TWI811252B - Glass-ceramics and glasses - Google Patents

Abstract

A glass-ceramic includes silicate-containing glass and crystalline phases, where the crystalline phase includes non-stoichiometric suboxides of tungsten and/or molybdenum, or alternatively titanium, forming ‘bronze’-type solid state defect structures in which vacancies are occupied with dopant cations.

Description

Glass ceramics and glass

This application claims priority rights to U.S. Application No. 62/575,763, filed on October 23, 2017, and is a priority of U.S. Application No. 15/840,040, filed on December 13, 2017. For partial continuation applications, the contents of these applications are fully incorporated into this article by reference.

The present disclosure relates generally to articles including glass and/or glass ceramics, and more particularly, to the composition of such articles and methods of forming such articles.

Silicate glass ceramics containing alkali that absorb metallic ultraviolet ("UV") and near infrared ("NIR") rays are a type of glass ceramic that exhibit optical properties that depend on the wavelength of light incident on the glass ceramic . Conventional UV/IR blocking glasses (with low or high visible light transmittance) are made by introducing specific cationic species such as Fe2+ to absorb NIR wavelengths and Fe23+ to absorb UV wavelengths, and others such as Co, Ni, and Se. Dopants are formed to modify the visible light transmittance), and these specific cationic species are combined with the glass network. Traditionally, these glass ceramics are made by melting the components together to form a glass, followed by a post-heat treatment to form submicron precipitates in situ to form the glass ceramic. These submicroscopic precipitates (eg, tungstate-containing crystals and molybdate-containing crystals) absorb light in a wavelength band that gives the glass ceramic its optical properties. These conventional glass ceramics can be produced in both transparent and opalescent forms.

It is believed that conventional silicate glasses containing tungsten and molybdenum alkali are combined with specific and narrow compositional ranges to produce glasses and glass ceramics that are transparent at visible wavelengths. The believed composition range is based on the recognized solubility limits of tungsten oxide in overbased glasses. For example, when batched and melted in a conventional manner, tungsten oxide can react with alkali metal oxides in the batch to form concentrated alkali tungstate at low temperature during the initial stage of melting immediately after being placed in the melting furnace. Liquid (e.g., reaction occurs at about 500°C). Due to the high density of this phase, it separates rapidly at the bottom of the crucible. At significantly higher temperatures (eg, above about 1000°C), the silicate component begins to melt and, due to its lower density, remains atop the alkali tungstate liquid. Density differences in the components result in stratification of the different liquids, which give the appearance to those skilled in the art that they are immiscible with each other. This effect is particularly observed when _R2O ( _eg , _Li2O , _Na2O , _K2O , _Rb2O , _Cs2O ) minus _Al2O3 is about 0 mol% or greater. The apparent liquid immiscibility achieved at the melting temperature causes the tungsten-rich phase to separate and crystallize as it cools, manifesting itself as opalescent, opaque crystals. This problem also exists in molybdenum-containing melts.

One of ordinary skill in the art has observed that the tungsten and/or molybdenum-rich phase separates from the silicate-rich phase, and they recognize that there are solubility limitations for tungsten and/or molybdenum within the silicate-rich phase (e.g., about 2.5 mol%). The recognized solubility limitations prevent the glass from becoming supersaturated with tungsten or molybdenum oxides, thereby preventing transmission of either component from forming a controlled precipitation upon heat treatment to produce a glass ceramic having a crystalline phase that includes these elements. Thus, the perceived solubility prevents the development of glass-ceramic compositions that achieve sufficient amounts of soluble tungsten and/or molybdenum to allow the formation of wavelength-dependent submicroscopic crystals of tungsten and/or molybdenum through subsequent heat treatment.

In view of these limitations, there is a need for new compositions and methods of making them that promote improved near-infrared and ultraviolet blocking (eg, through higher tungsten and molybdenum solubility).

It has been found that a homogeneous single phase of a W or Mo containing overbased melt can be obtained by using a "bound" alkali as described herein. Exemplary bound bases may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali aluminosilicates, and/or other naturally occurring and artificially occurring alkali-containing bases and one or more aluminum and/or silicates Atoms of minerals. By introducing the base in a bound form, the base may not react with the W or Mo present in the melt to form concentrated alkali tungstate and/or alkali molybdate liquids. Additionally, _this batch material change may allow for the melting of strongly overbased compositions (e.g., _R2O - _Al2O3 = about 2.0 mol% or greater) without any alkali tungstate and/or alkali molybdate substituents phase formation. This has also allowed the melting temperature and mixing method to vary while still producing a single phase homogeneous glass.

According to aspects of the present disclosure, a glass ceramic includes a silicate-containing glass and a crystalline phase that includes non-stoichiometric amounts of tungsten and/or molybdenum, or alternatively titanium suboxides, forming a "bronze" - type solid-state defect structure, in which the vacancies are occupied by dopant cations.

In some specific implementations, the glass ceramic includes an amorphous phase and a crystalline phase. The crystalline phase includes a plurality of precipitates of the formula M _x WO ₃ and/or M _x MoO ₃ , where 0<x<1 and M is a dopant cation. In some of these implementations, the precipitates have a length from about 1 nm to about 200 nm as measured by an electron microscope. The precipitates of the crystalline phase can be distributed substantially uniformly within the glass ceramic.

Furthermore, glass ceramics may include an amorphous phase and a crystalline phase. The crystalline phase includes a plurality of precipitates of the formula M _x TiO ₂ , where 0 < x < 1 and M is a doping cation. In some of these implementations, the precipitate has a length from about 1 nm to about 200 nm, or from 1 nm to about 300 nm, or from 1 nm to about 500 nm, as measured by an electron microscope. The precipitates of the crystalline phase can be distributed substantially uniformly within the glass ceramic.

In some embodiments, the glass ceramic includes a silicate-containing glass, and crystals of non-stoichiometric tungsten and/or molybdenum suboxides intercalated with doped cations uniformly distributed within the silicate-containing glass. . The glass ceramic may have a transmittance of 5% or greater per mm over at least a 50 nm wide light wavelength band in the range from about 400 nm to about 700 nm. 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 of these embodiments, at least some of the crystals are at a depth greater than about 10 μm from the outer surface of the glass ceramic. The crystals may have a rod-shaped morphology.

In some embodiments, the glass ceramic includes a silicate-containing glass phase and a crystalline phase. The crystalline phase includes tungsten and/or molybdenum suboxides to form a solid defect structure, and the pores in the solid defect structure are occupied by dopant cations. . The volume fraction of the crystalline phase in the glass ceramic can be from about 0.001% to about 20%.

In other embodiments, the glass-ceramic includes silicate-containing glass, and non-stoichiometric titanium suboxide with intercalated dopant cations uniformly distributed within the silicate-containing glass; and/or silicic acid-containing glass. The salt glass phase and the crystalline phase, the crystalline phase contains titanium suboxide, form a solid defect structure, and the pores in the solid defect structure are occupied by dopant cations.

In some embodiments, the object includes at least one amorphous phase and one crystalline phase, and the object includes from about 1 mol% to about 95 mol% SiO ₂ as a batch component. The crystalline phase includes from about 0.1 mol% to about 100 mol% of an oxide of at least one of the following: (i) W, (ii) Mo, (iii) V and alkali metal cations, and (iv) Ti and alkali Metal cations. The object may be substantially free of Cd and Se.

In still other specific implementations, for example, glass that is a glass precursor for glass ceramics, the batch components include: from about 25 mol% to about 99 mol% SiO ₂ and from about 0 mol% to about 50 mol% Al ₂ O ₃ , from about 0.35 mol % to about 30 mol % WO ₃ plus MoO ₃ , from about 0.1 mol % to about 50 mol % R ₂ O, where R ₂ O is Li ₂ O, Na ₂ O, K ₂ O , one or more of Rb ₂ O and Cs ₂ O, and wherein R ₂ O minus Al ₂ O ₃ is from about -35 mol% to about 7 mol%. In some of these implementations, at least one of the following: (i) RO is in the range from about 0.02 mol% to about 50 mol% and (ii) _SnO2 is from about 0.01 mol% to about 5 mol %, where RO is one or more of MgO, CaO, SrO, BaO and ZnO. In some such embodiments, if the WO ₃ is from about 1 mol % to about 30 mol %, the glass further includes about 0.9 mol % or less Fe ₂ O ₃ , or the SiO ₂ is from about 1 mol % to about 30 mol %. 60 mol% to about 99 mol%. If WO ₃ is from about 0.35 mol % to about 1 mol %, the glass may contain from about 0.01 mol % to about 5.0 mol % SnO ₂ . If MoO ₃ is from about 1 mol% to about 30 mol%, SiO ₂ can range from about 61 mol% to about 99 mol%, or Fe ₂ O ₃ can be about 0.4 mol% or less and R ₂ O is greater than RO. If MoO ₃ is from about 0.9 mol% to about 30% and SiO ₂ is from about 30 mol% to about 99 mol%, the glass may further include from about 0.01 mol% to about 5 mol% SnO ₂ .

In some embodiments, a method of forming a glass ceramic includes the following steps: melting (1) bound alkali, (2) silica, and (3) tungsten and/or molybdenum together to form a glass melt; solidify into glass; and precipitate crystalline phases within the glass to form glass-ceramic objects. Glass can be a single homogeneous solid phase. The crystalline phase may include tungsten and/or molybdenum. Furthermore, in some of these specific implementations, the bound base includes: (A) feldspar, (B) nepheline, (C) sodium borate, (D) spodumene, (E) albite, (F) potassium Feldspar, (G) alkali aluminosilicate, (H) alkali silicate, and/or (I) bonded to (I-i) alumina, (I-ii) boria and/or (I- iii)Alkali of silica.

In other embodiments, a method of forming a glass ceramic includes the following steps: melting silica and tungsten and/or molybdenum together to form a glass melt; solidifying the glass melt to form glass; and precipitating in the glass a material containing tungsten and/or molybdenum. / or molybdenum bronze-type crystals. The precipitated crystalline phase may include thermally processing the glass. In at least some of these embodiments, the method further includes the step of growing the precipitate of the crystalline phase to a length of at least about 1 nm and no more than about 500 nm.

In other embodiments, the glass ceramic includes a silicate-containing glass phase; and a crystalline phase, the crystalline phase includes titanium suboxide, the titanium suboxide includes a solid defect structure, and the pores in the solid defect structure are formed by dopants. cations occupy.

In other specific implementations, the glass ceramic includes an amorphous phase; and a crystalline phase. The crystalline phase includes a plurality of precipitates of the formula M _x TiO ₂ , where 0<x<1 and M is a doping cation.

In other embodiments, the glass ceramic includes a silicate-containing glass; and a plurality of crystals uniformly distributed within the silicate-containing glass, wherein the crystals include non-stoichiometric titanium suboxide, and further wherein the crystals are intercalated There are dopant cations.

In other embodiments, the glass ceramic object includes at least an amorphous phase and a crystalline phase; and from about 1 mol% to about 95 mol% of SiO ₂ ; wherein the crystalline phase includes from about 0.1 mol% to about 100 mol% of the crystalline phase. Non-stoichiometric titanium suboxide, the oxide containing at least one of the following: (i) Ti, (ii) V and an alkali metal cation.

In other embodiments, a method of forming a glass ceramic includes the steps of: melting components including silica and titanium together to form a glass melt; and solidifying the glass melt to form a glass, wherein the glass includes first average near infrared rays. Absorbance; and precipitating a crystalline phase in the glass to form a glass-ceramic, the glass-ceramic comprising: (a) a second average near-infrared absorbance, wherein the 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.

