / or shape, but can still have many different colors depending on the identity and concentration "x" of the dopant "M". Heat processing of such articles can produce near- complete color reds in a single article. Furthermore, by applying a thermal gradient to the article, the color gradient can be stretched or compressed over some physical distance. In other examples, the article can be laser patterned to locally tune the color of the article. Such articles can be advantageous for the production of tinted sunglass lens blanks, cell phone and / or tablet covers, and / or other products that can be composed of glass-ceramics and can have aesthetic colors. Since the precipitates are located within the glass-ceramic, scratch resistance and environmental durability are higher than in cases where conventional metal color layers and polymer color layers are applied to provide color. Since the color of the article can be changed based on heat processing, a single pot of glass melt can be used to continuously produce blanks that can be heat processed to have specific colors as indicated by consumer demand. Furthermore, articles made from these glass compositions can absorb UV and / or IR radiation, similar to other compositions disclosed herein.

[0113] According to various examples of the present disclosure, the articles can be suitable for use in various fusion forming processes. For example, various compositions of the present disclosure can be used in single fusion laminates or dual fusion laminates where transparent tungsten, molybdenum, mixed tungsten molybdenum, and / or titanium glasses are used as cladding material around a substrate to form a laminated article. After application as cladding, the cladding can transform from a glass state to a glass-ceramic state. The glass-ceramic state cladding of the fusion laminates can have a thickness of about 50 pm to about 200 pm and can have strong UV and IR attenuation and high average visible light transmission (e.g., about 75% to about 85% for automotive windshields and / or architectural glazing), strong UV and IR attenuation and low visible light transmission (e.g., about 5% to about 30% for automotive sidelights, automotive roof panels, and privacy glazing), and / or laminates that can have tunable visible and infrared absorption by treatment in a gradient furnace, localized heating, and / or localized bleaching. Further, the use of the compositions as cladding to form articles provides a new process to fully realize the purpose of tunable optical properties while producing strengthened monolithic glass sheets.

[0114] According to various examples, articles produced from the compositions of the present disclosure can be powdered or granulated and added to various materials. For example, powdered articles can be added to paints, adhesives, polymeric materials (e.g., polyvinyl butyral), sol-gels, and / or combinations thereof. Such features can be advantageous to impart one or more properties of the articles to the materials described above.

[0115] According to various examples, the article can comprise Ti02. The article can comprise Ti02in a concentration of about 0.25 mole percent, or about 0.50 mole percent, or about 0.75 mole percent, or about 1.0 mole percent, or about 2.0 mole percent, or about 3.0 mole percent, or about 4.0 mole percent, or about 5.0 mole percent, or about 6.0 mole percent, or about 7.0 mole percent, or about 8.0 mole percent, or about 9.0 mole percent, or about 10.0 mole percent, or about 11.0 mole percent, or about 12.0 mole percent, or about 13.0 mole percent, or about 14.0 mole percent, or about 15.0 mole percent, or about 16.0 mole percent, or about 17.0 mole percent, or about 18.0 mole percent, or about 19.0 mole percent, or about 20.0 mole percent, or about 21.0 mole percent, or about 22.0 mole percent, or about 23.0 mole percent, or about 24.0 mole percent, or about 25.0 mole percent, or about 26.0 mole percent, or about 27.0 mole percent, or about 28.0 mole percent, or about 29.0 mole percent, or about 30.0 mole percent, or any and all values and ranges therebetween. For example, the article can comprise Ti02in a concentration of about 0.25 mole percent to about 30 mole percent, or about 1 mole percent to about 30 mole percent Ti02, or about 1.0 mole percent to about 15 mole percent Ti02, or about 2.0 mole percent to about 15 mole percent Ti02, or about 2.0 mole percent to about 15.0 mole percent Ti02. It will be appreciated that any and all values and ranges between the recited ranges of Ti02are contemplated.

[0116] According to various examples, the article can include one or more metal sulfides. For example, the metal sulfide can include MgS, Na2S, and / or ZnS. According to various examples, the article can include one or more metal sulfides. For example, the metal sulfide can include MgS, Na2S, and / or ZnS. The article can include a metal sulfide at a concentration of about 0.25 mole percent, or about 0.50 mole percent, or about 0.75 mole percent, or about 1.0 mole percent, or about 2.0 mole percent, or about 3.0 mole percent, or about 4.0 mole percent, or about 5.0 mole percent, or about 6.0 mole percent, or about 7.0 mole percent, or about 8.0 mole percent, or about 9.0 mole percent, or about 10.0 mole percent, or about 11.0 mole percent, or about 12.0 mole percent, or about 13.0 mole percent, or about 14.0 mole percent, or about 15.0 mole percent, or about 16.0 mole percent, or about 17.0 mole percent, or about 18.0 mole percent, or about 19.0 mole percent, or about 20.0 mole percent, or about 21.0 mole percent, or about 22.0 mole percent, or about 23.0 mole percent, or about 24.0 mole percent, or about 25.0 mole percent, or about 26.0 mole percent, or about 27.0 mole percent, or about 28.0 mole percent, or about 29.0 mole percent, or about 30.0 mole percent, or any and all values and ranges therebetween. For example, the article can include a metal sulfide at a concentration of about 0.25 mole percent to about 30 mole percent, or about 1.0 mole percent to about 15 mole percent, or about 1.5 mole percent to about 5 mole percent.

[0117] Similar to the oxides of tungsten and molybdenum described above, examples of articles including titanium can also produce a crystalline phase that includes precipitates of oxides of titanium. The crystalline phase includes oxides of Ti and alkali metal cations (about 0.1 mole percent to about 100 mole percent of the crystalline phase). Without being bound by theory, it is believed that during thermal processing (e.g., heat treatment) of the article, titanium cations cluster and form crystalline precipitates near and on the metal sulfides, transitioning from a glassy state to a glass-ceramic state. The metal sulfides can play a dual role, acting both as a nucleating agent (i.e., because the metal sulfides can have a higher melting temperature than the melt, acting as seeds on which titanium can cluster) and as a reducing agent (i.e., the metal sulfides are high reducing agents and can thereby reduce the clustered titanium to the 3+ state). Thus, due to the metal sulfides, the titanium present in the precipitates can be reduced or partially reduced. For example, the titanium in the precipitates can have an oxidation state of 0 to about +4. For example, the precipitates can have a chemical structure of approximately TiO2. However, it is also possible that a significant portion of the titanium is in the +3 oxidation state, and in some cases, these Ti 3+Cations can be inserted into the channels in the titanium oxide lattice to charge-stabilize the material, forming compounds known as non-stoichiometric, low-valence oxides of titanium, "titanium bronzes" or "bronze-type" titanium crystals. One or more of the above-mentioned alkali metals and / or dopants can be present in the precipitate to compensate for the +3 charge of Ti. Titanium bronzes are M x a group of non-stoichiometric, low-valence oxides of titanium in the general chemical formula form of TiO2, where M = one or more dopant cations from H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce, and where 0 < x < 1. M x The TiO2structure is thought to be a solid-state defect structure, where the holes in the network of reduced TiO2(i.e., the vacancies or channels in the lattice) are randomly occupied by M atoms, which dissociate into M + cations and free electrons. Depending on the concentration of "M", the material properties can range from metallic to semiconducting, enabling tuning of various optical absorption and electrical properties. The more Ti3+, the more M+cations are needed to compensate and the larger the value of x.

[0118] In accordance with the foregoing disclosure, titanium bronze is a compound of the general formula M x TiO2, where M is a cation dopant, such as some other metal, most commonly an alkali metal, and x is a variable less than 1. For clarity, although referred to as 'bronze', these compounds are not structurally or chemically related to metallic bronze, which is an alloy of copper and tin. Titanium bronze is a solid phase spectrum with homogeneity varying with x. Depending on the dopant M and corresponding concentration x, the material properties of titanium bronze can range from metallic to semiconducting and exhibit tunable optical absorption. The structure of these bronzes is a solid-state defect structure, where M' dopant cations are inserted into (i.e., occupy) the holes or channels of the binary oxide matrix and dissociate into M+cations and free electrons.

[0119] For clarity, M x TiO2is a nomenclature convention for a complex system of non-stoichiometric or'sub-stoichiometric' compounds with varying crystal structures, which can be monoclinic, hexagonal, tetragonal, cubic, or pyrochlore, where M can be one or a combination of certain elements from the periodic table, where x varies from 0 < x < 1, where the oxidation state of the bronze-forming element (in this case, Ti) is in its highest oxidation state (Ti 4+ ) and lower oxidation states (e.g., Ti3+ ) of a mixture of substances, and wherein the number two ("2") in Ti02indicates that the number of oxygen anions can be between 1 and 2. Thus, as an alternative, M x Ti02may be expressed as M x TiO Z in chemical form, where 0 < x < 1 and 1 < z < 2, or can be expressed as M x TiO 2-z , where 0 < x < 1 and 0 < z < 1. However, for convenience, for such non-stoichiometric crystals, M x Ti02is used. Similarly, 'bronze' is generally applicable to ternary metal oxides of the form M' x M" y O z , where (i) M" is a transition metal, (ii) M" y O z is its highest binary oxide, (iii) M' is some other metal, and (iv) x is a variable falling in the range 0 < x < 1.

[0120] According to various examples, the glass-ceramic articles containing titanium can be substantially free of W, Mo, and rare earth elements. As described above, the ability of titanium to form its own sub-valent oxides can eliminate the need for tungsten and molybdenum, and the sub-valent oxides of titanium can not require rare earth elements.

[0121] According to various examples, the glass-ceramic articles can have a low concentration of iron or can be free of iron. For example, the articles can contain about 1 mol% or less Fe, or about 0.5 mol% or less Fe, or about 0.1 mol% or less Fe, or 0.0 mol% Fe, or any and all values and ranges therebetween.