In other embodiments, the glass includes in the batch composition: from about 1 mol% to about 90 mol% SiO ₂ ; from about 0 mol% to about 30 mol% Al ₂ O ₃ ; from about 0.25 mol % to about 30 mol% TiO ₂ ; from about 0.25 mol% to about 30 mol% metal sulfide; from about 0 mol% to about 50 mol% R ₂ O, where R ₂ O is Li ₂ O, Na One or more of ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O; and from about 0 mol% to about 50 mol% RO, where RO is one of BeO, MgO, CaO, SrO, BaO and ZnO or more, wherein the glass is substantially free of Cd.

By referring to the following specification, patent claims and accompanying drawings, one of ordinary skill in the art will further understand and identify these and other features, advantages, and objects of the present disclosure.

Before referring to the following detailed description of exemplary embodiments and the accompanying drawings, it should be understood that the technology of the present invention is not limited to the details or methods set forth in the embodiments or illustrated in the drawings. For example, as one of ordinary skill in the art will understand, the words shown in one of the accompanying drawings or related to one of the specific implementations describe what is associated with a specific implementation. Features and attributes may also apply to other embodiments shown in another figure or described elsewhere herein.

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

In this document, relational terms, such as first and second, top and bottom, etc., are only used to distinguish one entity or action from another entity or action and do not necessarily require or imply a relationship between these entities or actions. any actual relationship or sequence.

Modifications of the present invention will be contemplated by those of ordinary skill in the art and who make or use the present disclosure. Therefore, it is understood that the specific embodiments shown in the drawings and described above are for illustrative purposes only and are not intended to limit the scope of the present disclosure, which shall be conducted in accordance with the principles of patent law (including the doctrine of equality). Interpretation is defined by the following patent application scope.

One of ordinary skill in the art will understand that the structure and other components of the described disclosure are not limited to any particular material. Other exemplary implementations of the disclosure disclosed herein may be formed from a variety of materials unless otherwise described herein.

For the purposes of this disclosure, the term "coupled" (all forms: couple, coupling, coupled, etc.) generally means that two components are directly or indirectly joined to each other (electrically or mechanically). This joint may be essentially immobile or essentially movable. This joining may be achieved by the two components (electrical or mechanical) and any additional intermediate member integrally forming a single unitary body with either or both components. The engagement may be permanent in nature, or removable or releasable in nature, unless otherwise stated.

As used herein, the term "about" means that quantities, dimensions, formulas, parameters, and other quantities and characteristics are not and need not be exact, but may be as close as desired and/or are larger or smaller, reflecting tolerances, Conversion factors, rounded values, measurement errors, etc., and other factors known to those of ordinary skill in the art. When the term "about" is used to describe a value or an endpoint of a range, it is understood that the present disclosure includes the specific value or endpoint mentioned. Regardless of whether the range of numerical values or endpoints in the specification states "approximately", the range of numerical values or endpoints is intended to include two specific implementations: one modified with "approximately", and one not modified with "approximately". It will be further understood that each endpoint of a range is significant both relative to and independent of the other endpoint.

As used herein, the terms "substantially," "substantially," and variations thereof are intended to indicate that the described characteristic is equal to or approximately equal to a value or statement. For example, a "substantially planar" surface is intended to mean that the surface is planar or approximately planar. Additionally, "substantially" attempts to indicate that two values are equal or approximately equal. In some implementations, "substantially" may mean values that are within about 10% of each other, such as values that are within about 5% of each other, or values that are within about 2% of each other.

Directional terms, such as up, down, left, right, front, back, top, bottom, as used herein, are used only with reference to the drawings and are not intended to imply absolute directions.

As used herein, the terms "the," "a" or "an" mean "at least one" and shall not be limited to "only one" unless expressly stated otherwise. Thus, for example, reference to "a component" includes embodiments having two or more such components, unless the context clearly dictates otherwise.

All compositions are expressed in as-batched molar percent (mol%) unless otherwise indicated. It will be understood by those of ordinary skill in the art that various melt components (e.g., fluorine, alkali metals, boron, etc.) may be subject to varying degrees of volatilization (e.g., as vapor pressure, melt pressure, etc.) during the melting of the components. function of time and/or melting temperature). Thus, with respect to these components, the term "about" is intended to encompass values within about 0.2 mol% when the final article is measured compared to the fresh batch compositions provided herein. In view of the foregoing, it is expected that there will be substantial compositional equivalence between the final object and the fresh batch composition.

For the purposes of this disclosure, the terms "bulk," "whole composition," and/or "overall composition" are intended to include the entire composition of the entire object, which may be distinguished from "partial composition" or "localized composition." The "local composition" or "localized composition" may differ from the overall composition due to the formation of crystalline and/or ceramic phases.

Also as used herein, the terms "object", "glass object", "ceramic object", "glass ceramic", "glass element", "glass ceramic object" and "glass ceramic object" are used interchangeably and in their broadest sense. "Glass-ceramic objects" are intended to include any object made in whole or in part from glass and/or glass-ceramic materials.

As used herein, "glassy" means the inorganic amorphous phase material within the articles of the present disclosure, which is the product of a fusion that has been cooled to rigid conditions without crystallization. As used herein, "glass-ceramic state" means the inorganic material within the articles of the present disclosure, which includes both the glassy state and "crystalline phases" and/or "crystalline precipitates" as described herein.

The coefficient of thermal expansion (CTE) is expressed as 10 ^-7 /°C and represents values measured over a temperature range from about 0°C to about 300°C, unless otherwise specified.

As used herein, "transmission" and "transmittance" mean external transmission or transmittance, which takes into account absorptivity, scattering, and reflection. Freel reflection is not excluded from the transmission and transmittance values described in this article.

As used herein, "optical density units,""OD" and "OD units" are used interchangeably in this disclosure to refer to optical density units, generally understood as a measurement of the absorbance of a material being tested, using spectrometric measurements The measurement is expressed as OD= -log (I/I ₀ ), where I ₀ is the intensity of light incident on the sample and I is the intensity of light transmitted through the sample. Furthermore, the term "OD/mm" or "OD/cm" as used in this disclosure is a standardized measurement of absorbance by dividing the optical density unit (i.e., as measured by an optical spectrometer) by the thickness of the sample (for example, the unit is millimeters or centimeters). In addition, reference is given to any optical density unit 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) as the average of the optical density units over the specific wavelength range. .

As used herein, the term "haze" means the percentage of transmitted light scattered outside a ±2.5° angle cone in a sample with a transmission path of approximately 1 mm, and is measured according to ASTM Procedure D1003.

Also as used herein, the term "[glass or glass-ceramic] without [component]" (e.g., "glass-ceramic without cadmium and selenium") means the complete absence or substantial absence (i.e., <500 ppm) A glass or glass-ceramic of the listed components and prepared so that the listed components are not actively, intentionally or purposefully added or batched to the glass or glass-ceramic.

With regard to the glass ceramics and glass ceramic materials and objects disclosed herein, surface stress is evaluated using, for example, the SCALP220 scattered light polarimeter manufactured by GlaStress, Ltd. (Tallinn, Estonia) and accompanying software version 5, or by Orihara Compressive stress and depth of compression ("DOC") are measured with a commercially available instrument, the FSM-6000 manufactured by Co., Ltd. (Tokyo, Japan), unless otherwise noted herein. Measurements by both instruments must be converted into stress optical retardation by converting the stress optical coefficient ("SOC") of the material under test. Therefore, stress measurement relies on accurate measurement of SOC, which is related to the birefringence of the glass. SOC is in turn measured according to a modified version of Procedure C ("Modified Procedure C") described in ASTM Standard C770-98 (2013) entitled "Standard Test Method for Stress Optical Coefficient of Glass", by Its contents are incorporated into this article by full-text citation. Modified Procedure C involves the use of glass or glass ceramic disks as specimens with a thickness of 5 to 10 mm and a diameter of 12.7 mm. The disc is isotropic and homogeneous, as well as centrally drilled and has two polished and parallel faces. Modified procedure C also includes calculating the maximum force Fmax applied to the disk. The force should be sufficient to create a compressive stress of at least 20 MPa. Calculate Fmax using the following equation: Fmax=7.854*D*h where Fmax is the maximum force (N), D is the diameter of the disk (mm), and h is the thickness of the light path (mm). For each applied force, the stress is calculated using the following equation: σ (MPa)=8F/(π*D*h) where F is the force (N), D is the diameter of the disk (mm), and h is the thickness of the light path (mm).

Also as used herein, the terms "sharp cutoff wavelength" and "cutoff wavelength" are used interchangeably and mean a cutoff wavelength in the range of about 350 nm to 800 nm, with the cutoff wavelength (λc ), glass-ceramics have substantially higher transmittance above the cut-off wavelength (λc). The cutoff wavelength (λc) is the wavelength at the midpoint between the "absorption rate limiting wavelength" and the "high transmittance limiting wavelength" in a given spectrum for glass ceramics. The "absorbance limiting wavelength" is specified as the wavelength at which the transmission rate is 5%; and the "high transmission wavelength" is defined as the wavelength at which the transmission rate is 72%. It will be understood that a "sharp UV cutoff" as used herein may be a sharp cutoff wavelength as described above for cutoff wavelengths that occur within the ultraviolet band of the electromagnetic spectrum.

Articles of the present disclosure are composed of glass and/or glass ceramics having one or more of the compositions outlined herein. Objects can be used in any number of applications. For example, articles in the form of substrates, components, lenses, covers, and/or other components may be employed in any number of optically related and/or aesthetic applications.

Objects are formed from freshly batched compositions and cast into a glassy state. The article may then be annealed and/or thermally processed (eg, heat treated) 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 article may crystallize directly and become a glass-ceramic without the need for additional heat treatment (eg, cast substantially in a glass-ceramic state). In instances where post-heat treatment is employed, some, most, substantially all, or all of the object may be converted from the glassy state to the glass-ceramic state. Thus, while the composition of an object may be described with respect to the glassy and/or glass-ceramic states, the overall composition of the object may remain substantially unchanged when transitioning between the glassy and glass-ceramic states, although localized portions of the object may have Different compositions (i.e., due to the formation of ceramics or crystallized precipitates).

According to various examples, the articles may include Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , WO ₃ , MO ₃ , R ₂ O, where R ₂ O is Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and one or more of Cs ₂ O; RO, where RO is one or more of MgO, CaO, SrO, BaO and ZnO; and some dopants. It will be understood that some other components (eg, F, As, Sb, Ti, P, Ce, Eu, La, Cl, Br, etc.) do not depart from the teachings provided herein.

According to the first example, the object may include from about 58.8 mol% to about 77.58 mol% SiO ₂ , from about 0.66 mol% to about 13.69 mol% Al ₂ O ₃ , from about 4.42 mol% to about 27 mol% B ₂ O ₃ , from about 0 mol% to about 13.84 mol% R ₂ O, from about 0 mol% to about 0.98 mol% RO, from about 1.0 mol% to about 13.24 mol% WO ₃ and from about 0 mol% % to about 0.4 mol% SnO ₂ . These instances of objects may generally relate to instances 1-109 of Table 1.

According to the second example, the object may include from about 65.43 mol% to about 66.7 mol% SiO ₂ , from about 9.6 mol% to about 9.98 mol% Al ₂ O ₃ , from about 9.41 mol% to about 10.56 mol% B ₂ O ₃ , from about 6.47 mol% to about 9.51 mol% R ₂ O, from about 0.96 mol% to about 3.85 mol% RO, from about 1.92 mol% to about 3.85 mol% WO ₃ , from about 0 mol % to about 1.92 mol% MoO ₃ and from about 0 mol% to about 0.1 mol% SnO ₂ . These instances of objects may generally relate to instances 110-122 of Table 2.

According to a third example, the object may include from about 60.15 mol% to about 67.29 mol% SiO ₂ , from about 9.0 mol% to about 13.96 mol% Al ₂ O ₃ , from about 4.69 mol% to about 20 mol% B ₂ O ₃ , from about 2.99 mol% to about 12.15 mol% R ₂ O, from about 0.00 mol% to about 0.14 mol% RO, from about 0 mol% to about 7.03 mol% WO ₃ , from about 0 mol % to about 8.18 mol% MoO ₃ , from about 0.05 mol% to about 0.15 mol% SnO ₂ and from about 0 mol% to about 0.34 mol% V ₂ O ₅ . These instances of objects may generally relate to instances 123-157 of Table 3.

According to the fourth example, the object may include from about 54.01 mol% to about 67.66 mol% SiO ₂ , from about 9.55 mol% to about 11.42 mol% Al ₂ O ₃ , from about 9.36 mol% to about 15.34 mol% B ₂ O ₃ , from about 9.79 mol% to about 13.72 mol% R ₂ O, from about 0.00 mol% to about 0.22 mol% RO, from about 1.74 mol% to about 4.48 mol% WO ₃ , from about 0 mol % to about 1.91 mol% MoO ₃ , from about 0.0 mol% to about 0.21 mol% SnO ₂ , from about 0 mol% to about 0.03 mol% V ₂ O ₅ , from about 0 mol% to about 0.48 mol% of Ag and from about 0 mol% to about 0.01 mol% of Au. These instances of objects may generally relate to instances 158-311 of Table 4.

According to the fifth example, the object may include from about 60.01 mol% to about 77.94 mol% SiO ₂ , from about 0.3 mol% to about 10.00 mol% Al ₂ O ₃ , from about 10 mol% to about 20 mol% B ₂ O ₃ , from about 0.66 mol% to about 10 mol% R ₂ O, from about 1.0 mol% to about 6.6 mol% WO ₃ and from about 0.0 mol% to about 0.1 mol% SnO ₂ . These instances of objects may generally relate to instances 312-328 of Table 5.

The article may have from about 1 mol% to about 99 mol% SiO ₂ , or from about 1 mol% to about 95 mol% SiO ₂ , or from about 45 mol% to about 80 mol% SiO ₂ , or from about 60 mol% to about 99 mol% SiO ₂ , or from about 61 mol% to about 99 mol% SiO ₂ , or from about 30 mol% to about 99 mol% SiO ₂ , or from about 58 mol% to about 78 mol% SiO ₂ , or from about 55 mol% to about 75 mol% SiO ₂ , or from about 50 mol% to about 75 mol% SiO ₂ , or from about 54 mol% to about 68 mol% SiO _2. Or from about 60 mol% to about 78 mol% SiO ₂ , or from about 65 mol% to about 67 mol% SiO ₂ , or from about 60 mol% to about 68 mol% SiO ₂ , or from about 56 mol% to about 72 mol% SiO ₂ , or from about 60 mol% to about 70 mol% SiO ₂ . It will be understood that any and all values and ranges between the SiO2 ranges noted above are contemplated. SiO ₂ can serve as the main glass-forming oxide and affect the stability, devitrification resistance and/or viscosity of the object.

The article may include from about 0 mol% to about 50 mol% Al ₂ O ₃ , or from about 0.5 ml % to about 20 mol % Al ₂ O ₃ , or from about 0.5 mol % to about 15 mol % Al ₂ O ₃ , or from about 7 mol% to about 15 mol% Al ₂ O ₃ , or from about 0.6 mol% to about 17 mol% Al ₂ O ₃ , or from about 0.6 mol% to about 14 mol% Al ₂ O ₃ , or from about 7 mol% to about 14 mol% Al ₂ O ₃ , or from about 9.5 mol% to about 10 mol% Al ₂ O ₃ , or from about 9 mol% to about 14 mol% Al ₂ O ₃ , from about 9.5 mol% to about 11.5 mol% Al ₂ O ₃ , or from about 0.3 mol% to about 10 mol% Al ₂ O ₃ , or from about 0.3 mol% to about 15 mol% Al ₂ O ₃ , or from about 2 mol% to about 16 mol% Al ₂ O ₃ , or from about 5 mol% to about 12 mol% Al ₂ O ₃ , or from about 8 mol% to about 12 mol% Al ₂ O ₃ , or from about 5 mol% to about 10 mol% Al ₂ O ₃ . It will be understood that any and all values and ranges between the Al ₂ O ₃ ranges noted above are contemplated. Al ₂ O ₃ can be used as a conditional network former and contribute to stable objects with low CTE, object stiffness, and to facilitate melting and/or shaping.

Objects may include WO ₃ and/or MoO ₃ . For example, WO ₃ plus MoO ₃ can be from about 0.35 mol% to about 30 mol%. MoO ₃ can be about 0 mol% and WO ₃ can be from about 1.0 mol% to about 20 mol%, or MoO ₃ can be about 0 mol% and WO ₃ can be from about 1.0 mol% to about 14 mol%, or MoO ₃ is from about 0 mol% to about 8.2 mol% and WO ₃ is from about 0 mol% to about 16 mol%, or MoO ₃ is from about 0 mol% to about 8.2 mol% and WO ₃ is from about 0 mol% to About 9 mol%, or MoO ₃ from about 1.9 mol% to about 12.1 mol% and WO ₃ from about 1.7 mol% to about 12 mol%, or MoO ₃ from about 0 mol% to about 8.2 mol% and WO ₃ is from about 0 mol% to about 7.1 mol%, or MoO ₃ is from about 1.9 mol% to about 12.1 mol% and WO ₃ is from about 1.7 mol% to about 4.5 mol%, or MoO ₃ is about 0 mol% and WO ₃ is from about 1.0 mol% to about 7.0 mol%. Regarding MoO ₃ , the glass composition may have from about 0.35 mol % to about 30 mol % MoO ₃ , or from about 1 mol % to about 30 mol % MoO ₃ , or from about 0.9 mol % to about 30 mol % MoO ₃ , or from about 0.9 mol% to about 20% MoO ₃ , or from about 0 mol% to about 1.0 mol% MoO ₃ , or from about 0 mol% to about 0.2 mol% MoO ₃ . Regarding WO ₃ , the glass composition may have from about 0.35 mol % to about 30 mol % WO ₃ , or from about 1 mol % to about 30 mol % WO ₃ , or from about 1 mol % to about 17 mol % WO 3 _3. Or from about 1.9 mol% to about 10 mol% WO ₃ , or from about 0.35 mol% to about 1 mol% WO ₃ , or from about 1.9 mol% to about 3.9 mol% WO ₃ , or from about 2 mol% to about 15 mol% of WO ₃ , or from about 4 mol% to about 10 mol% of WO ₃ , or from about 5 mol% to about 7 mol% of WO ₃ . It will be understood that any and all values and ranges between the WO ₃ and/or MoO ₃ ranges noted above are contemplated.

The article may include from about 2 mol% to about 40 mol% B ₂ O ₃ , or from about 4 mol% to about 40 mol% B ₂ O ₃ , or from about 4.0 mol% to about 35 mol% B ₂ O ₃ , or from about 4.0 mol% to about 27 mol% B ₂ O ₃ , or from about 5.0 mol% to about 25 mol% B ₂ O ₃ , or from about 9.4 mol% to about 10.6 mol% B ₂ O ₃ , or from about 5 mol% to about 20 mol% B ₂ O ₃ , or from about 4.6 mol% to about 20 mol% B ₂ O ₃ , or from about 9.3 mol% to about 15.5 mol% B ₂ O ₃ , or from about 10 mol % to about 20 mol % B ₂ O ₃ , or from about 10 mol % to about 25 mol % B ₂ O ₃ . It will be understood that any and all values and ranges between _{the B2O3} ranges noted above are contemplated. B ₂ O ₃ can be a glass-forming oxide used to reduce CTE, density, and viscosity to produce glasses that are easier to melt and form at lower temperatures.

The article may include at least one alkali metal oxide. The alkali metal oxide can be represented by the chemical formula R ₂ O, wherein R ₂ O is one or more of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O and/or combinations thereof. The article may have from about 0.1 mol% to about 50 mol% R ₂ O, or from about 0 mol% to about 14 mol% R ₂ O, or from about 3 mol% to about 14 mol% R ₂ O, Or from about 5 mol% to about 14 mol% R ₂ O, or from about 6.4 mol% to about 9.6 mol% R ₂ O, or from about 2.9 mol% to about 12.2 mol% R ₂ O, or from About 9.7 mol% to about 12.8 mol% R ₂ O, or from about 0.6 mol% to about 10 mol% R ₂ O, or from about 0 mol% to about 15 mol% R ₂ O, or from about 3 It consists of an alkali metal oxide from about 7 mol% to about 10 mol% of R ₂ O, or from about 7 mol% to about 10 mol% of R ₂ O. It will be understood that any and all values and ranges between the _R2O ranges noted above are contemplated. Alkali metal oxides (eg, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O) may be incorporated into articles for a variety of reasons: (i) to lower the melting temperature, (ii) Species that increase formability, (iii) enable chemical strengthening by ion exchange, and/or (iv) act as segregators in certain grains.

According _to various examples, _R2O minus _Al2O3 ranges from about -35 mol% to about 7 mol%, or from about -12 mol% to about 2.5 mol%, or from about -6% to About 0.25%, or from about -3.0 mol% to about 0 mol%. It will be understood that any and all values and ranges between the R ₂ O minus Al ₂ O ₃ range noted above are considered.

The article may include at least one alkaline earth metal oxide. Alkaline earth metal oxides can be represented by the chemical formula RO, where RO is one or more of MgO, CaO, SrO, BaO and ZnO. The object may include RO, from about 0.02 mol% to about 50 mol% RO, or from about 0.01 mol% to about 5 mol% RO, or from about 0.02 mol% to about 5 mol% RO, or from about 0.05 mol% to about 10 mol% RO, or from about 0.10 mol% to about 5 mol% RO, or from about 0.15 mol% to about 5 mol% RO, or from about 0.05 mol% to about 1 mol% RO, or from about 0.5 mol% to about 4.5 mol% RO, or from about 0 mol% to about 1 mol% RO, or from about 0.96 mol% to about 3.9 mol% RO, or from about 0.2 mol% to about 2 mol% RO, or from about 0.01 mol% to about 0.5 mol% RO, or from about 0.02 mol% to about 0.22 mol% RO. It will be understood that any and all values and ranges between the RO ranges noted above are considered. According to various examples, R ₂ O may be greater than RO. Furthermore, objects can have no RO. Alkaline earth metal oxides (such as MgO, CaO, SrO, and BaO) and other divalent oxides such as ZnO can improve the melting behavior of the object and can also be used to increase the CTE, Young's modulus, and shear modulus of the object .

The article may include from about 0.01 mol% to about 5 mol% SnO ₂ , or from about 0.01 mol% to about 0.5 mol% SnO ₂ , or from about 0.05 mol% to about 0.5 mol% SnO ₂ , or from about 0.05 mol% to about 2 mol% SnO ₂ , or from about 0.04 mol% to about 0.4 mol% SnO ₂ , or from about 0.01 mol% to about 0.4 mol% SnO ₂ , or from about 0.04 mol% to about 0.16 mol% SnO ₂ , or from about 0.01 mol% to about 0.21 mol% SnO ₂ , or from about 0 mol% to about 0.2 mol% SnO ₂ , or from about 0 mol% to about 0.1 mol% SnO ₂ . It will be understood that any and all values and ranges between the SnO ₂ ranges noted above are contemplated. Articles may also include a small concentration of SnO ₂ as a fining agent (e.g., other fining agents may include CeO ₂ , As ₂ O ₃ , Sb ₂ O ₃ , Cl-, F-, or the like) to aid in the elimination of gaseous phases during melting pack. Certain fining agents may also act as redox couples, color centers, and species that nucleate and or intercalate the grains formed in the object.