[0122] According to various examples, the glass-ceramic articles can have a low concentration of lithium or can be free of lithium. For example, the articles can contain about 1 mol% or less Li, or about 0.5 mol% or less Li, or about 0.1 mol% or less Li, or 0.0 mol% Li, or any and all values and ranges therebetween.

[0123] According to various examples, the glass-ceramic articles can have a low concentration of zirconium or can be free of zirconium. For example, the articles can contain about 1 mol% or less Zr, or about 0.5 mol% or less Zr, or about 0.1 mol% or less Zr, or 0.0 mol% Zr, or any and all values and ranges therebetween.

[0124] Similar to the forming of tungsten-containing or molybdenum-containing articles, titanium-containing articles can be formed by a method comprising: melting together components comprising silica and titanium to form a glass melt; solidifying the glass melt to form a glass; and precipitating bronze-type crystals comprising titanium in the glass to form a glass-ceramic. According to various examples, the precipitation of bronze-type crystals can be performed by one or more heat treatments. For titanium bronze-type crystals, the temperature at which the heat treatment is performed can be from about 400 °C to about 900 °C, or from about 450 °C to about 850 °C, or from about 500 °C to about 800 °C, or from about 500 °C to about 750 °C, or from about 500 °C to about 700 °C, or any and all values and ranges therein. In other words, the precipitation of bronze-type crystals is performed at a temperature of from about 450 °C to about 850 °C, or the precipitation of bronze-type crystals is performed at a temperature of from about 500 °C to about 700 °C. The time period over which the heat treatment is performed can be from about 15 minutes to about 240 minutes, or from about 15 minutes to about 180 minutes, or from about 15 minutes to about 120 minutes, or about 15 minutes, or about 90 minutes, or from about 30 minutes to about 90 minutes, or from about 60 minutes to about 90 minutes, or any and all values and ranges therein. In other words, the precipitation of bronze-type crystals is performed over a time period of from about 15 minutes to about 240 minutes, or the precipitation of bronze-type crystals is performed over a time period of from about 60 minutes to about 90 minutes. The heat treatment can be performed in ambient air, in an inert atmosphere, or in a vacuum.

[0125] The formation of titanium suboxides in the titanium-containing examples of the articles can result in different absorption and transmission rates in different wavelength bands of light. In the ultraviolet (UV) band of light (e.g., from about 200 nm to about 400 nm), the article in the glassy state can have an average UV transmission of from about 18% to about 30% before the precipitation of titanium suboxides. For example, the article in the glassy state can have an average UV transmission of about 18%, or about 19%, or about 20%, or about 21%, or about 22%, or about 23%, or about 24%, or about 25%, or about 26%, or about 27%, or about 28%, or about 29%, or about 30%, or any and all values and ranges therebetween. After the formation or precipitation of titanium suboxides, the article in the glass-ceramic state can have an average UV transmission of from about 0.4% to about 18%. For example, the article in the glass-ceramic state can have an average UV transmission of about 0.4%, or about 0.5%, or about 1%, or about 2%, or about 3%, or about 4%, or about 5%, or about 6%, or about 7%, or about 8%, or about 9%, or about 10%, or about 11%, or about 12%, or about 13%, or about 14%, or about 15%, or about 16%, or about 17%, or about 18%, or any and all values and ranges therebetween. It will be appreciated that the transmission values described above can be present in articles having a thickness or optical path length of from about 0.4 mm to about 1.25 mm.

[0126] In the visible band of light (e.g., about 400 nm to about 750 nm), the article in the glassy state can have an average visible light transmittance of about 60% to about 85% prior to precipitation of the sub-valent titanium oxide. For example, the article in the glassy state can have an average visible light transmittance of about 60%, or about 61%, or about 62%, or about 63%, or about 64%, or about 65%, or about 66%, or about 67%, or about 68%, or about 69%, or about 70%, or about 71%, or about 72%, or about 73%, or about 74%, or about 75%, or about 76%, or about 77%, or about 78%, or about 79%, or about 80%, or about 81%, or about 82%, or about 83%, or about 84%, or about 85%, or any and all values and ranges therein. After formation or precipitation of the sub-valent titanium oxide, the article in the glass-ceramic state can have an average visible light transmittance of about 4% to about 85%. For example, the article in the glass-ceramic state can have an average UV transmittance of about 4%, or about 5%, or about 10%, or about 20%, or about 30%, or about 40%, or about 50%, or about 60%, or about 70%, or about 80%, or about 85%, or any and all values and ranges therein. It will be appreciated that the transmittance values described above can be present in articles having a thickness or optical path length of about 0.4 mm to about 1.25 mm.

[0127] In the near infrared (NIR) band of light (e.g., about 750 nm to about 1500 nm), the article in the glassy state can have an average NIR transmittance of about 80% to about 90% prior to precipitation of the sub-valent titanium oxide. For example, the article in the glassy state can have an average NIR transmittance of about 80%, or about 81%, or about 82%, or about 83%, or about 84%, or about 85%, or about 86%, or about 87%, or about 88%, or about 89%, or about 90%, or any and all values and ranges therein. After formation or precipitation of the sub-valent titanium oxide, the article in the glass-ceramic state can have an average NIR transmittance of about 0.1% to about 10%. For example, the article in the glass-ceramic state can have an average UV transmittance of about 1%, or about 2%, or about 3%, or about 4%, or about 5%, or about 6%, or about 7%, or about 8%, or about 9%, or about 10%, or any and all values and ranges therein. It will be appreciated that the transmittance values described above can be present in articles having a thickness or optical path length of about 0.4 mm to about 1.25 mm.

[0128] In the NIR band of light, the article in the glassy state without the titanium suboxide can have an average optical density per mm (i.e., a first near infrared absorbance) of about 0.4 or less, or about 0.35 or less, or about 0.3 or less, or about 0.25 or less, or about 0.2 or less, or about 0.15 or less, or about 0.1 or less, or about 0.05 or less, or any and all values and ranges therebetween. After precipitation of the titanium suboxide, the article in the glass-ceramic state with the titanium suboxide can have an optical density per mm (i.e., a second near infrared absorbance) of about 6.0 or less, or about 5.5 or less, or about 5.0 or less, or about 4.5 or less, or about 4.0 or less, or about 3.5 or less, or about 3.0 or less, or about 2.5 or less, or about 2.0 or less, or about 2.0 or less, or about 1.5 or less, or about 1.0 or less, or about 0.5 or less, or any and all values and ranges therebetween. Thus, in some cases, the ratio of the second average near infrared absorbance to the first average near infrared absorbance can be about 1.5 or greater, or about 2.0 or greater, or about 2.5 or greater, or about 3.0 or greater, or about 5.0 or greater, or about 10.1 or greater. In such examples, the average optical density per mm of the article in the glass-ceramic state with the titanium suboxide at visible wavelengths can be 1.69 or less.

[0129] According to various examples, the articles can exhibit low haze. For example, the articles can exhibit a haze of about 20% or less, or about 15% or less, or about 12% or less, or about 11% or less, or about 10.5% or less, or about 10% or less, or about 9.5% or less, or about 9% or less, or about 8.5% or less, or about 8% or less, or about 7.5% or less, or about 7% or less, or about 6.5% or less, or about 6% or less, or about 5.5% or less, or about 5% or less, or about 4.5% or less, or about 4% or less, or about 3.5% or less, or about 3% or less, or about 2.5% or less, or about 2% or less, or about 1.5% or less, or about 1% or less, or about 0.5% or less, or about 0.4% or less, or about 0.3% or less, or about 0.2% or less, or about 0.1% or less, or any and all values and ranges therebetween. The haze of the articles is measured on 1 mm thick samples and according to the protocol described above with respect to haze measurements. According to various examples, the haze of the articles can be lower than conventional glass-ceramics due to the absence of beta-quartz (i.e., virgilite), which is common in certain glass-ceramics but which tends to increase haze. In other words, the glass-ceramic articles can be free of beta-quartz crystalline phase. Further, the haze of the articles can be due to a small amount of large crystallites or the absence of large crystallites (e.g., about < 100 nm, or about < 60 nm, or about < 40 nm), which tend to scatter light.

[0130] Articles comprising crystals of Ti02or non-stoichiometric titanium bronze can provide a number of advantages. X Articles comprising crystals of Ti02or non-stoichiometric titanium bronze can provide a number of advantages.

[0131] First, the heat processing time to produce the sub-valent oxides of titanium can be shorter than for other glass-ceramics. Further, the heat processing temperature can be lower than the softening point of the article. Such features can be advantageous for reducing manufacturing complexity and cost.

[0132] Second, color packages (e.g., Ti02+ ZnS) can be introduced to a wide range of melt compositions, including those with ion exchangeable capability. In addition to this, the impact of such color packages on chemical durability and other relevant properties of the article can be small due to the low concentration of color package required.

[0133] Third, glass-ceramics using titanium-containing sub-valent oxides can provide fusion formable and chemically strengthenable materials for UV and / or IR blocking materials that can not have the difficulty of melting due to radiation capture. For example, for articles containing titanium sub-valent oxides, when melted or in the as-cast state (i.e., green state prior to heat treatment), they are highly transparent in the visible and NIR wavelengths, unlike Fe 2+ Doped glasses.

[0134] Examples

[0135] The following examples represent non-limiting examples of compositions of articles of the present disclosure.