The composition of certain components of an object may depend on the presence and/or composition of other components. For example, if the WO ₃ is from about 1 mol % to about 30 mol %, the article further includes about 0.9 mol % or less Fe ₂ O ₃ or SiO ₂ from about 60 mol % to about 99 mol %. In another example, if the WO ₃ is from about 0.35 mol% to about 1 mol%, the article includes from about 0.01 mol% to about 5.0 mol% SnO ₂ . In another example, if MoO ₃ is from about 1 mol% to about 30 mol%, SiO ₂ is from about 61 mol% to about 99 mol% or Fe ₂ O ₃ is about 0.4 mol% or less and R ₂ O is greater than RO. In another example, if MoO ₃ is from about 0.9 mol % to about 30 mol % and SiO ₂ is from about 30 mol % to about 99 mol %, the object includes from about 0.01 mol % to about 5 mol % SnO ₂ .

The article may be substantially free of cadmium and substantially free of selenium. According to various examples, the article may further include at least one dopant selected from the following group: Ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, Se, Ta, Bi, Ag, Ce , Pr, Nd, and Er to change UV, visible light, color, and/or near-infrared absorbance. The dopants in the article may have a concentration from about 0.0001 mol% to about 1.0 mol%. For example, the article may include from about 0.01 mol% to about 0.48 mol% Ag, from about 0.01 mol% to about 0.13 mol% Au, from about 0.01 mol% to about 0.03 mol% V ₂ O ₅ , from At least one of about 0 mol% to about 0.2 mol% Fe ₂ O ₃ , from about 0 mol% to about 0.2 mol% Fe ₂ O ₃ , and from about 0.01 mol% to about 0.48 mol% CuO. According to another example, the article may include from about 0.01 mol% to about 0.75 mol% Ag, from about 0.01 mol% to about 0.5 mol% Au, from about 0.01 mol% to about 0.03 mol% V ₂ O ₅ , and at least one of from about 0.01 mol% to about 0.75 mol% CuO. The article may include fluorine in the range of about 0 mol% to about 5 mol% to soften the glass. The article may include from about 0 mol% to about 5 mol% phosphorus to further modify the physical properties of the article and regulate crystal growth. The object may include Ga ₂ O ₃ , In ₂ O ₃ and/or GeO ₂ to further modify the physical and optical (eg, refractive index) properties of the object. The following trace impurities in the range of about 0.001 mol % to about 0.5 mol % may be present to further modify ultraviolet, visible (e.g., 390 nm to about 700 nm), and near infrared (e.g., about 700 nm to about 2500 nm) Absorbance and/or making objects fluoresce: 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. Furthermore, P ₂ O ₅ can be added in small amounts to certain compositions to further modify the physical properties and viscosity of the object.

It will be understood that each of the above noted _SiO2 , _Al2O3 , _WO3 , _MoO3 , _WO3 plus _MoO3 , _B2O3 , _{R2O ,} RO, _V2O5 , Ag, Au, _CuO The compositions and composition ranges of , SnO ₂ , and dopants may be used with any other compositions and/or composition ranges of other components of the articles as outlined herein.

As explained previously, the formation of conventional tungsten, molybdenum, or mixed tungsten-molybdenum alkali glasses is hindered by the separation of melt components during the melting process. Separation of the glass components during the melting process results in solubility limitations of the alkali tungstate within the molten glass and therefore the recognition of objects cast from such melts. Conventionally, when the tungsten, molybdenum, or mixed tungsten-molybdenum melt is even slightly overbased (e.g., R ₂ O-Al ₂ O ₃ = about 0.25 mol% or greater), the molten borosilicate Glass forms both glass and concentrated liquid secondary phases. Although the concentration of alkali tungstate secondary phases can be reduced by thorough mixing, melting at high temperatures, and using small batch sizes (~1000 g), the formation of harmful secondary phases cannot be completely eliminated. It is believed that the formation of this alkali tungstate phase occurs during 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 relative to the formed borosilicate glass, they rapidly segregate and/or stratify, concentrating on the bottom of the crucible and not due to the significant difference in density. Will dissolve quickly in glass. Since the _R2O component can provide beneficial properties to the glass composition, it may not be desirable to simply reduce the presence of the _R2O component in the melt.

The inventors of the present disclosure have discovered that a homogeneous single phase W or Mo containing overbased melt can be obtained by using a "tethered" base. For the purposes of this disclosure, a "bound" base is an alkali element bound to alumina, boron oxide, and/or silica, and a "free" or "unbound" base is an alkali carbonate, alkali nitrate, and /or alkali sulfates in which the base is not bound to silica, boron oxide or alumina. Exemplary bound bases may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali aluminosilicates, alkali silicates and/or others containing alkali and one or more aluminum, boron and/or silicates Atoms of naturally occurring and artificially produced minerals. By introducing the base in a bound form, the base may not react with the W or Mo present in the melt to form concentrated alkali tungstate and/or alkali molybdate liquids. Additionally, this _batch material change may allow strongly overbased compositions (e.g., _R2O - _Al2O3 = about 2.0 mol% or greater) to melt without forming any alkali tungstates and/or alkali molybdates Salt phase. This has also allowed varying melting temperatures and mixing methods while still producing a single phase homogeneous glass. It will be appreciated that since the alkali tungstate phase and the borosilicate glass are not completely immiscible, extended stirring may also allow mixing of the two phases to cast single phase objects.

Once the glass melt has been cast and solidified into a glassy object, the object can be annealed, heat treated, or thermally treated to form a crystalline phase within the object. Therefore, the object can be transformed from the glassy state to the glass-ceramic state. The crystalline phase of the glass-ceramic state can have various forms. According to various examples, a crystalline phase is formed as a plurality of precipitates within heat-treated areas of the article. As such, the precipitate may have a generally crystalline structure.

As used herein, "crystalline phase" means the inorganic material within the articles of the present disclosure, which is a solid composed of atoms, ions, or molecules arranged in a three-dimensional periodic pattern. Furthermore, unless otherwise expressly stated, the "crystalline phase" referred to in this disclosure is determined to exist using the following method. First, powder X-ray diffraction (“XRD”) is used to detect the presence of crystallized precipitates. Second, in cases where XRD is unsuccessful (eg, due to size, quantity, and/or chemistry of the precipitates), Raman spectroscopy ("Raman") is used to detect the presence of crystalline precipitates. Optionally, transmission electron microscopy ("TEM") is used to visually confirm or confirm the identification of crystallized precipitates obtained through XRD and/or Raman techniques. In some cases, the amount and/or size of the precipitates may be low enough to make visual identification of the precipitates particularly difficult. As such, the larger sample sizes of XRD and Raman can be advantageous when sampling larger amounts of material to determine the presence of precipitates.

The crystallized precipitates may have a substantially rod-shaped or needle-shaped morphology. The precipitate can have a thickness of from about 1 nm to about 500 nm, or from about 1 nm to about 400 nm, or from about 1 nm to about 300 nm, or from about 1 nm to about 250 nm, or from about 1 nm to about 200 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about 75 nm, or from about 1 nm to about 50 nm, or from about 1 nm to about 25 nm, or from about 1 nm to about 20 nm nm or the longest length from about 1 nm to about 10 nm. The size of the precipitates can be measured using an electron microscope. For the purposes of this disclosure, the term "electron microscopy" means first visually measuring the longest length of a precipitate using a scanning electron microscope, and then using a transmission electron microscope if the precipitate cannot be resolved. Since the crystallized precipitate may generally have a rod-like or needle-like morphology, the precipitate may have a width from about 2 nm to about 30 nm, or from about 2 nm to about 10 nm, or from about 2 nm to about 7 nm. It will be understood that the size and/or morphology of the precipitates may be uniform, substantially uniform, or may vary. In general, the peraluminous composition of the object produces precipitates with a needle-like shape having a length from about 100 nm to about 250 nm and a width from about 5 nm to about 30 nm. The overbased composition of the article can produce needle-like precipitates having a length from about 10 nm to about 30 nm and a width from about 2 nm to about 7 nm. Examples of articles containing Ag, Au, and/or can produce rod-shaped precipitates having a length from about 2 nm to about 20 nm and a width, or diameter, from about 2 nm to about 10 nm. The volume fraction of the crystalline phase in the article may range from about 0.001% to about 20%, or from about 0.001% to about 15%, or from about 0.001% to about 10%, or from about 0.001% to about 5% , or from about 0.001% to about 1%.

When in the glass-ceramic state, the relatively small size of the precipitates can help reduce the amount of light scattered by the precipitates, resulting in high optical clarity of the object. As will be explained in more detail below, the size and/or number of precipitates can be varied across the object so that different parts of the object can have different optical properties. For example, portions of an article in which precipitates are present can result in absorbance, color, reflection of light, and/or when compared to portions of an article with different precipitates (e.g., size and/or amount) and/or in which no precipitates are present. or changes in transmission and refractive index.

The precipitate may consist of tungsten oxide and/or molybdenum oxide. The crystalline phase includes from about 0.1 mol% to about 100 mol% of the crystalline phase of an oxide of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation. Without being bound by theory, it is believed that during thermal treatment (eg, heat treatment) of an object, tungsten and/or molybdenum cations coalesce to form crystalline precipitates, thereby converting the glassy state to the 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 precipitate may have an oxidation state between 0 and about +6. According to various examples, molybdenum and/or tungsten may have a +6 oxidation state. For example, the precipitate may have the general chemical structure of _WO3 and/or _MoO3 . However, there may also be significant proportions of tungsten and/or molybdenum in the +5 oxidation state and the precipitates may be referred to as non-stoichiometric tungsten suboxide, non-stoichiometric molybdenum suboxide, "molybdenum bronze" and/or "Tungsten Bronze". One or more of the alkali metals and/or dopants noted above may be present in the precipitate to compensate for the +5 charge on W or Mo. Tungsten and/or molybdenum bronze is a group of non-stoichiometric tungsten and/or molybdenum suboxides with the general chemical formula M _x WO ₃ or M _x MoO ₃ , where M = 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 one or more of U, and where 0<x<1. Structures M _x WO ₃ and M _x MoO ₃ are considered solid-state defect structures in which the holes (i.e., vacancies or channels in the crystal lattice) in the reduced WO ₃ or MoO ₃ network are randomly occupied by M atoms, which Decomposed into M+ cations and free electrons. Depending on the concentration of "M", material properties can range from metallic to semiconducting, thereby allowing a variety of optical absorption and electronic properties to be tuned. The more 5+W or Mo there is, the more M+ cations may have to be compensated and the greater the value of x.

Tungsten bronze is a non-stoichiometric compound with the general formula M _x WO ₃ , where M is a cationic dopant, such as some other metal, most commonly a base, and x is a variable less than 1. For the sake of clarity, although called "bronze", these compounds are not structurally or chemically related to metallic bronze, which is an alloy of copper and tin. Tungsten bronze is a series of solid phases whose homogeneity varies as a function of x. Depending on the dopant M and the corresponding concentration x, the material properties of tungsten bronze can range from metallic to semiconducting, and exhibit adjustable optical absorption. The structure of these bronzes is a solid defect structure in which M' cations are inserted into the pores or channels of the binary oxide host and dissociate into M+ cations and free electrons. For the sake of clarity _{, M} A changing crystal structure, where M can be one or a combination of certain elements on the periodic table, where x varies from 0<x<1, and where the oxidation state of the bronze-forming species (W in this case) is A mixture of species in their highest oxidation state (W ⁶⁺ ) and lower oxidation states (e.g., W ⁵⁺ ), and the number three (“3”) in WO ₃ represents a species that may be between 2 and 3 The number of oxygen anions. Therefore, _MxWO3 may alternatively be represented by the chemical form _MxWOZ , where 0<x<1, and 2<z _< 3, or as _{MxWO3 -z} , where 0<x<1 and ₀ <z<1. However, for the sake of simplicity, M _x WO ₃ is used for non-stoichiometric crystals of this family. Similarly, "bronze" is generally applied to ternary metal oxides of the formula M' _x M" _y O _z , where (i) M" is a transition metal and (ii) M" _y O _z is its highest binary oxide , (iii) M' is some other metal, (iv) x is a variable falling in the range of 0 < x < 1.

Some, most, substantially all, or all of the article may be thermally treated to form a precipitate. Thermal treatment techniques may include, but are not limited to, furnaces (eg, heat treatment furnaces), microwaves, lasers, and/or other techniques for local and/or overall heating of an object. During thermal treatment, crystallized precipitates are nucleated in a homogeneous manner within the object, wherein the object is thermally treated to transform the glassy state into the glass-ceramic state. Thus, in some examples, an object may include both a glassy state and a glass-ceramic state. In instances where the entire object is thermally treated (eg, placing the entire object in a furnace), precipitates may form uniformly throughout the object. In other words, precipitates may exist from the outer surface of the object throughout the entirety of the object (i.e., greater than approximately 10 µm from the surface). In the case where the object is partially thermally treated (e.g., via laser), precipitates may only exist where the thermal treatment reaches a sufficient temperature (e.g., on the surface and throughout the object near the heat source). It will be understood that articles may be subjected to more than one thermal treatment to produce precipitates. Additionally or alternatively, thermal treatment may be used to remove and/or modify precipitates that have formed (eg, as a result of previous thermal treatment). For example, thermal treatment can cause the decomposition of precipitates.

According to various examples, both where precipitates are present and where no precipitates are present (i.e., in portions of the glassy or glass-ceramic state), in the visible region of the electromagnetic spectrum (i.e., from about 400 nm to about 700 nm) , objects can be optically transparent. As used herein, the term "optically transparent" means penetration over a 1 mm path length over a wavelength band of light that is at least 50 nm wide in the range from about 400 nm to about 700 nm. The rate is greater than approximately 1% (e.g., in %/mm). In some examples, the object has a wavelength band of about 5%/mm or greater, about 10%/mm or greater, about 15%/mm or greater over at least a 50 nm wide wavelength band of light in the visible region of the spectrum. Larger, about 20%/mm or larger, about 25%/mm or larger, about 30%/mm or larger, about 40%/mm or larger, about 50%/mm or larger, about 60 %/mm or greater, about 70%/mm or greater, about 80%/mm or greater, and greater than all lower limits between these values.

According to various examples, based on the presence of precipitates, the glass-ceramic state of the article absorbs light in the ultraviolet ("UV") region (ie, wavelengths less than about 400 nm) without the use of additional coatings or films. In some implementations, the glass-ceramic state of the object is characterized by low transmittance for light in at least a 50 nm wide wavelength band of light in the UV region of the spectrum (e.g., about 200 nm to about 400 nm) Below 10%/mm, below 9%/mm, below 8%/mm, below 7%/mm, below 6%/mm, below 5%/mm, below 4%/mm, below 3%/mm, less than 2%/mm, and even less than 1%/mm. In some examples, the glass-ceramic state absorbs or has at least 90%/mm, at least 91%/mm, at least 92%/mm, for light in at least a 50 nm wide wavelength band of light in the UV region of the spectrum. An absorption rate of 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. The glass ceramic state may have a sharp UV cutoff wavelength from about 320 nm to about 420 nm. For example, the glass-ceramic state can have at 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, Sharp UV cutoff at about 420 nm, about 430 nm, or anything in between.

In some examples, the glass-ceramic state of the object has greater than about 5% over at least a 50 nm wide wavelength band of light in the near-infrared region (NIR) of the spectrum (e.g., from about 700 nm to about 2700 nm) /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 limits between these values. In still other examples, the glass-ceramic state of the object has about 90%/mm, less than about 80%/mm, less than about 70% over at least a 50 nm wide wavelength band of light in the NIR region of the spectrum /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 below 0.1%/mm and below all upper limits between these values. In other examples, the glass-ceramic state of the object may have an absorption of at least 90%/mm, at least 91%/mm, or at least 92%/mm for light in at least a 50 nm wide wavelength band of light in the NIR region of the spectrum. 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 absorption rate.

Various examples of the present disclosure may provide a variety of properties and advantages. It will be understood that, although certain properties and advantages may be disclosed in relation to certain compositions, the various properties and advantages disclosed may apply equally to other compositions.

With respect to the compositions in Tables 1 and 5 below, articles made from the disclosed compositions can exhibit low coefficients of thermal expansion ("CTE"). For example, over a temperature range from about 0°C to about 300°C, the object may have a coefficient of thermal expansion from about 10x10 ^"7 °C" ¹ and about 60x10" ⁷ °C ^"1 . This low CTE allows items to withstand large and rapid temperature swings, making them suitable for operation in harsh environments. Regarding optical properties, objects may exhibit less than 1% transmittance at wavelengths of about 368 nm or less, optical transparency in the visible light system (e.g., from about 500 nm to about 700 nm), and NIR wavelengths ( For example, strong attenuation (e.g., blocking) from about 700 nm to about 1700 nm). An advantage of these objects over conventional NIR management solutions may be that no coatings or films are used on the object (eg, it may be mechanically fragile, sensitive to UV light and moisture). Since the object is impervious to oxygen, moisture, and UV wavelengths (i.e., due to its glassy or glass-ceramic nature), NIR-absorbing precipitates are protected from harsh environmental conditions (e.g., moisture, corrosive acids, bases and gases) and rapid changes in temperature. Furthermore, through the subsequent heat treatment, the UV cutoff wavelength and refractive index of the glass-ceramic state of the object are changed to be adjustable. The glass-ceramic state of an object can exhibit changes in UV cutoff or refractive index as a result of its crystallized precipitates. The glassy state of the object can have a refractive index between about 1.505 and about 1.508, and the glass-ceramic state of the object can have a refractive index from about 1.520 to about 1.522. By changing the heat treatment conditions created after the object, thermally modifiable UV cutoff and refractive index can enable a slot of glass to meet dynamically generated multiple UV cutoff glass specifications. Thermal modulation of the refractive index can create large refractive index deltas (10 ^-2 ). Because the heat treatment required to modulate UV absorbance is accomplished at high viscosities (eg, between 10 ⁸ and 10 ¹² poise), the final object can be heat treated without damaging the surface or causing decomposition.

Regarding the compositions of Tables 1 and 2, objects fabricated from these compositions provide a novel family of nontoxic, cadmium- and selenium-free objects that exhibit optical extinction with sharp and tunable cutoff wavelengths. Unlike Cd-free alternatives to CdSe filter glass containing Se, these items contain no Resource and Recovery Act (“RCRA”) metals or other hazardous media. In addition, objects can be composed of lower-cost elements, unlike Cd-free alternatives containing indium and/or gallium. Regarding optical properties, objects fabricated from these compositions can provide high transparency (eg, greater than about 90%) in the NIR extending to 2.7 microns. Furthermore, objects can exhibit sharp visible light cutoff wavelengths ranging from approximately 320 nm to 525 nm, which are tunable by thermal processing conditions (eg, time and temperature), and by composition.

Regarding the compositions of Table 3, articles of these exemplary compositions may use molybdenum instead of tungsten, which may be advantageous because molybdenum is generally less expensive than tungsten. In addition, objects made from these compositions can be thermally treated to a glass-ceramic state, which can provide a variety of optical properties. For example, at a thickness of about 0.5 mm, the transmittance of objects of such composition in the visible spectrum (e.g., about 400 nm to about 700 nm) can range from about 4% to about 30% in the NIR (e.g., about 700 nm to about 1500 nm), about 5% to about 15% at wavelengths below about 370 nm, and about 1% or less at wavelengths from about 370 nm to about 390 nm. The wavelength of nm is about 5% or less. According to some examples, mixed molybdenum and tungsten instances of objects can absorb 92.3% of the solar spectrum. These optical properties can be visually recognized as the tint of the object. Similar to other compositions, these optical properties arise through the growth of precipitates, and thus, the hue can vary across the object based on thermal treatment. This thermally variable hue can be used to create tonal gradients within an object, such as the formation of shadow edges or borders within an object's windshield or skylight applications. This feature can facilitate removal of glass frit baked onto the surface of conventional windshields and sunroofs. This thermally adjustable tint can also be used to create gradient absorption across an object. Additionally, objects produced from these compositions are bleachable and patternable by laser (e.g., operating at wavelengths of 355 nm, 810 nm, and 10.6 μm). When laser is exposed to these wavelengths, the exposed areas of the object will change from blue or gray (e.g., due to the color of the precipitates) to a clear, watery white or yellowish tint due to thermal decomposition of UV- and NIR-absorbing precipitates. . Patterns can be created within an object by rasterizing laser light along the surface of the object to selectively bleach desired areas. When an article is bleached, the resulting glassy state is no longer NIR absorbing, making the bleaching process self-limiting (ie, because the NIR absorbing precipitates have been broken down). Additionally, selective laser exposure can produce not only patterns but also variable UV and NIR absorbance across the object. According to yet other examples, objects can be powdered into sufficiently small sizes and functionalized for use as photothermal sensitive agents for cancer treatment (ie, due to their NIR absorbing optical properties).

Regarding the compositions of Table 4, objects made from these compositions may be thermally treated after formation (e.g., to form a glass-ceramic state) to both modulate optical absorbance and create a wide range of colors from a single composition. Furthermore, such examples may be capable of fusion formation and/or ion exchange. Conventional colored glass compositions using Ag, Au and/or Cu generally rely on the formation of nanoscale metal precipitates to produce color. As discovered by the inventors of the present disclosure, Ag ¹⁺ cations can be inserted into tungsten and molybdenum oxides to form silver tungsten bronze and/or silver molybdenum bronze, which can provide objects with polychromatic nature. Surprisingly, by adding small concentrations of Ag ₂ O or AgNO ₃ to M _x WO ₃ or M _x MoO ₃ to the composition of the object, many objects produce a variety of colors (eg , red, orange, yellow, green, blue, various browns and/or combinations thereof). It will be appreciated that Au and/or Cu may be utilized in a similar manner. Analysis demonstrates that the color tunability is not due to the formation of a collection of metal nanoparticles on top of the template in a crystalline phase (eg, M _x WO ₃ or M _x MoO ₃ ). Instead, the color tunability of these polychromatic objects is thought to originate from changes in the bandgap energy of the doped tungsten and/or molybdenum oxide precipitates, resulting from the insertion of alkali cations and Ag. The concentration of ¹⁺ , Au and/or Cu cations in the precipitate to form varying stoichiometry of soda ash, pure metal and/or mixed alkali metal, tungsten and/or molybdenum bronze. Changes in the bandgap energy of a precipitate result from its stoichiometry and are primarily independent of precipitate size and/or shape. Therefore, doped _MxWO3 or _MxMoO3 precipitates can maintain the same size and/or shape, but can be many different _colors depending on the dopant "M" _body and concentration "x". Thermal treatment of these objects can create an almost complete rainbow of colors within a single object. Furthermore, the color gradient can be stretched or compressed over some physical distance by the heat gradient applied to the object. In yet other examples, objects can be laser patterned to locally change the color of the object. Such articles may facilitate the manufacture of tinted sunglass lens blanks, phone and/or tablet covers, and/or other products that may be composed of glass ceramics and may be aesthetically tinted. Since the precipitates are located within the glass ceramic, the scratch resistance and environmental durability are superior to conventional metallic and polymeric color layers applied to provide coloration. Since the color of an object can change based on heat treatment, a tank of glass melt can be used to continuously create blanks that can be heat treated to a specific color specified by the customer. Additionally, similar to other compositions disclosed herein, objects made from these glass compositions may absorb UV and/or IR radiation.