[0136] Referring now to Table 1, the articles can have: S1O2 from about 58.8 mol% to about 77.58 mol%, AI2O3 from about 0.66 mol% to about 13.69 mol%, B2O3 from about 4.42 mol% to about 27 mol%, R2O from about 0 mol% to about 13.84 mol%, RO from about 0 mol% to about 0.98 mol%, WO3 from about 1.0 mol% to about 13.24 mol%, and Sn02 from about 0 mol% to about 0.4 mol%. It will be understood that any of the exemplary compositions of Table 1 can include: Mn02 from about 0 mol% to about 0.2 mol%, Fe203 from about 0 mol% to about 0.1 mol%, Ti02 from about 0 mol% to about 0.01 mol%, As205 from about 0 mol% to about 0.17 mol%, and / or Eu203 from about 0 mol% to about 0.1 mol%. The compositions of Table 1 are provided in the as- batched state in the crucible.

[0137] Table 1:

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] Referring now to Table 2, the article can have: S1O2 from about 65.43 mol% to about 66.7 mol%, AI2O3 from about 9.6 mol% to about 9.98 mol%, B2O3 from about 9.41 mol% to about 10.56 mol%, R2O from about 6.47 mol% to about 9.51 mol%, RO from about 0.96 mol% to about 3.85 mol%, WO3 from about 1.92 mol% to about 3.85 mol%, MoO3 from about 0 mol% to about 1.92 mol%, and SnO2 from about 0 mol% to about 0.1 mol%. The compositions of Table 2 are provided as just batched in a crucible.

[0144] Table 2

[0145]

[0146]

[0147] Referring now to Table 3, the article can have: S1O2 from about 60.15 mol% to about 67.29 mol%, AI2O3 from about 9.0 mol% to about 13.96 mol%, B2O3 from about 4.69 mol% to about 20 mol%, R2O from about 2.99 mol% to about 12.15 mol%, RO from about 0.00 mol% to about 0.14 mol%, WO3 from about 0 mol% to about 7.03 mol%, MoO3 from about 0 mol% to about 8.18 mol%, SnO2 from about 0.05 mol% to about 0.15 mol%, and V2O5 from about 0 mol% to about 0.34 mol%. It will be appreciated that any of the exemplary compositions of Table 3 can include Fe2O3 from about 0 mol% to about 0.0025 mol%. The compositions of Table 3 are provided as just batched in a crucible.

[0148] Table 3

[0149]

[0150]

[0151] Referring now to Table 4, the article may have the following components: SiO2 about 54.01 mol% to about 67.66 mol%, Al2O3 about 9.55 mol% to about 11.42 mol%, B2O3 about 9.36 mol% to about 15.34 mol%, R2O about 9.79 mol% to about 13.72 mol%, RO about 0.00 mol% to about 0.22 mol%, WO3 about 1.74 mol% to about 4.48 mol%, MoO3 about 0 mol% to about 1.91 mol%, SnO2 about 0.0 mol% to about 0.21 mol%, V2O5 about 0 mol% to about 0.03 mol%, Ag about 0 mol% to about 0.48 mol%, and Au about 0 mol% to about 0.01 mol. It will be understood that any exemplary composition of Table 4 may comprise: CeO2 about 0 mol% to about 0.19 mol%, CuO about 0 mol% to about 0.48 mol%, Br- about 0 mol% to about 0.52 mol%, Cl- about 0 mol% to about 0.2 mol%, TiO2 about 0 mol% to about 0.96 mol%, and / or Sb2O3 about 0 mol% to about 0.29 mol%. The compositions of Table 4 are provided in the state of freshly prepared ingredients in a crucible.

[0152] Table 4

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] Referring now to Table 5, the article may have: SiO2 about 60.01 mol% to about 77.94 mol%, Al2O3 about 0.3 mol% to about 10.00 mol%, B2O3 about 10 mol% to about 20 mol%, R2O about 0.66 mol% to about 10 mol%, WO3 about 1.0 mol% to about 6.6 mol%, and SnO2 about 0.0 mol% to about 0.1 mol%. It will be understood that any exemplary composition of Table 5 may contain about 0 mol% to about 0.09 mol% of Sb2O3. The compositions of Table 5 are provided in the state of freshly prepared material in a crucible.

[0160] Table 5

[0161]

[0162]

[0163] Referring now to Table 6, a list of comparative example glass compositions are provided that form a liquid alkali tungstate that separates during the melting process when they are melted with unbound alkali batch materials (e.g., alkali carbonates) instead of bound alkali species (e.g., nepheline). As explained above, the second liquid alkali tungstate phase can solidify as a separate crystal, which can make the substrates made therefrom milky.

[0164] Table 6

[0165]

[0166]

[0167] Example Applications

[0168] In the interest of context, cadmium and selenium containing glasses ("CdSe glasses") can be characterized by their toxicity because they have appreciable amounts of cadmium and selenium. Some efforts have been made to develop non-toxic or low-toxicity alternatives to CdSe glasses. For example, some conventional alternatives include Cd-free glass compositions. However, these compositions still contain selenium and other expensive dopants such as indium and gallium. In addition, conventional Cd-free selenium containing glasses are characterized by having a poor cutoff wavelength and / or visual angle dependence relative to CdSe glasses. Thus, Applicants believe that there is a need for cadmium and selenium free materials that have comparable or improved optical properties relative to conventional CdSe glasses. Preferably, these materials have tunable bandgaps and sharp cutoffs as non-toxic alternatives to CdSe glasses. There is also a need for non-toxic CdSe glass alternatives to have low coefficients of thermal expansion (CTE), durability, thermal stress resistance, and / or relatively simple and low cost manufacturing and processing requirements for targeted applications of these materials.

[0169] According to some aspects of the disclosure, a glass-ceramic is provided that includes an aluminoborosilicate glass; WO3 from about 0.7 to about 15 mol.%; at least one alkali metal oxide from about 0.2 to about 15 mol.%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol.%.

[0170] According to some aspects of the disclosure, a glass-ceramic is provided that includes an aluminoborosilicate glass; WO3 from about 0.7 to about 15 mol.%; at least one alkali metal oxide from about 0.2 to about 15 mol.%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol.%. In addition, the glass-ceramic includes an optical transmittance of at least 90% from 700 nm to 3000 nm, and a sharp cutoff wavelength from about 320 nm to about 525 nm.

[0171] According to other aspects of the disclosure, a glass-ceramic is provided that includes an aluminoborosilicate glass; WO3about 0.7 to about 15 mol.%; at least one alkali metal oxide about 0.2 to about 15 mol.%; and at least one alkaline earth metal oxide about 0.1 to about 5 mol.%. Further, the glass-ceramic includes at least one of: an alkaline earth, an alkali, and a mixed alkaline earth-alkali tungstate crystalline phase in either stoichiometric or non-stoichiometric form.

[0172] In some implementations of the foregoing aspects of the glass-ceramic, the aluminoborosilicate glass includes: SiO2about 55 to about 80 mol.%, Al2O3about 2 to about 20 mol.%, and B2O3about 5 to about 40 mol.%, SiO268 to 72 mol.%, Al2O38 to 12 mol.%, and B2O35 to 20 mol.%. Further, the at least one alkaline earth metal oxide can include MgO 0.1 to 5 mol.%. The at least one alkali metal oxide can include Na2O 5 to 15 mol.%. Further, the difference in the amount of the at least one alkali metal oxide and Al2O3in the aluminoborosilicate glass can range from -6 mol.% to +2 mol.%.

[0173] In other implementations of the foregoing aspects of the glass-ceramic, the glass-ceramic can be substantially free of cadmium and substantially free of selenium. Further, the glass-ceramic can also include at least one dopant selected from the group consisting of: F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te, and Bi. In other implementations of the foregoing aspects of the glass-ceramic, the glass-ceramic can also include MoO3, which is from 0% to about 50% of the WO3present in the glass-ceramic.

[0174] According to another aspect of the disclosure, an article is provided that includes a substrate including a major surface and a glass-ceramic composition that includes: an aluminoborosilicate glass; WO3about 0.7 to about 15 mol.%; at least one alkali metal oxide about 0.2 to about 15 mol.%; and at least one alkaline earth metal oxide about 0.1 to about 5 mol.%. Further, in some implementations of this aspect, the substrate also includes a compressive stress region extending from the major surface to a first selected depth in the substrate and is a result of an ion exchange process. Further, in some implementations of this aspect, the substrate can include: an optical transmittance of at least 90% from 700 nm to 3000 nm, and a sharp cut-off wavelength from about 320 nm to about 525 nm.

[0175] According to another aspect of the disclosure, a method of making a glass-ceramic is provided, comprising: mixing a batch material comprising an aluminoborosilicate glass, WO3 from about 0.7 to about 15 mol%, at least one alkali metal oxide from about 0.2 to about 15 mol%, and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%; melting the batch material at from about 1500 °C to about 1700 °C to form a melt; annealing the melt at from about 500 °C to about 600 °C to define an annealed melt; and heat treating the annealed melt at from about 500 °C to about 1000 °C for from about 5 minutes to about 48 hours to form the glass-ceramic.

[0176] In some implementations of the foregoing method of making a glass-ceramic, the heat treating comprises heat treating the annealed melt at from about 600 °C to about 800 °C for from about 5 minutes to about 24 hours to form the glass-ceramic. Further, the heat treating comprises heat treating the annealed melt at from about 650 °C to about 725 °C for from about 45 minutes to about 3 hours to form the glass-ceramic. In some implementations of the method, the glass-ceramic can comprise at least 90% optical transmittance from 700 nm to 3000 nm, and a sharp cut-off wavelength from about 320 nm to about 525 nm.

[0177] As described in detail herein, provided are glass-ceramic materials that are free of cadmium and selenium having comparable or improved optical properties compared to conventional CdSe glasses. In implementations, these materials have tunable bandgaps and sharp cut-offs as non-toxic alternatives to CdSe glasses. Implementations of these materials can also be characterized by low coefficient of thermal expansion (CTE), durability, thermal stress resistance, and / or relatively simple and low cost manufacturing and processing requirements.

[0178] More generally, the glass-ceramic materials and articles containing them disclosed herein comprise a balance of an aluminoborosilicate glass, a tungsten oxide, at least one alkali metal oxide, and at least one alkaline earth metal oxide. These glass-ceramic materials can be characterized by at least 90% optical transmittance from 700 nm to 3000 nm, and a sharp cut-off wavelength from about 320 nm to about 525 nm. Further, these materials can comprise at least one alkaline earth tungstate phase, for example, established via particular heat treatment conditions following formation of the glass-ceramic. Further, implementations of these glass-ceramic materials are characterized by tunable cut-offs by selection of particular heat treatment conditions. As such, these glass-ceramic materials provide non-toxic, cadmium and selenium free glass-ceramics as alternatives to conventional CdSe glasses.

[0179] Various embodiments of the glass-ceramic materials of the present disclosure can be used in the form of substrates, elements, coverings, and other elements in any of the following applications: security and surveillance filters configured to suppress visible light for infrared illumination; airport runway lights; laser safety glasses; gratings for motion control of motors; bar code readers; atomic force microscopes; nano-imprint machines; laser interferometer metrology solutions; laser-based dynamic calibration systems; photolithography solutions for integrated circuit manufacturing; photonic bit error rate test solutions; photonic digital communications analyzers; photonic jitter generation and analysis systems; optical modulation analyzers; optical power meters; optical attenuators; light sources; optical wave composition analyzers; gas chromatographs; spectrometers; fluorescence microscopes; traffic monitoring cameras; environmental waste, water, and exhaust gas monitoring equipment; spectral filters for cameras; radiation thermometers; imaging brightness chroma meters; industrial image processing; controllable wavelength light sources for forgery detection; scanners for digitizing color images; astronomical filters; Humphrey field analyzers in medical diagnostic equipment; and filters for ultra-short pulse lasers. Embodiments of these glass-ceramic materials are also suitable for various artistic attempts and applications utilizing colored glass, glass-ceramics, and ceramics, such as glass blowers, pyromancers, stained glass artists, and the like.

[0180] The glass-ceramic materials, and articles containing them, offer various advantages over conventional glass, glass-ceramic, and ceramic materials in the same field (including over CdSe glass). As described above, the glass-ceramic materials of the present disclosure are cadmium and selenium free, while providing a sharp visible light extinction similar to that of conventional CdSe filter glass in the orange color. The glass-ceramic materials of the present disclosure also provide a sharper visible light extinction than semiconductor-doped glasses (conventional alternatives to CdSe glass). Furthermore, the glass-ceramic materials of the present disclosure are formulated with lower cost materials than conventional alternatives to CdSe glass that employ indium, gallium, and / or other high cost metals and components. Another advantage of these glass-ceramic materials is that they can be characterized as having a cutoff wavelength that can be adjusted by selection of heat treatment temperature and time conditions. Another advantage of these glass-ceramics is that they are transparent in the near infrared ("NIR") spectrum and do not exhibit a drop in transmittance at 900 to 1100 nm wavelengths (unlike CdSe glass). Furthermore, these glass-ceramic materials can be produced by conventional melt-quenching processes, unlike conventional CdSe glass alternatives that require additional semiconductor synthesis and milling steps (e.g., semiconductor-doped glasses containing indium and gallium).

[0181] Referring now to Figure 1The article 100, as shown, includes a substrate 10 that includes a glass-ceramic composition according to the present disclosure. These articles can be used for any of the applications listed above (e.g., optical filters, airport runway lights, bar code readers, etc.). Thus, in some embodiments, the substrate 10 can be characterized by at least 90% optical transmission from 700 nm to 3000 nm, and a sharp cut-off wavelength from about 320 nm to about 525 nm. The substrate 10 includes a pair of opposed major surfaces 12, 14. In some embodiments of the article 100, the substrate 10 includes a compressive stress region 50. As shown in Figure 1 the compressive stress region 50 of the article 110 is exemplary and extends from the major surface 12 to a first selected depth 52 within the substrate. Some embodiments of the article 100 (not shown) include a comparable additional compressive stress region 50 that extends from the major surface 14 to a second selected depth (not shown). Further, some embodiments of the article 100 (not shown) include a plurality of compressive stress regions 50 that extend from the major surfaces 12, 14 of the substrate 10. Further still, some embodiments of the article 100 (not shown) include a plurality of compressive stress regions 50 that extend from respective major surfaces 12, 14, and also from the short edges (i.e., edges that are orthogonal to the major surfaces 12, 14) of the substrate 10. As will be appreciated by those skilled in the art of the present disclosure, various combinations of compressive stress regions 50 can be incorporated in the article 100, depending on the processing conditions used to produce these compressive stress regions 50 (e.g., fully immersing the substrate 10 in a molten salt ion exchange bath, partially immersing the substrate 10 in a molten salt ion exchange bath, fully immersing the substrate 10 with certain edges and / or surfaces shielded, etc.).

[0182] As used herein, "selected depth" (e.g., selected depth 52), "depth of compression," and "DOC" can be used interchangeably to define the depth in the substrate 10 described herein where the stress changes from compressive to tensile. The DOC can be measured by a surface stress meter (e.g., FSM-6000) or a scattered light polariscope (SCALP), depending on the ion exchange process. When stresses are created in a substrate 10 having a glass or glass-ceramic composition by ion exchanging potassium into the glass substrate, the DOC is measured using a surface stress meter. When stresses are created in a glass article by ion exchanging sodium into the glass article, the DOC is measured using a SCALP. When stresses are created in a substrate 10 having a glass or glass-ceramic composition by ion exchanging both potassium and sodium into the glass, the DOC is measured by SCALP because it is believed that the exchange depth of sodium represents the DOC and the exchange depth of potassium represents the change in magnitude of the compressive stress (rather than the stress changing from compressive to tensile); in such glass substrates, the exchange depth of potassium is measured by a surface stress meter. Also as used herein, "maximum compressive stress" is defined as the maximum compressive stress within the compressive stress region 50 in the substrate 10. In some embodiments, the maximum compressive stress is obtained at or immediately proximate to the one or more major surfaces 12, 14 defining the compressive stress region 50. In other embodiments, the maximum compressive stress is obtained between the one or more major surfaces 12, 14 and the selected depth 52 of the compressive stress region 50.

[0183] Referring again to Figure 1 , the substrate 10 of the article 100 can be characterized by a glass-ceramic composition. In embodiments, the glass-ceramic composition of the substrate 10 has: WO3 is 0.7 to 15 mole percent, at least one alkali metal oxide is 0.2 to 15 mole percent, at least one alkaline earth metal oxide is 0.1 to 5 mole percent, and a balance of silicate-containing glass. These silicate-containing glasses include: aluminoborosilicate glass, borosilicate glass, aluminosilicate glass, soda-lime glass, and chemically strengthened versions of these silicate-containing glasses.

[0184] Further, in Figure 1 embodiments of the article 100 shown, the substrate 10 can have a selected length and width or diameter to define its surface area. The substrate 10 can have at least one edge defined by its length and width or defined by its diameter between the major surfaces 12, 14 of the substrate 10. The substrate 10 can also have a selected thickness. In some embodiments, the substrate has a thickness of about 0.2 mm to about 1.5 mm, about 0.2 mm to about 1.3 mm, and about 0.2 mm to about 1.0 mm. In other embodiments, the substrate has a thickness of about 0.1 mm to about 1.5 mm, about 0.1 mm to about 1.3 mm, or about 0.1 mm to about 1.0 mm.

[0185] In some embodiments of the article 100, as shown in the exemplary form of Figure 1 The substrate 10 can be selected from a chemically strengthened aluminoborosilicate glass having a compressive stress region 50 extending to a first selected depth 52 of greater than 10 pm, with a maximum compressive stress of greater than 150 MPa. In other embodiments, the substrate 10 can be selected from a chemically strengthened aluminoborosilicate glass having a compressive stress region 50 extending to a first selected depth 52 of greater than 25 pm, with a maximum compressive stress of greater than 400 MPa. The substrate 10 of the article 100 can also include one or more compressive stress regions 50 extending from one or more of the major surfaces 12, 14 to a selected depth 52 (or depths) with a maximum compressive stress of greater than about 150 MPa, greater than 200 MPa, greater than 250 MPa, greater than 300 MPa, greater than 350 MPa, greater than 400 MPa, greater than 450 MPa, greater than 500 MPa, greater than 550 MPa, greater than 600 MPa, greater than 650 MPa, greater than 700 MPa, greater than 750 MPa, greater than 800 MPa, greater than 850 MPa, greater than 900 MPa, greater than 950 MPa, greater than 1000 MPa, and all maximum compressive stress levels between these values. In some embodiments, the maximum compressive stress is 2000 MPa or less. Further, the depth of compression (DOC) or first selected depth 52 can be set to 10 pm or greater, 15 pm or greater, 20 pm or greater, 25 pm or greater, 30 pm or greater, 35 pm or greater, and to even greater depths depending on the thickness of the substrate 10 and the processing conditions associated with creating the compressive stress region 50. In some embodiments, the DOC is less than or equal to 0.3 times the thickness (t) of the substrate 10, e.g., 0.3t, 0.28t, 0.26t, 0.25t, 0.24t, 0.23t, 0.22t, 0.21t, 0.20t, 0.19t, 0.18t, 0.15t, or 0.1t.