According to various examples of the present disclosure, objects may be adapted to various fusion formation processes. For example, various compositions of the present disclosure may be utilized in single or dual fused build-ups using transparent tungsten, molybdenum, mixed tungsten-molybdenum, and/or titanium glass as cladding materials surrounding a substrate to form a laminated object. . After application as a cladding layer, the glassy cladding layer can be transformed into a glass-ceramic state. The glass-ceramic cladding of the fused laminated article may have a thickness from about 50 µm to about 200 µm and may have a high average visible light transmittance (e.g., from about 75 for automotive windshields and/or architectural glazing) % to about 85%) strong UV and IR attenuation, strong UV and IR attenuation with low visible transmittance (such as about 5% to about 30% for car side lights, car sunroofs, and privacy inlaid glass) and/or laminations in which visible and infrared absorbance can be adjusted by treatment in a gradient oven, localized heating and/or localized bleaching. Furthermore, using the composition as a cladding layer to form an object provides novel processes to fully trade off tunable optical properties while simultaneously fabricating a strengthened monolithic glass sandwich.

According to various examples, articles made from compositions of the present disclosure may be powdered or granulated and a variety of materials added. For example, powdered articles may be added to paints, adhesives, polymeric materials (eg, polyvinyl butyral), sol-gels, and/or combinations thereof. This feature may be useful in imparting one or more properties of the object to the materials described above.

According to various examples, the article may include _TiO2 . The object may include a concentration of about 0.25 mol%, or about 0.50 mol%, or about 0.75 mol%, or about 1.0 mol%, or about 2.0 mol%, or about 3.0 mol%, or about 4.0 mol%, or about 5.0 mol% %, or about 6.0 mol%, or about 7.0 mol%, or about 8.0 mol%, or about 9.0 mol%, or about 10.0 mol%, or about 11.0 mol%, or about 12.0 mol%, or about 13.0 mol%, Or about 14.0 mol%, or about 15.0 mol%, or about 16.0 mol%, or about 17.0 mol%, or about 18.0 mol%, or about 19.0 mol%, or about 20.0 mol%, or about 21.0 mol%, or about 22.0 mol%, or about 23.0 mol%, or about 24.0 mol%, or about 25.0 mol%, or about 26.0 mol%, or about 27.0 mol%, or about 28.0 mol%, or about 29.0 mol%, or about 30.0 mol % of TiO ₂ or any and all numbers and ranges therebetween. For example, the article may include a concentration of TiO ₂ from about 0.25 mol % to about 30 mol %, or from about 1 mol % to about 30 mol % TiO ₂ , or from about 1.0 mol % to about 15 mol %. TiO ₂ , or from about 2.0 mol% to about 15 mol% TiO ₂ , or from about 2.0 mol% to about 15.0 mol% TiO ₂ . It will be understood that any and all values and ranges between the TiO ₂ ranges noted above are considered.

According to various examples, the article may include one or more metal sulfides. For example, metal sulfides may include MgS, _Na2S , and/or ZnS. According to various examples, the article may include one or more metal sulfides. For example, metal sulfides may include MgS, _Na2S , and/or ZnS. The object may include a concentration of about 0.25 mol%, or about 0.50 mol%, or about 0.75 mol%, or about 1.0 mol%, or about 2.0 mol%, or about 3.0 mol%, or about 4.0 mol%, or about 5.0 mol% %, or about 6.0 mol%, or about 7.0 mol%, or about 8.0 mol%, or about 9.0 mol%, or about 10.0 mol%, or about 11.0 mol%, or about 12.0 mol%, or about 13.0 mol%, Or about 14.0 mol%, or about 15.0 mol%, or about 16.0 mol%, or about 17.0 mol%, or about 18.0 mol%, or about 19.0 mol%, or about 20.0 mol%, or about 21.0 mol%, or about 22.0 mol%, or about 23.0 mol%, or about 24.0 mol%, or about 25.0 mol%, or about 26.0 mol%, or about 27.0 mol%, or about 28.0 mol%, or about 29.0 mol%, or about 30.0 mol % or any and all values and ranges of metal sulfides therebetween. For example, the article may include a metal sulfide in a concentration from about 0.25 mol% to about 30 mol%, or from about 1.0 mol% to about 15 mol%, or from about 1.5 mol% to about 5 mol%.

Similar to the tungsten and molybdenum oxides highlighted above, examples of articles including titanium can also produce crystalline phases consisting of precipitates of titanium oxide. The crystalline phase includes from about 0.1 mol% to about 100 mol% of the Ti and alkali metal cation oxides of the crystalline phase. Without being bound by theory, it is believed that during thermal treatment (e.g., heat treatment) of an object, titanium cations coalesce to form crystalline precipitates near and or on the metal sulfide, thereby converting the glassy state to glass Ceramic state. Metal sulfides can play a dual role, serving as nucleating agents (i.e., serving as seed crystals onto which titanium can coalesce due to their higher melting temperatures compared to the melt) and Both as reducing agents (ie, metal sulfides are highly reducing agents and titanium so coalesced can be reduced to the 3+ state). In this way, the titanium present in the precipitate due to the metal sulfide can be reduced, or partially reduced. For example, titanium in the precipitate may have an oxidation state between 0 and about +4. For example, the precipitate may have the general chemical structure of _TiO2 . However, there can also be a significant fraction of titanium in the +3 oxidation state, and in some cases, these Ti ³⁺ cations can be charge stabilized by species inserted into the channels in the titanium oxide crystal lattice, forming what is known as A compound of non-stoichiometric titanium suboxide, "titanium bronze", or "bronze-type" titanium crystals. One or more of the alkali metals and/or dopants noted above may be present in the precipitate to compensate for the +3 charge on Ti. Titanium bronze is a group of non-stoichiometric titanium suboxides with the general chemical form M _x TiO ₂ , where M = 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, one or more dopant cations, and where 0<x<1. _{Structure M _} . Depending on the concentration of "M", material properties can range from metallic to semiconducting, allowing for tuning of a wide variety of optical absorption and electronic properties. The more 3+Ti, the more M+ cations may be needed to compensate and the larger the value of x.

Consistent with the foregoing revelations, titanium bronze is a non-stoichiometric compound with the general formula M _x TiO ₂ , where M is a cationic dopant, such as some other metal, most commonly a base, and x is a variable less than 1. For the sake of clarity, although called "bronze", these compounds are not structurally or chemically related to metallic bronze, which is an alloy of copper and tin. Titanium bronze is a series of solid phases whose homogeneity varies as a function of x. Depending on the dopant M and the corresponding concentration x, the material properties of titanium bronze can range from metallic to semiconducting, and exhibit adjustable optical absorption. The structure of these bronzes is a solid defect structure in which M' dopant cations insert (ie, occupy) the pores or channels of the binary oxide host and dissociate into M+ cations and free electrons.

For the sake _of clarity, _M The varying crystal structure of stone, where M can be one or a combination of certain elements on the periodic table, where x varies from 0<x<1, where the oxidation state of the bronze-forming species (Ti in this case) is A mixture of species in their highest oxidation state (Ti ⁴⁺ ) and lower oxidation states (e.g., Ti ³⁺ ), and where the number two ("2") in TiO ₂ represents something that can be between 1 and 2 the number of oxygen anions. Therefore _{, MxTiO2} may alternatively be represented by the chemical form _MxTiOz , _where 0& _{lt ;} <z<1. However, for simplicity, _MxTiO2 is used for this family _of non-stoichiometric crystals. Similarly, "bronze" is generally applied to ternary metal oxides of the formula M' _x M" _y O _z , where (i) M" is a transition metal and (ii) M" _y O _z is its highest binary oxide , (iii) M' is some other metal, (iv) x is a variable falling in the range of 0 < x < 1.

According to various examples, glass ceramic articles including titanium can be substantially free of W, Mo, and rare earth elements. As emphasized above, the ability of titanium to form its own suboxide can eliminate the need for tungsten and molybdenum and the titanium suboxide can eliminate the need for rare earth elements.

According to various examples, glass ceramic articles may have low concentrations of iron or no iron. For example, the article may include 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 therebetween. All values and ranges.

According to various examples, glass ceramic articles may have low concentrations of lithium or no lithium. For example, the article may include 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 therebetween. All values and ranges.

According to various examples, the glass ceramic article may have a low concentration of zirconium or no zirconium. For example, the article may include 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 therebetween. All values and ranges.

Similar to the formation of articles containing tungsten or molybdenum, articles including titanium may be formed by a process including the steps of: melting components including silica and titanium together to form a glass melt; solidifying the glass melt to form a glass; and Bronze-type crystals including titanium are precipitated within the glass to form a glass ceramic. According to various examples, precipitation of bronze-type crystals may be performed via one or more thermal treatments. For titanium bronze-type crystals, 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 The thermal treatment is performed to a temperature of about 750°C, or from about 500°C to about 700°C, or any and all values and ranges therebetween. In other words, the precipitation of bronze-type crystals is performed at a temperature from about 450°C to about 850°C or the precipitation of bronze-type crystals is performed at a temperature from about 500°C to about 700°C. The thermal treatment may last 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 from about 15 minutes, or about 90 minutes, or from about 30 minutes to A period of approximately 90 minutes, or from approximately 60 minutes to approximately 90 minutes, or any and all values and ranges therebetween. In other words, precipitation of bronze-type crystals is performed for a period of from about 15 minutes to about 240 minutes or precipitation of bronze-type crystals is performed for a period of from about 60 minutes to about 90 minutes. Thermal treatment can be performed in an atmospheric environment, an inert atmosphere, or in a vacuum.

The formation of titanium suboxide in titanium-containing examples of objects can cause differences in absorbance and transmittance of different wavelength bands of light. In ultraviolet (UV) band light (e.g., from about 200 nm to about 400 nm), before the precipitation of titanium suboxide, glassy objects can have an average UV transmittance of about 18% to about 30% . For example, the average UV transmittance of an object in a glassy state may be 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 the titanium suboxide, the glass-ceramic object may have an average UV transmittance of about 0.4% to about 18%. For example, the average UV transmittance of the glass-ceramic object may be 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 understood that the transmittance values noted above may exist in articles having thicknesses or optical path lengths from about 0.4 mm to about 1.25 mm.

In light in the visible light band (eg, from about 400 nm to about 750 nm), before the precipitation of titanium suboxide, the object in the glassy state can have an average visible light transmittance of about 60% to about 85%. For example, the average visible light transmittance of an object in a glassy state may be 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 part thereof and all values and ranges. After the formation or precipitation of the titanium suboxide, the object in the glass ceramic state may have an average visible light transmittance of about 4% to about 85%. For example, the average UV transmittance of an object in the glass-ceramic state can be 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 therebetween. It will be understood that the transmittance values noted above may exist in articles having thicknesses or optical path lengths from about 0.4 mm to about 1.25 mm.

In light of the near-infrared (NIR) band (e.g., from about 750 nm to about 1500 nm), before the precipitation of titanium suboxide, an object in the glassy state can have an average NIR penetration of about 80% to about 90% Rate. For example, the average NIR transmittance of an object in a glassy state may be 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 therebetween. After the formation or precipitation of the titanium suboxide, the object in the glass-ceramic state may have an average NIR transmission of about 0.1% to about 10%. For example, the average UV transmittance of an object in the glass-ceramic state can be 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 therebetween. It will be understood that the transmittance values noted above may exist in articles having thicknesses or optical path lengths from about 0.4 mm to about 1.25 mm.

In light in the NIR band, an object in a glassy state without titanium suboxide may have a per mm 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 An average optical density (i.e., first near-infrared absorbance) of 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 object having the titanium suboxide in the glass-ceramic state may have a thickness per mm of about 6.0 or less, or about 5.5 or less, or about 5.0 or less, or about 4.5 or more. Low, 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 an optical density (i.e., second near-infrared absorbance) of 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 may 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 10.0 or greater. In such examples, the average optical density per mm of the object having titanium suboxide in the glass-ceramic state at visible wavelengths may be 1.69 or less.