[0186] As described above, the glass-ceramic materials of the present disclosure, including the substrate 10 for the article 100, see Figure 1)Characterized by the following glass-ceramic composition: 0.7 to 15 mol% of WO3; 0.2 to 15 mol% of at least one alkali metal oxide; 0.1 to 5 mol% of at least one alkaline earth metal oxide; and the balance being a silicate-containing glass, such as an aluminoborosilicate glass. In an embodiment, the glass-ceramic material can be characterized by: an optical transmittance of at least 90% from 700 nm to 3000 nm, and a sharp cut-off wavelength from about 320 nm to about 525 nm. In some practical embodiments, the glass-ceramic material can also be characterized by the presence of at least one alkaline earth tungstate crystal phase and / or at least one alkali metal tungstate crystal phase. For example, the alkaline earth tungstate crystal phase can be M x WO3, where M is at least one of Be, Mg, Ca, Sr, Ba, and Ra, and where 0 < x < 1. In an embodiment of the glass-ceramic of the present disclosure, the at least one alkaline earth tungstate crystal phase is one or both of the following: MgWO4 crystal phase (see, for example, Figure 5 and its corresponding description) and MgW2O7 crystal phase (see, for example, Figures 6A-6C Figures 7A & 7B and their corresponding descriptions). Again, for example, the alkali metal tungstate crystal phase can be M x WO3, where M is at least one of Li, Na, K, Cs, Rb, and where 0 < x < 1. Again, for example, the tungstate crystal phase can be M x WO3, where M is a combination of an alkaline earth substance selected from Be, Mg, Ca, Sr, Ba, and Ra and an alkali metal selected from Li, Na, K, Cs, Rb, and where 0 < x < 1.

[0187] In an embodiment, the glass-ceramic of the present disclosure is optically transparent in the visible light region of the spectrum (i.e., from about 400 nm to about 700 nm). As used herein, the term "optically transparent" means having a transmittance greater than about 1% (e.g., in units of % / mm) over at least one 50-nm-wide wavelength band of light in the range from about 400 nm to about 700 nm for a 1-mm path length. In some embodiments, for at least one 50-nm-wide wavelength band of light in the visible spectral region, the glass-ceramic has a transmittance of at least greater than about 5% / mm, greater than about 10% / mm, greater than about 15% / mm, greater than about 20% / mm, greater than about 25% / mm, greater than about 30% / mm, greater than about 40% / mm, greater than about 50% / mm, greater than about 60% / mm, greater than about 70% / mm, and greater than all lower limit values between these values.

[0188] Embodiments of the glass-ceramics of the present disclosure absorb light in the ultraviolet ("UV") region of the spectrum (i.e., wavelengths less than about 370 nm) and / or the near infrared ("NIR") region (i.e., wavelengths from about 700 nm to about 1700 nm) without the use of additional coatings or films. In some embodiments, the glass-ceramics are characterized by a transmittance of less than 10% / mm, less than 9% / mm, less than 8% / mm, less than 7% / mm, less than 6% / mm, less than 5% / mm, less than 4% / mm, less than 3% / mm, less than 2% / mm, and even less than 1% / mm for at least one 50 nm wide band of light in the UV region of the spectrum. In some embodiments, the glass-ceramics absorb or have an absorption of at least 90% / mm, at least 91% / mm, at least 92% / mm, at least 93% / mm, at least 94% / mm, at least 95% / mm, at least 96% / mm, at least 97% / mm, at least 98% / mm, or even at least 99% / mm for at least one 50 nm wide band of light in the UV region of the spectrum. In other embodiments, the glass-ceramics are characterized by a transmittance of less than 10% / mm, less than 9% / mm, less than 8% / mm, less than 7% / mm, less than 6% / mm, less than 5% / mm, less than 4% / mm, less than 3% / mm, less than 2% / mm, and even less than 1% / mm for at least one 50 nm wide band of light in the NIR region of the spectrum. In other embodiments, the glass-ceramics absorb or have an absorption of at least 90% / mm, at least 91% / mm, at least 92% / mm, at least 93% / mm, at least 94% / mm, at least 95% / mm, at least 96% / mm, at least 97% / mm, at least 98% / mm, or even at least 99% / mm for at least one 50 nm wide band of light in the NIR region of the spectrum.

[0189] Embodiments of the glass-ceramic materials of the present disclosure include an alumino-boro-silicate glass (e.g., containing Si02, AI2O3, and B203), W03, at least one alkali metal oxide, and at least one alkaline earth metal oxide. In some embodiments, the alumino-boro-silicate glass comprises from about 55 mol% to about 80 mol% Si02, from about 60 mol% to about 74 mol% Si02, or from about 64 mol% to about 70 mol% Si02. Further, the alumino-boro-silicate glass of the glass-ceramics can comprise from about 2 mol% to about 40 mol% B203, from about 5 mol% to about 16 mol% B203, or from about 6 mol% to about 12 mol% B203. Further, the alumino-boro-silicate glass of the glass-ceramics can comprise from about 0.5 mol% to about 16 mol% AI2O3, from about 2 mol% to about 20 mol% AI2O3, or from about 6 mol% to about 14 mol% AI2O3.

[0190] The glass-ceramic materials of the present disclosure include from about 0.7 mol% to about 15 mol% WO3. In some embodiments, the glass-ceramic materials include from about 1 mol% to about 6 mol% WO3or from about 1.5 mol% to about 5 mol% WO3. In some embodiments, the glass-ceramics can also include from about 0% to about 50% of the MoO3present in the composition as WO3(i.e., from about 0% to 5 mol% MoO3). In some embodiments, the glass-ceramics also include from about 0 mol% to about 3 mol% or from about 0 mol% to about 2 mol% MoO3.

[0191] The glass-ceramic materials of the present disclosure include at least one alkali metal oxide. In embodiments, the glass-ceramic materials include from about 0.2 mol% to about 15 mol% of the at least one alkali metal oxide. The at least one alkali metal oxide can be selected from the group consisting of Li2O, Na2O, K2O, Rb2O, and Cs2O. In some embodiments, the difference between the amount of the at least one alkali metal oxide and Al2O3in the aluminoborosilicate glass ranges from -6 mol% to +2 mol%.

[0192] The glass-ceramic materials of the present disclosure also include at least one alkaline earth metal oxide. In embodiments, the glass-ceramics include from about 0.1 mol% to about 5 mol% of the at least one alkaline earth metal oxide. The at least one alkaline earth metal oxide can be selected from the group consisting of MgO, SrO, and BaO. In other embodiments, the glass-ceramic materials of the present disclosure include from about 0 mol% to about 0.5 mol%, from about 0 mol% to about 0.25 mol%, or from about 0 mol% to about 0.15 mol% SnO2.

[0193] According to preferred embodiments, the glass-ceramic materials of the present disclosure are substantially free of cadmium and substantially free of selenium. In embodiments, the glass-ceramics can also include at least one dopant selected from the group consisting of F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te, and Bi. In some embodiments, the at least one dopant present in the glass-ceramics is from about 0 mol% to about 0.5 mol% as oxide.

[0194] Non-limiting compositions of the glass-ceramics according to the principles of the present disclosure are found in Tables 1A (recorded as wt%) and 1B (recorded as mol%) below.

[0195] Table 1A

[0196]

[0197] Table 1A (continued)

[0198]

[0199]

[0200] Table IB

[0201]

[0202] Table IB (continued)

[0203]

[0204]

[0205] According to embodiments, the glass-ceramic materials of the present disclosure can be manufactured by employing a melt-quenching process. The components can be mixed by turbulent mixing and / or ball milling and compounding in appropriate proportions. The batch materials can include, but are not limited to, one or more of the following: sand, spodumene, petalite, nepheline, syenite, alumina, borax, boric acid, carbonates and nitrates of alkali and alkaline earth metals, tungsten oxides, and ammonium tungstate. The batched materials are then melted at a temperature of about 1500°C to about 1700°C for a predetermined time. In some embodiments, the predetermined time ranges from about 6 to about 12 hours, after which the resulting melt can be cast or shaped and then annealed, as understood by one skilled in the art of the present disclosure. In some embodiments, the melt can be annealed at a temperature of about 500°C to about 600°C to define an annealed melt.

[0206] At this stage of the method, the annealed melt is heat treated at a temperature of about 500°C to about 1000°C for a time period of about 5 minutes to about 48 hours to form a glass-ceramic. In embodiments, the heat treatment step is performed at or slightly above the annealing point of the glass-ceramic and below its softening point to establish one or more crystalline tungstate phases.

[0207] In some embodiments, the annealed melt is heat treated at a temperature of about 600°C to about 800°C for a time period of about 5 minutes to about 24 hours to form a glass-ceramic. According to some embodiments, the annealed melt is heat treated at a temperature of about 650°C to about 725°C for a time period of about 45 minutes to about 3 hours to form a glass-ceramic. In another embodiment, the annealed melt is heat treated according to temperatures and times to obtain specific optical properties, such as at least 90% optical transmittance from 700 nm to 3000 nm and a sharp cut-off wavelength of about 320 nm to about 525 nm. Further, other heat treatment temperatures and times can be employed to obtain glass-ceramic materials, as described in the examples below.

[0208] Examples of exemplary applications

[0209] The following examples represent certain non-limiting examples of glass-ceramic materials and articles of the present disclosure, including methods of making the same.

[0210] Referring now to Figure 2A and 2B , plots of transmittance versus wavelength are provided for a comparative CdSe glass ("Comparative Example 1") and a heat-treated glass-ceramic ("Example 1"). Note that, Figure 2B is Figure 2A an image of the same, rescaled to show the cutoff wavelength of the comparative CdSe glass and the heat-treated glass-ceramic samples. In this example, the comparative CdSe glass (Comparative Example 1) has a conventional CdSe glass composition according to: 40-60% Si02, 5-20% B203, 0-8% P205, 1.5-6% Al203, 4-8% Na20, 6-14% K20, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2-1% S, and 0-1% Se; while the heat-treated glass-ceramic has the same composition as the Example 1 sample shown in Tables 1A and IB. Further, Figure 2A and 2B , the glass-ceramics shown in Figs. Figure 2A and 2B both have a normalized path length of 4 mm. It is evident from these figures that the glass-ceramic sample heat-treated at 700°C for 1 hour (Example 1) exhibits a sharp cutoff and acuity in the same approximate wavelength range as the CdSe glass sample (Comparative Example 1).

[0211] Referring now to Figure 3A and 3B , plots of transmittance versus wavelength are provided for a comparative CdSe glass ("Comparative Example 1") and a heat-treated glass-ceramic ("Examples 1A-1K"). Note that, Figure 3B is Figure 3Aof the comparative CdSe glass and the heat treated glass-ceramic samples. In this example, the comparative CdSe glass (Comparative Example 1) had a conventional CdSe glass composition according to: 40-60% Si02, 5-20% B203, 0-8% P205, 1.5-6% AI2O3, 4-8% Na20, 6-14% K20, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2-1% S, and 0-1% Se; while the heat treated glass-ceramic samples had the same compositions as the Example 1 samples shown in Tables 1A and IB, respectively. In addition, Figure 3A and 3B The glass-ceramics shown in FIGS. 1A-1K were each prepared according to the methods of making glass-ceramic materials described above in the disclosure, including the following heat treatment steps after annealing: 525°C for 1 hour and 40 minutes (Example 1A); 525°C for 10 hours and 39 minutes (Example IB); 550°C for 3 hours and 10 minutes (Example 1C); 600°C for 6 hours and 24 minutes (Example ID); 600°C for 15 hours and 20 minutes (Example IE); 650°C for 2 hours (Example IF); 650°C for 3 hours (Example 1G); 650°C for 5 hours and 35 minutes (Example 1H); 650°C for 23 hours and 10 minutes (Example II); 700°C for 1 hour (Example 1J); and 700°C for 2 hours (Example IK). In addition, Figure 3A and 3B All of the samples shown in FIGS. 1A-1K had a normalized path length of 4 mm. As evidenced by these figures, all of the glass-ceramic samples (Examples 1A-1K) heat treated according to the various conditions exhibited sharp cut-offs and acuity in the same approximate wavelength range as the CdSe glass (Comparative Example 1). In addition, as evidenced by these figures, various heat treatment temperature and time conditions can be employed to vary and adjust the cut-off wavelength and its acuity in the range of about 320 nm to about 525 nm.

[0212] According to another example, a comparative CdSe glass and glass-ceramic samples heat treated at 700°C and 800°C according to various conditions were prepared and their optical properties were evaluated. Figure 4A FIG. 2 is a plot of the transmittance versus wavelength of a comparative CdSe glass ("Comparative Example 1") and glass-ceramic samples heat treated at 700°C and 800°C according to various conditions (Examples IK and 2A). Note that, Figure 4B is Figure 4Aof Comparative Example CdSe glass and glass-ceramic samples heat treated according to various conditions. In this example, Comparative Example CdSe glass (Comparative Example 1) has a conventional CdSe glass composition according to: 40-60% Si02, 5-20% B203, 0-8% P205, 1.5-6% AI2O3, 4-8% Na20, 6-14% K20, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2-1% S, and 0-1% Se; the heat treated glass-ceramic sample (Example IK) has the same composition as the Example 1 sample shown in Tables 1A and IB; and the heat treated glass-ceramic sample (Example 2A) has the same composition as the Example 2 sample shown in Tables 1A and IB. Further, Figure 4A and 4B The glass-ceramics shown in Tables 1A and IB were each prepared according to the methods of making glass-ceramic materials described above in the disclosure, and included the following heat treatment steps after annealing: 700 °C for 2 hours (Example IK); and 800 °C for 1 hour 4 minutes (Example 2A). Further, Figure 4A and 4B All samples shown in Tables 1A and IB have a normalized path length of 4 mm. It is evident from these figures that all glass-ceramic samples heat treated according to various conditions (Examples IK and 2A) exhibit sharp cut-offs and acuity in the same wavelength range as CdSe glass (Comparative Example 1). Further, it is also evident from these figures and the respective compositions of these glass-ceramics (see Tables 1A and IB) that these magnesium-tungsten glass-ceramic compositions can be used to vary and tune the cut-off wavelength and its acuity in the range of about 320 nm to about 525 nm through specific heat treatment conditions. It is also apparent that the higher magnesium content in the Example 2A glass-ceramic (about 3.84 mole %) can contribute to its lower cut-off wavelength and to its higher transmittance in the NIR range compared to the Example IK glass-ceramic (about 0.95 mole %). Thus, and without being bound by theory, varying the magnesium content in these glass-ceramic compositions and varying the heat treatment conditions can have an effect on varying the spectrum and cut-off wavelength of the glass-ceramic.

[0213] Referring now to Figure 4C again provided are Figure 4AImages and transmittance versus wavelength graphs of comparative example CuInSe and CuInS glass samples ("Comparative Example 2" and "Comparative Example 3", respectively). Spectra of Comparative Example 2 and Comparative Example 3 were obtained from the "Exemption Renewal Request 13(b)" submitted by Spectaris eV to Oko-Institute.V. on March 26, 2015. Furthermore, Figure 4 is magnified to show the cutoff wavelengths of comparative example CdSe glass (Comparative Example 1), glass-ceramic samples heat-treated under various conditions (Examples 1K and 2A), and comparative example CuInSe and CuInS samples (Comparative Example 2 and Comparative Example 3). Figure 4C It has been confirmed that the glass-ceramic materials according to this disclosure (Examples 1K and 2A) are superior to the comparative CuInSe and CuInS glasses in terms of their cutoff wavelengths, which are close to those of the comparative CdSe glass. In other words, these glass-ceramics exhibit optical properties that are closer to those of CdSe glass than other semiconductor-doped glass alternatives (CuInSe and CuInS).

[0214] See now Figure 5 X-ray diffraction (“XRD”) patterns of at least one heat-treated glass-ceramic (Example 1L, see Tables 1A and 1B) according to this disclosure are provided. This sample was heat-treated at 700°C for 17 hours and 16 minutes. From the peak evidence of the listed d-spacing (e.g., d = 3.6127, d = 3.2193, etc.), the glass-ceramic of Example 1L would comprise a crystalline MgWO4 tungsten oxide phase. Not limited to theory, Figure 5 The XRD pattern also suggests that the glass-ceramic comprises a non-stoichiometric MgWO4 phase or a mixed basic MgWO4 phase, which can be described as M x WO4 crystals, wherein M = Mg or M = Mg and one or more alkali metals selected from Li, Na, K, Rb and Cd, and 0 <x<1。

[0215] See now Figures 6A-6C It provides splat-quenched glass-ceramic samples (i.e., Figure 6A Example 1 (without heat treatment after annealing) and glass-ceramic samples according to examples of this disclosure that were heat-treated at 650°C for 5 hours and 35 minutes and at 700°C for 17 hours and 16 minutes respectively (Examples 1H and 1L). Figure 6B and 6C The Raman spectrum is shown. As in the previous examples, all glass-ceramic materials tested by Raman microscopy had the glass-ceramic composition according to Example 1 in Tables 1A and 1B. Figure 6BThe specific numerical designations associated with the data series in &6C (e.g., "#1", "#2-orange", "#2-gray", etc.) correspond to specific evaluation locations on the sample subjected to Raman spectroscopy testing (including the sample color at these locations). Figure 6A The sample subjected to spray quenching without further heat treatment (Example 1) exhibited various increased strength levels (e.g., 470 cm⁻¹) indicating the absence of a crystalline phase. -1 The network bonds at the location are Si-O, Al-O, and BO). Conversely, Figure 6B and 6C It was confirmed that the heat-treated samples (Examples 1H and 1L) exhibited significantly higher intensity levels at the same Raman shift locations, which were correlated with the lower intensity levels observed in the spray-quenched sample (Example 1), indicating the presence of a crystalline phase (e.g., 846 & 868 cm⁻¹). -1 The WOW associated with MgW₂O₇ appears to confirm that heat treatment conditions led to the establishment of a crystalline tungsten oxide phase (e.g., MgW₂O₇), evidenced by Raman shift positions (including but not limited to 345, 376, 404, 464, 718, 846, and 868 cm⁻¹). -1 There is a signal peak. Figure 6B and 6C It also suggests that the heat treatment conditions led to the establishment of a low-valence oxide phase of crystalline tungsten (i.e., a non-stoichiometric phase), as the crystalline tungsten oxide phase (i.e., the M mentioned above). x Combinations or substitutions of WO4 crystal phase.

[0216] See now Figure 7A and 7B Raman spectra are provided for glass-ceramic samples heat-treated at 650°C for 5 hours and 35 minutes and at 700°C for 17 hours and 16 minutes, respectively (Examples 1H and 1L), as well as for glass-ceramic samples that have just been sprayed and quenched (i.e., Example 1, without heat treatment after annealing). As in the previous embodiments, all glass-ceramic materials subjected to Raman microscopy have the glass-ceramic composition of Example 1 according to Tables 1A and 1B. Specific numerical designations associated with the data series in these figures (e.g., "#1", "#2 - orange", etc.) correspond to specific evaluation locations (including the sample color at these locations) on the samples subjected to Raman spectroscopy. Most importantly, Figure 7A and 7B It was confirmed that the spray-quenched sample (Example 1) exhibited a significantly lower intensity level at the same Raman shift position associated with the high intensity level of samples subjected to specific heat treatment conditions (Examples 1H and 1L). This confirms that the heat treatment conditions lead to the establishment of a crystalline tungsten oxide phase (e.g., Figure 7A and7B MgW2O7) and / or crystalline tungsten suboxide phases (i.e., non-stoichiometric phases).