According to various examples, objects may exhibit low haze. For example, the object may exhibit 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 more Low, 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 A haze of 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. Measure the haze of the object on a 1 mm thick sample according to the haze measurement procedures outlined above. According to various examples, the haze of the article may be lower than that of conventional glass ceramics due to the lack of beta-quartz (i.e., almanite) that is often present in some glass ceramics but tends to increase haze. In other words, the glass-ceramic article can be free of the beta-quartz crystalline phase. Furthermore, the haze of an object can be attributed to a low amount or absence of large grains that tend to scatter light (eg, about <100 nm, or about <60 nm, or about <40 nm).

The use of articles including titanium suboxides, crystals with the general _{formula M}

First, compared to the production of other glass ceramics, the time required for thermal treatment to produce titanium suboxide can be shorter. Furthermore, the heat treatment temperature can be below the softening point of the object. These features can help reduce manufacturing complexity and cost.

Second, color packages (eg, TiO ₂ + ZnS) can be introduced to a wide range of melt compositions, including those with ion exchange capabilities. Additionally, because relatively low concentrations of color encapsulation are required, the addition of such color encapsulation may have less impact on chemical durability and other related object properties.

Third, for UV and/or IR blocking materials that may not have melting difficulties due to radiation trapping, the use of titanium suboxide-containing glass ceramics provides a fusion-formable and chemically strengthenable material. For example, objects including titanium suboxide are highly transparent to visible and NIR wavelengths when molten or in the as-cast state (i.e., the green state before heat treatment), unlike doped Fe ^{2 +} glass, which absorbs strongly in the near infrared even when molten.

Example

The following examples represent certain non-limiting examples of compositions of objects of the present disclosure.

Referring now to Table 1, the object may have from about 58.8 mol% to about 77.58 mol% SiO ₂ , from about 0.66 mol% to about 13.69 mol% Al ₂ O ₃ , and from about 4.42 mol% to about 27 mol% B. ₂ O ₃ , from about 0 mol% to about 13.84 mol% R ₂ O, from about 0 mol% to about 0.98 mol% RO, from about 1.0 mol% to about 13.24 mol% WO ₃ and from about 0 mol% % to about 0.4 mol% SnO ₂ . It will be understood that any of the exemplary compositions of Table 1 may include from about 0 mol% to _about 0.2 mol% _MnO2 , from about 0 mol% to about 0.1 mol% _Fe2O3 , from about 0 mol% mol% to about 0.01 mol% TiO ₂ , from about 0 mol% to about 0.17 mol% As ₂ O ₅ , and/or from about 0 mol% to about 0.1 mol% Eu ₂ O ₃ . The composition of Table 1 is provided in the batch state within the crucible.

Table 1:

Referring now to Table 2, the object may have from about 65.43 mol% to about 66.7 mol% SiO ₂ , from about 9.6 mol% to about 9.98 mol% Al ₂ O ₃ , and from about 9.41 mol% to about 10.56 mol% B. ₂ O ₃ , from about 6.47 mol% to about 9.51 mol% R ₂ O, from about 0.96 mol% to about 3.85 mol% RO, from about 1.92 mol% to about 3.85 mol% WO ₃ , from about 0 mol % to about 1.92 mol% MoO ₃ and from about 0 mol% to about 0.1 mol% SnO ₂ . The composition of Table 2 is provided in the batch state within the crucible.

Table 2

Referring now to Table 3, the object may have from about 60.15 mol% to about 67.29 mol% SiO ₂ , from about 9.0 mol% to about 13.96 mol% Al ₂ O ₃ , and from about 4.69 mol% to about 20 mol% B. ₂ O ₃ , from about 2.99 mol% to about 12.15 mol% R ₂ O, from about 0.00 mol% to about 0.14 mol% RO, from about 0 mol% to about 7.03 mol% WO ₃ , from about 0 mol % to about 8.18 mol% MoO ₃ , from about 0.05 mol% to about 0.15 mol% SnO ₂ and from about 0 mol% to about 0.34 mol% V ₂ O ₅ . It will be understood that any of the exemplary compositions _of Table 3 may include from about 0 mol% to about 0.0025 mol% _Fe2O3 . The composition of Table 3 is provided in the batch state within the crucible.

table 3

Referring now to Table 4, the object may have from about 54.01 mol% to about 67.66 mol% SiO ₂ , from about 9.55 mol% to about 11.42 mol% Al ₂ O ₃ , and from about 9.36 mol% to about 15.34 mol% B. ₂ O ₃ , from about 9.79 mol% to about 13.72 mol% R ₂ O, from about 0.00 mol% to about 0.22 mol% RO, from about 1.74 mol% to about 4.48 mol% WO ₃ , from about 0 mol % to about 1.91 mol% MoO ₃ , from about 0.0 mol% to about 0.21 mol% SnO ₂ , from about 0 mol% to about 0.03 mol% V ₂ O ₅ , from about 0 mol% to about 0.48 mol% of Ag and from about 0 mol% to about 0.01 mol% of Au. It will be understood that any of the exemplary compositions of Table 4 may include from about 0 mol% to about 0.19 mol% _CeO2 , from about 0 mol% to about 0.48 mol% CuO, from about 0 mol% to About 0.52 mol% Br-, from about 0 mol% to about 0.2 mol% Cl-, from about 0 mol% to about 0.96 mol% _TiO2 , and/or from about 0 mol% to about 0.29 mol% Sb ₂ O ₃ . The composition of Table 4 is provided in the batch state within the crucible.

Table 4

Referring now to Table 5, the object may have from about 60.01 mol% to about 77.94 mol% SiO ₂ , from about 0.3 mol% to about 10.00 mol% Al ₂ O ₃ , and from about 10 mol% to about 20 mol% B. ₂ O ₃ , from about 0.66 mol% to about 10 mol% R ₂ O, from about 1.0 mol% to about 6.6 mol% WO ₃ and from about 0.0 mol% to about 0.1 mol% SnO ₂ . It will be understood that any of the exemplary compositions of Table 5 may include from about 0 mol% to about 0.09 mol% Sb ₂ O ₃ . The composition of Table 5 is provided in the batch state within the crucible.

table 5

Reference is now made to Table 6, which provides a list of comparative exemplary glass compositions that form the liquid that separates during the melting process when melted using an unbound base bulk material (e.g., alkali carbonate) in place of a bound base (e.g., nepheline) Alkali tungstate. As explained above, the secondary, liquid, alkali tungstate phase can solidify as separate crystals that can opalify the substrate formed therefrom.

Table 6 Example application

In this context, a characteristic of cadmium and selenium-containing glasses ("CdSe glasses") may be their toxicity, since they have considerable amounts of cadmium and selenium. Some efforts have been made to develop non-toxic or less toxic alternatives to CdSe glass. For example, some conventional alternatives include Cd-free glass compositions. But these compositions still contain selenium and other expensive dopants such as indium and gallium. Furthermore, it is known that conventional Cd-free, selenium-containing glass has poor cutoff wavelength and/or viewing angle dependence compared to CdSe glass. Therefore, applicants believe that there is a need for cadmium- and selenium-free optical materials with comparable or improved optical properties compared to conventional CdSe glasses. Preferably, these materials have tunable bandgaps and sharp cutoffs as non-toxic alternatives to CdSe glass. Given the intended applications of these materials, there is also a need for non-toxic CdSe glass alternatives that feature low coefficient of thermal expansion (CTE), durability, resistance to thermal stress, and/or relatively simple and low-cost manufacturing and handling requirements.

According to some aspects of the present disclosure, a glass ceramic is provided, which includes aluminoborosilicate glass; from about 0.7 to about 15 mol% of WO ₃ ; from about 0.2 to about 15 mol% of at least one alkali metal oxide; and From about 0.1 to about 5 mol% of at least one alkaline earth metal oxide.

According to some aspects of the present disclosure, a glass ceramic is provided, which includes aluminoborosilicate glass; from about 0.7 to about 15 mol% of WO ₃ ; from about 0.2 to about 15 mol% of at least one alkali metal oxide; and From about 0.1 to about 5 mol% of at least one alkaline earth metal oxide. Furthermore, 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.

According to further aspects of the present disclosure, a glass ceramic is provided, which includes aluminoborosilicate glass; from about 0.7 to about 15 mol% WO ₃ ; from about 0.2 to about 15 mol% at least one alkali metal oxide; and From about 0.1 to about 5 mol% of at least one alkaline earth metal oxide. Furthermore, the glass ceramic contains at least one of alkaline earth, alkali and mixed alkaline earth alkali tungstate crystalline phases, and the crystalline phase is in a stoichiometric or non-stoichiometric form.

In some implementations of the aforementioned aspects of glass ceramics, the aluminoborosilicate glass includes from about 55 to about 80 mol% SiO ₂ , from about 2 to about 20 mol% Al ₂ O ₃ , and from about 5 To about 40 mol% B ₂ O ₃ , from 68 to 72 mol% SiO ₂ , from 8 to 12 mol% Al ₂ O ₃ and from 5 to 20 mol% B ₂ O ₃ . Furthermore, at least one alkaline earth metal oxide may include from 0.1 to 5 mol% MgO. The at least one alkali metal oxide may include from 5 to 15 mol% _Na2O . In addition, the difference between the at least one alkali metal oxide and Al ₂ O ₃ in the aluminoborosilicate glass may range from -6 mol% to +2 mol%.

In additional implementations of the aforementioned aspects of the glass ceramic, the glass ceramic may be substantially free of cadmium and substantially free of selenium. Furthermore, the glass ceramic may further include at least one dopant selected from the following composition groups: F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi. In further implementations of the aforementioned aspects of the ceramic glass, the glass ceramic may further include 0% to about 50% MoO ₃ of the WO ₃ present in the glass ceramic.

According to another aspect of the present disclosure, an article is provided including a substrate, the substrate including a primary surface and a glass ceramic composition including: aluminoborosilicate glass; from about 0.7 to about 15 mol% WO ₃ ; from about 0.2 to about 15 mol% of at least one alkali metal oxide; and from about 0.1 to about 5 mol% of at least one alkaline earth metal oxide. Furthermore, in some implementations of this aspect, the substrate further includes a compressive stress region extending from the major surface to a first selected depth in the substrate and derived from the ion exchange process. Also, in some implementations of this aspect, the substrate may include 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.

According to a further aspect of the present disclosure, a method for making glass ceramics is provided. The method includes the following steps: mixing aluminoborosilicate glass, from about 0.7 to about 15 mol% WO ₃ , from about 0.2 to about 15 mol% WO 3 A batch of at least one alkali metal oxide, and from about 0.1 to about 5 mol % of at least one alkaline earth metal oxide; melting the batch between about 1500°C and about 1700°C to form a melt; at about 500°C annealing the melt between about 600°C and about 600°C to define the annealed melt; and heat treating the annealed melt between about 500°C and about 1000°C for from about 5 minutes to about 48 hours to form a glass ceramic.

In some implementations of the foregoing methods before making the glass ceramic, the heat treatment includes heat treating the annealed melt between about 600°C and about 800°C for about 5 minutes to about 24 hours to form the glass ceramic. Furthermore, the heat treatment may include heat treating the annealed melt between about 650°C and about 725°C for about 45 minutes to about 3 hours to form the glass ceramic. In some embodiments of the method, the glass-ceramic may include 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.

As detailed in this disclosure, cadmium and selenium-free glass ceramic materials are provided with comparable or improved optical properties compared to conventional CdSe glasses. In specific implementations, these materials have tunable bandgaps and sharp cutoffs as non-toxic alternatives to CdSe glass. Characteristics of implementations of these materials may also be low coefficient of thermal expansion (CTE), durability, resistance to thermal stress, and/or relatively simple and low-cost manufacturing and processing requirements.