[0217] Referring now to Figure 8 , a plot of residual stress (MPa) versus substrate depth (mm) is provided for two glass-ceramic samples (Example 10-IOXA and Example 10-IOXB) having compressive stress regions derived from two respective ion exchange process conditions. In Figure 8 , the y-axis is residual stress in the substrate, with positive values referring to tensile residual stress and negative values referring to compressive residual stress. Further, in Figure 8 , the x-axis is depth in each substrate, with values at 0 mm and 1.1 mm indicating the major surfaces of the substrate (e.g., major surfaces 12 and 14 of substrate 10 as shown in Figure 1 ). Each glass-ceramic sample in this example (Example 10-IOXA and Example 10-IOXB) has the same composition as the Example 10 samples shown in Tables 1A and IB. Further, each sample was melted and cast onto a steel table to form an optical cake, consistent with the methods described above in the disclosure. Each sample was then annealed at 570 °C for one hour and then cooled to ambient temperature at the furnace rate. The samples were then ground and polished to a size of 25 mm x 25 mm x ~1.1 mm to form the annealed optical cake. Finally, the Example 10-IOXA sample was immersed in a 100% NaNO3 molten salt bath at 390 °C for eight hours (8 hours) to form its compressive stress region. Similarly, the Example 10-IOXB was immersed in a 100% NaNO3 molten salt bath at 390 °C for sixteen hours (16 hours) to form its compressive stress region. It is noted that the actual thicknesses of the Example 10-IOXA and 10-IOXB were measured to be 1.10 mm and 1.06 mm, respectively.

[0218] It is demonstrated by Figure 8 that longer ion exchange durations tend to increase the DOC, the stored strain energy, and the magnitude of the peak tensile stress (i.e., the maximum tensile stress in the central tension region) of the glass-ceramic, while decreasing its maximum compressive stress. Specifically, the glass-ceramic sample having the shorter ion exchange duration (Example 10-IOXA) exhibited a compressive stress region having a compressive depth (DOC) of 136.7 μm, a maximum compressive stress of about -320 MPa, a central tension (CT) region given by a peak tensile stress of 57 MPa, and a stored strain energy of 16.6 J / m2. In contrast, the glass-ceramic sample having the longer ion exchange duration (Example 10-IOXB) exhibited a compressive stress region having a DOC of 163.6 μm, a maximum compressive stress of about - 280 MPa, a CT region given by a peak tensile stress of 68 MPa, and a stored strain energy of 22.6 J / m2. 2DOC of 168.0 μm, a maximum compressive stress of about -270 MPa, a CT region given by a peak tensile stress of 72 MPa, and a stored strain energy of 25 J / m 2 In contrast, the glass-ceramic sample with the longer ion exchange duration (Example 10-IOXB) exhibited a DOC of 168.0 μm, a maximum compressive stress of about -270 MPa, a CT region given by a peak tensile stress of 72 MPa, and a stored strain energy of 25 J / m

[0219] While the above glass-ceramic samples shown in Figure 8 exhibit a compressive stress region established by immersion in a molten salt bath of 100% NaNO3, the present disclosure also contemplates other alternatives. For example, the glass-ceramics can also be ion exchanged in a bath of molten KNO3, a mixture of NaNO3and KNO3, or sequentially in NaNO3first and then KNO3to increase the level of compressive stress on and near the surface of the substrate. Thus, sulfates, chlorides and other salts of ion-exchangeable metal ions (e.g., Na + , K + , etc.) can also be employed in these baths. In addition, the ion exchange temperature can vary from about 350°C to 550°C, with a preferred range of 370°C to about 450°C to prevent salt decomposition and stress relaxation.

[0220] Referring generally to Figures 9 to 11B , different sized crystalline regions are found in the tungsten bronze and multicolor tungsten bronze glass-ceramics described above. The crystal size depends on the base glass composition, but can also be slightly adjusted by the heat treatment time and temperature. In addition, with the addition of small amounts of calcium oxide (CaO), the crystallization rate is significantly increased, believed to be due to the interaction of the tungsten oxide to form nanocrystals of scheelite or scheelite-like structures that can act as nucleation sites.

[0221] Referring now to Figure 9 , larger crystals are found in the highly alumina tungsten bronze melts (e.g., M x WO3glass-ceramics) described above, and as Figure 9As shown. These crystals have a needle-like shape, with a length of 100-250 nm and a width of 5-30 nm. In the immediate quenched state (rapid quenching between two iron plates, i.e., spray quenching), these glass-ceramic materials are X-ray amorphous and scanning electron microscopy (SEM) analysis confirms the absence of precipitates (crystals, microcrystals). After quenching, the glass was heat-treated at 700 °C for 30 minutes or longer and then cooled to room temperature at 10 °C / min, resulting in tungsten bronze precipitates and alumina-enriched needle-like structures. The precipitate concentration increased with increasing heat treatment time and temperature, for example, after heat treatment at 700 °C for 1 hour and 40 minutes and cooling to room temperature at 10 °C / min. X-ray energy-dispersive X-ray spectroscopy (EDS) of the microcrystals formed after heat treatment shows that they contain tungsten, oxygen, and potassium.

[0222] See Figure 10A and 10B For at least some superalkaline tungsten bronze melts (R2O-AL2O3>0), the crystallite size is smaller than that in superaluminous melts. Figure 9 Furthermore, no alumina-enriched needle-like structures formed. Similar to over-aluminate melts, this over-alkaline material is X-ray amorphous when quenched between two iron plates (i.e., spray quenching). Microscopic images show that no microcrystals were present in the material prior to heat treatment. After heat treatment involving spray quenching at 550°C for 15 to 30 hours, followed by cooling at 1°C / min to 475°C, and then furnace-cooled to room temperature, TEM analysis revealed the formation of high aspect ratio needle-like tungsten bronze microcrystals, such as... Figures 10A to 10B As shown. Most of the needle-like structures obtained had diameters of 2 to 7 nm and lengths of 10 to 30 nm. X-ray EDS analysis of the heat-treated, spray-quenched samples revealed that the microcrystals contained tungsten.

[0223] See Figure 11A and 11B Silver-tungsten bronze glass-ceramics comprise microcrystals that are generally rod-shaped with an aspect ratio of 2 to 4, most commonly with a length of about 2-20 nm, a diameter of about 2-10 nm, and a volume of about 11 to 14.8 times that of the glass-ceramic material. Figure 11A and 11B The sample shown was heat-treated at 550°C for 4 hours, cooled to 475°C at a rate of 1°C / min, and then cooled to room temperature at a furnace rate. The rod was then placed in a gradient furnace for 5 minutes, so that one end of the rod remained at room temperature while the other end was at 650°C. The area between each end was exposed to a nearly uniform temperature gradient between 25°C and 650°C. In the region above approximately 575°C, the color began to shift from blue to green, then to yellow, then to orange, and finally to red. All colors were highly transparent.

[0224] As disclosed above, according to some example embodiments, the glass-ceramics have a transmittance of about 5% per mm or more over at least one 50 nm wide band of wavelengths in the range from about 400 nm to about 700 nm. However, in other embodiments, the glass-ceramics have lower transmittance, such as those cases that are opaque. According to at least some such embodiments, these glass-ceramics are unique in that they have strong absorption but do not scatter light and have very low haze. According to various such embodiments, the glass-ceramics have an optical density per mm (OD / mm) of at least 0.07 for at least some (e.g., a majority of, >90%) of light in the 200-400 nm wavelength range, up to 25 OD / mm for the same wavelengths, and / or have a haze of less than 10%, where the optical density is calculated by measuring optical absorption with a spectrophotometer and the haze is measured by a hazemeter wide angle scatter test. According to various such embodiments, the glass-ceramics have an optical density per mm (OD / mm) of at least 0.022 for at least some (e.g., a majority of, >90%) of light in the 400-750 nm wavelength range, up to 10 OD / mm for the same wavelengths, and / or have a haze of less than 10%. According to various such embodiments, the glass-ceramics have an optical density per mm (OD / mm) of at least 0.04 for at least some (e.g., a majority of, >90%) of light in the 750-2000 nm wavelength range, up to 15 OD / mm for the same wavelengths, and / or have a haze of less than 10%.

[0225] Embodiments comprising titanium

[0226] Referring now to Tables 8A and 8B, a list of example glass-ceramic compositions for articles comprising titanium are provided.

[0227] Table 8A

[0228]

[0229] Table 8B

[0230]

[0231]

[0232] Referring now to Table 8C and Figures 12A-17B , optical data for the composition samples of Tables 8A and 8B are provided.

[0233] Table 8C

[0234]

[0235]

[0236] Various compositions of Table 8C and Figures 12A-17B were prepared by weighing out the batch components, mixing the batch components by a vibrating mixer or ball mill, and melting in a fused silica crucible at a temperature of 1300°C to 1650°C for 4 to 32 hours. The glass was cast onto a metal table to produce a 0.5 mm thick glass patty. Some of the melt was poured onto a steel table and then rolled into a sheet using a steel roller. To establish and control the optical transmittance and absorptance, the samples were heat treated in an ambient air electric oven at a temperature of 425°C to 850°C for 5 to 500 minutes. The sample patties were then polished to a thickness of 0.5 mm and tested.

[0237] The data from Table 8C and Figures 12A-17B demonstrate that the as-fabricated state of the titanium-containing glasses are highly transparent in the NIR region and largely transparent at visible wavelengths. After heat treatment at a temperature of about 500°C to about 700°C, crystalline phases (i.e., low-valence oxides of titanium) precipitate and the optical transmittance of these samples decreases and some become strongly absorbing in the NIR.

[0238] Powder X-ray diffraction was performed on each of the compositions of Table 8C, demonstrating that for the as-fabricated and unannealed state, all of the compositions were X-ray amorphous. Heat treated samples showed evidence of some titanium oxide containing crystalline phases, including anatase (889FLY) and rutile (889FMC and 889FMD). The samples exhibited low haze (i.e., about 10% or less, or about <5% or less, or about 1% or less, or about 0.1% or less). Without being bound by theory, the low haze exhibited by these compositions in the as-fabricated and heat treated states is a result of the fact that the crystallites are very small (i.e., about 100 nm or less) and of low abundance (i.e., due to the fact that the Ti02was introduced at only about 2 mole%). Thus, it is believed that the species formed in these materials are below the detection limit of conventional powder XRD in size and abundance. This hypothesis was confirmed by TEM microscopy.

[0239] Referring now to Figure 18A -D, TEM micrographs of titanium oxide containing crystals in a glass number composition 889FMC sample heat treated at 700°C for 1 hour are provided at four different magnifications. These crystals have a rod-like appearance and have an average width of about 5 nm and an average length of about 25 nm.

[0240] Referring now to Figure 19A and 19B , TEM micrographs of a heat treated sample of glass number composition 889FMC are provided at Figure 19A and the corresponding EDS elemental maps are provided at Figure 19B . From Figure 19AIt can be seen that the sample includes a plurality of crystallites. The EDS map was set to detect titanium. It can be seen that the EDS plot of titanium closely follows the crystallite tracks, indicating that the crystallites are enriched in titanium. In this map, the bright or 'white' areas indicate the presence of Ti.

[0241] Referring now to Table 9A, exemplary glass compositions are provided that do not contain titanium.

[0242] Table 9A

[0243]

[0244]

[0245] Table 9B provides solar performance measurements for various glasses. In Table 9B, composition 196KGA was combined as a cladding layer (i.e., total cladding glass-ceramic thickness = 0.2 mm) in a dual fusion laminated stack, where the core composition of the stack was a chemically strengthened glass from Corning Incorporated (Corning® Gorilla® Glass 2). Composition 196KGA is 1 mm thick, heat treated at 550 °C for 30 minutes, and cooled at 1 °C per minute to 475 °C. The 889FMD sample is 5 mm thick, heat processed at 600 °C for 1 hour. The 889FMG sample is 0.5 mm thick, heat processed at 700 °C for 2 hours. The VG10 sample refers to a glass sold under the trade name SGG VENUS (VG 10) by Saint-Gobain and the thicknesses are different from each other.

[0246] Table 9B

[0247]

[0248]

[0249] ​​​In Table 9B, T_L is the total visible light transmittance (this is the weight average transmittance of light in the 380 nm to 780 nm wavelength range through the glazing and is tested according to ISO 9050 section 3.3). T_TS is the total transmittance solar energy (also known as the solar factor ("SF") or total solar heat transmittance ("TSHT"), which is T_DS (total direct solar energy) plus the sum of the portion absorbed by the glazing and then re-radiated into the vehicle interior, according to ISO 13837-2008 Appendix B & ISO 9050-2003 section 3.5). In this case, T_TS is calculated for a parked condition with a wind speed of 4 m / s (14 km / hour) and T_TS equals (%T_DS) + 0.276*(%solar energy absorption). T_DS is the total direct solar energy transmittance (also known as "solar transmittance" ("Ts") or "energy transmittance", which is the weight average transmittance of light in the 300 nm to 2500 nm wavelength range through the glazing, measured according to ISO 13837 section 6.3.2). R_DS is the reflected solar energy component (i.e., a nominal 4% Fresnel reflection). T_E is the solar direct transmittance. T_UV is the UV transmittance, measured according to ISO 9050 and ISO 13837A. T_IR is the infrared transmittance, measured according to Volkswagen standard TL957.

[0250] As evidenced by the data in Table 9B, glass No. 196KGA has the best optical performance and is able to produce the lowest UV, visible light, and NIR transmittance in a very short path length (0.2 mm). At a thickness of 0.5 mm, the titanium-containing compositions 889FMD and 889FMG produce optical performance superior to that of VG10 glass for a path length of 3.85 mm or less. In other words, the performance of the titanium-containing compositions 889FMD and 889FMG is superior to that of VG10 glass despite having a shorter path length.

[0251] Further, with respect to at least some of the glass-ceramics disclosed or contemplated herein, the glass-ceramics include an amorphous phase and a crystalline phase, wherein the crystalline phase includes (e.g., comprises, is, is primarily) a bronze structure as disclosed herein, e.g., of the chemical formula M x TiO2, M xprecipitates of WO3, etc., as disclosed herein. The volume fraction of the crystalline phase can be about 0.001% to about 20%, or about 1% to about 20%, or about 5% to about 20%, about 10% to about 20%, or about 10% to about 30%, or about 0.001% to about 50%. In other embodiments, the volume fraction of the crystalline phase can be about 0.001% to about 20%, or about 0.001% to about 15%, or about 0.001% to about 10%, or about 0.001% to about 5%, or about 0.001% to about 1%. In other contemplated embodiments, the volume fraction of the crystalline phase in the glass-ceramic can be greater than 50%.

[0252] Further to at least some of the glass-ceramics disclosed or contemplated herein, the glass-ceramic comprises an amorphous phase and a crystalline phase, wherein the crystalline phase comprises (e.g., includes, is, is primarily) a bronze structure as disclosed herein, e.g., of the chemical formula M x TiO2, M x precipitates of WO3, etc., as disclosed herein, where M represents a dopant cation as disclosed herein, and the precipitates (e.g., crystals) are sub-valent oxides, where 0 < x < 1, e.g., where 0 < x < 1, 0 < x < 0.9, e.g., where 0 < x < 0.75, e.g., where 0 < x < 0.5, e.g., where 0 < x < 0.2, and / or e.g., where 0.01 < x < 1, e.g., where 0.01 < x < 1, e.g., where 0.1 < x < 1, e.g., where 0.2 < x < 1, and / or where 0.5 < x < 1, e.g., where 0.001 < x < 0.999, e.g., where 0.01 < x < 0.99, e.g., where 0.1 < x < 0.9, e.g., where 0.2 < x < 0.9, or where 0.1 < x < 0.8.

[0253] The construction and arrangement of the methods and the products shown are illustrative only. Although only a few embodiments have been described in detail in this disclosure, many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. Some elements shown as integrally formed can be constructed of multiple parts or elements, the position of elements can be reversed or otherwise varied, and the nature or number of discrete elements or positions can be altered or varied. The order or sequence of any process, logical algorithm, or method steps can be varied or re-sequenced without materially affecting the disclosure. Other substitutions, modifications, changes and omissions can be made in the design, operating conditions and arrangement of the various example embodiments without departing from the spirit of the present inventive technology as expressed in the appended claims.

Claims

1. An article made from a glass-ceramic of a precipitate comprising a chemical formula of M x WO3 and / or M x MoO3, where 0 < x < 1 and M is a dopant cation, the method comprising: The region of the glass-ceramic is bleached so that the precipitate concentration of the bleached region is lower than in the adjoining glass-ceramic.

2. A glass-ceramic article comprising: M x WO3and / or M x precipitate of MoO3, where 0 < x < 1 and M is a dopant cation; and The bleached region of the article has a lower concentration of precipitates than the adjoining glass-ceramic of the article, wherein the precipitates are homogeneously distributed in the glass-ceramic adjoining the bleached region.

3. The article of claim 2, wherein, The length of the precipitates is 1 nm to 200 nm as measured by electron microscopy.

4. The article of claim 2, wherein, At least some of the precipitates are located at a depth of more than 10 pm from the surface of the article.

5. The article of claim 2, wherein, The volume fraction of the precipitates in the glass-ceramic adjoining the bleached region is 0.001% to 20%.

6. The article of claim 2, wherein, The dopant cations are: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Pd, Se, Ta, Bi, and / or Ce.

7. The article of claim 2, wherein, The glass-ceramic adjoining the bleached region has a transmittance of 1% / mm or more over at least one 50 nm wide optical wavelength band in the range of 400 nm to 700 nm.

8. The article of claim 7, wherein, The glass-ceramic adjoining the bleached region has an absorption of at least 90% / mm for light in at least one 50 nm wide optical wavelength band in the ultraviolet part of the optical spectrum.

9. The article of claim 7, wherein, The glass-ceramic adjoining the bleached region has an absorption of at least 90% / mm for light in at least one 50 nm wide optical wavelength band in the near infrared part of the optical spectrum, and the bleached region is non-absorbing in the near infrared part.

10. A glass-ceramic article comprising: M x WO3and / or M x MoO3precipitate, where 0 < x < 1 and M is a cation of Ag, Au and / or Cu; and The bleached region of the article has a lower concentration of precipitates than the adjoining glass-ceramic of the article, wherein the precipitates are homogeneously distributed in the glass-ceramic adjoining the bleached region.

11. The article of claim 10, wherein, The length of the precipitates is 1 nm to 200 nm as measured by electron microscopy.

12. The article of claim 10, wherein, At least some of the precipitates are located at a depth of more than 10 pm from the surface of the article.

13. The article of claim 10, wherein, The precipitates have a rod-like or needle-like morphology.

14. The article of claim 10, wherein, The volume fraction of the precipitates in the glass-ceramic adjoining the bleached region is 0.001% to 20%, and wherein the lower concentration in the bleached region is zero precipitates.

15. The article of claim 10, wherein, The glass-ceramic adjoining the bleached region has a transmittance of 1% / mm or more over at least one 50 nm wide optical wavelength band in the range of 400 nm to 700 nm.

16. The article of claim 15, wherein, The glass-ceramic adjoining the bleached region has an absorption of at least 90% / mm for light in at least one 50 nm wide optical wavelength band in the ultraviolet part of the optical spectrum.

17. The article of claim 15, wherein, The glass-ceramic adjoining the bleached region has an absorption of at least 90% / mm for light in at least one 50 nm wide optical wavelength band in the near infrared part of the optical spectrum, and the bleached region is non-absorbing in the near infrared part.

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