More generally, the glass ceramic materials disclosed herein, and articles containing the same, include a balance of aluminoborosilicate glass, tungsten oxide, at least one alkali metal oxide and at least one alkaline earth metal oxide. Characteristics of these glass ceramic materials may be an optical transmission of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm. Furthermore, these materials may include at least one newly developed alkaline earth tungstate crystalline phase, for example by special heat treatment conditions after formation of the glass ceramic. Furthermore, embodiments of these glass-ceramic materials feature adjustable cutoffs through the selection of specific heat treatment conditions. As such, these glass-ceramic materials provide non-toxic, cadmium- and selenium-free glass ceramics as alternatives to conventional CdSe glasses.

Various embodiments of the disclosed glass ceramic materials may be implemented in the form of substrates, components, housings, and other components in any of the following applications: security and surveillance filters configured to suppress visible light for infrared lighting; airport runways Lamps; laser eye protection lenses; light barriers for motion control in motors; barcode readers; atomic force microscopes; nanoindentation machines; laser interferometer measurement solutions; laser-based dynamic correction systems; applications Lithography solutions for integrated circuit manufacturing; photon bit error ratio test solutions; photon digital communication analyzers; photon jitter generation and analysis systems; optical modulation analyzers; optical power meters; optical attenuators; light sources; light wave components Analyzers; gas chromatographs; spectrometers; fluorescence microscopes; traffic surveillance cameras; environmental waste, water and exhaust gas monitoring equipment; spectral filters for photographic cameras; radiation thermometers; imaging photometric colorimeters; industrial image processing; Controlled wavelength light sources for counterfeit detection; scanners for digitizing color images; astronomy filters; Humphry field analyzers in medical diagnostic equipment; and optical filters for ultrashort pulse lasers. Embodiments of these glass ceramic materials are suitable for various artistic endeavors and applications using tinted glass, glass ceramics and ceramics, such as glass blowers, flame workers, colored glass artists, etc.

Glass-ceramic materials and articles containing them offer various advantages over conventional glasses, glass-ceramics and ceramic materials in the same field, including CdSe glass. As noted previously, the glass-ceramic materials of the present disclosure are cadmium and selenium free, thus providing sharp, visible extinction similar to the orange conventional CdSe filter glass. Compared with semiconductor-doped glass, a conventional alternative to CdSe glass, the disclosed glass ceramic material also provides sharper visible light extinction. Furthermore, the glass ceramic materials of the present disclosure are formulated with lower cost materials compared to conventional alternatives to CdSe glass that utilize indium, gallium and/or other high cost metals and components. Another advantage of these glass-ceramic materials is that their characteristics can be a cut-off wavelength that is tunable through the selection of heat treatment temperature and time conditions. A further advantage of these glass ceramics is that, unlike CdSe glasses, they are transparent in the near-infrared ("NIR") spectrum and do not exhibit reduced transmittance at wavelengths from 900 to 1100 nm. Furthermore, unlike other conventional CdSe glass alternatives such as semiconductor-doped glasses containing indium and gallium that require additional semiconductor synthesis and grinding steps, these glass-ceramic materials can be manufactured using conventional melt quench processes.

Referring now to FIG. 1 , an object 100 is depicted. The object 100 includes a substrate 10 including a glass ceramic composition according to the present disclosure. These items may be employed in any of the applications outlined previously (eg, optical filters, airport runway lights, barcode readers, etc.). Therefore, in some implementations, the characteristics of the substrate 10 may be at least 90% optical transmittance from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm. Substrate 10 includes a pair of opposing major surfaces 12,14. In some implementations of article 100 , substrate 10 includes a compressive stress region 50 . As shown in FIG. 1 , the compressive stress region 50 of article 110 is illustrative and extends from major surface 12 to a first selected depth 52 in the substrate. Some embodiments of article 100 (not shown) include additional, comparable compressive stress regions 50 extending from major surface 14 to a second selected depth (not shown). Furthermore, some implementations of article 100 (not shown) include multiple compressive stress regions 50 extending from major surfaces 12 , 14 of substrate 10 . Further, some embodiments (not shown) of article 100 include multiple compressive stress regions 50 extending respectively from major surfaces 12, 14 and also from short edges of substrate 10 (i.e., edges orthogonal to major surfaces 12, 14). ) compressive stress area. As will be understood by one of ordinary skill in the art of this disclosure, various combinations of compressive stress regions 50 may be incorporated into article 100, depending on the processing conditions employed to create these compressive stress regions 50 (e.g., , completely immersing the substrate 10 in the molten salt molten ion exchange bath, partially immersing the substrate 10 in the molten salt molten ion exchange bath, masking some edges and/or surfaces while fully immersing the substrate 10 , etc.).

As used herein, "selected depth" (eg, selected depth 52), "compression depth" and "DOC" are used interchangeably to define the depth at which stress in substrate 10 changes from compression to extension, as herein described. Depending on the ion exchange process, DOC can be measured by a surface stress meter such as FSM-6000, or a scattered light polarimeter (SCALP). A surface stress meter is used to measure DOC when the stress in the substrate 10 composed of glass or glass ceramic is generated by the exchange of potassium ions into the glass substrate. SCALP is used to measure DOC when the stress is the exchange of sodium ions into the glass object. When the stress in the substrate 10 composed of glass or glass ceramic is caused by the exchange of both potassium and sodium ions into the glass, DOC is measured by SCALP because it is considered that the exchange depth of sodium represents DOC and the exchange depth of potassium ions represents A change in the magnitude of compressive stress (but not a change in stress from compression to extension); a surface stress meter is used to measure the exchange depth of potassium ions in these glass substrates. 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 implementations, the maximum compressive stress is obtained at or immediately adjacent to one or more major surfaces 12 , 14 defining the compressive stress region 50 . In other embodiments, maximum compressive stress is achieved between one or more major surfaces 12 , 14 and a selected depth 52 of the compressive stress region 50 .

Referring again to FIG. 1 , the substrate 10 of the object 100 may be composed of glass ceramic. In a specific implementation, the glass ceramic composition of the substrate 10 is: 0.7 to 15 mol% WO ₃ , 0.2 to 15 mol% at least one alkali metal oxide, and 0.1 to 5 mol% at least one alkaline earth metal. Oxides and the remainder are silicate-containing glasses. These silicate-containing glasses include aluminoborosilicate glasses, borosilicate glasses, aluminosilicate glasses, soda-lime glasses, and chemically strengthened versions of these silicate-containing glasses.

Furthermore, in the specific implementation of the object 100 depicted in Figure 1, the substrate 10 may have a selected length and width, or diameter, to define its surface area. The substrate 10 may have at least one edge defined by its length and width, or diameter, between the major surfaces 12, 14 of the substrate 10. The substrate 10 may also have a selected thickness. In some implementations, the substrate has a thickness from about 0.2 mm to about 1.5 mm, from about 0.2 mm to about 1.3 mm, and from about 0.2 mm to about 1.0 mm. In other implementations, the substrate has a thickness from about 0.1 mm to about 1.5 mm, from about 0.1 mm to about 1.3 mm, or from about 0.1 mm to about 1.0 mm.

In some implementations of article 100, as depicted in the illustrative form in Figure 1, substrate 10 is selected from chemically strengthened aluminoborosilicate glass. For example, the substrate 10 may be selected from chemically strengthened aluminoborosilicate glass having a compressive stress region 50 greater than 10 µm extending to a first selected depth 52, with a maximum compressive stress greater than 150 MPa. In a further embodiment, the substrate 10 is selected from chemically strengthened aluminoborosilicate glass having a compressive stress region 50 greater than 25 µm extending to a first selected depth 52 and having a maximum compressive stress greater than 400 MPa. The substrate 10 of the article 100 may 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) having 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 implementations, the maximum compressive stress is 2000 MPa or less. Additionally, depending on the thickness of the substrate 10 and the processing conditions associated with generating the compressive stress region 50, the depth of compression (DOC) or first selected depth 52 may be set to 10 µm or greater, 15 µm or greater, 20 µm or greater. Large, 25 µm or greater, 30 µm or greater, 35 µm or greater, and even greater depths. In some implementations, the DOC is a thickness (t) less than or equal to 0.3 times of the substrate 10, such as 0.3 t, 0.28 t, 0.26 t, 0.25 t, 0.24 t, 0.23 t, 0.22 t, 0.21 t, 0.20 t , 0.19 t, 0.18 t, 0.15 t, or 0.1 t.

As previously outlined, the glass-ceramic materials of the present disclosure, including the substrate 10 employed in article 100 (see Figure 1), are characterized by the following glass-ceramic composition: from 0.7 to 15 mol% WO ₃ , from 0.2 to 15 mol% of at least one alkali metal oxide, from 0.1 to 5 mol% of at least one alkaline earth metal oxide and the balance is silicate-containing glass, such as aluminoborosilicate glass. In specific implementations, the characteristics of the glass ceramic material may be 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. In some implementations, the glass ceramic material may further be characterized by the presence of at least one alkaline earth tungstate crystalline phase and/or at least one alkali metal tungstate crystalline phase. For example, the alkaline earth tungstate crystalline phase may be M _x WO ₃ , where M is at least one of Be, Mg, Ca, Sr, Ba, and Ra, and where 0<x<1. In specific embodiments of the glass ceramics of the present disclosure, at least one alkaline earth tungstate crystalline phase is a MgWO ₄ crystalline phase (see, for example, Figure 5 and its corresponding description) and a MgW ₂ O ₇ crystalline phase (see, for example, Figure 5 and its corresponding description) One or both of Figures 6A-6C, Figures 7A and 7B and their corresponding descriptions. As another example, the alkali tungstate crystalline phase may be M _x WO ₃ , where M is at least one of Li, Na, K, Cs, Rb, and where 0<x<1. As a _further example, the tungstate crystalline phase may be _M A combination of alkali metals forming a group, and where 0&lt;x&lt;1.

In specific embodiments, the glass ceramics of the present disclosure are optically transparent in the visible region of the spectrum (ie, from about 400 nm to about 700 nm). As used herein, the term "optically transparent" means transmittance over a 1 mm path length over at least a 50 nm wide wavelength band of light in the range from about 400 nm to about 700 nm. Greater than approximately 1% (e.g., in %/mm). In some embodiments, the glass ceramic has at least greater than about 5%/mm, greater than about 10%/mm, greater than about 15% over at least a 50 nm wide light wavelength band in the visible light region of the spectrum. /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 penetrations greater than all lower limits between these values.

Embodiments of the glass ceramics of the present disclosure operate in the ultraviolet ("UV") region of the spectrum (i.e., wavelengths less than about 370 nm) and/or in 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 implementations, the glass ceramic is characterized by less than 10%/mm, less than 9%/mm, less than 8%/mm for light in a wavelength band of light of at least 50 nm wide in the UV region of the spectrum. 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 penetration rate. In some embodiments, the glass ceramic absorbs or has at least 90%/mm, at least 91%/mm, or at least 92%/mm for light in a wavelength band of light that is 50 nm wide in the UV region of the spectrum. , 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 absorption rate. In other implementations, for light in at least a 50 nm wide light wavelength band in the NIR region of the spectrum, the characteristics of the glass ceramic are less than 10%/mm, less than 9%/mm, and less than 8%/mm. 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 penetration rate. In other embodiments, the glass ceramic absorbs or has at least 90%/mm, at least 91%/mm, or at least 92%/mm for light in a wavelength band of light that is 50 nm wide in the NIR region of the spectrum. , 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 absorption rate.

Specific embodiments of the glass ceramic materials of the present disclosure include aluminoborosilicate glass (e.g., containing SiO ₂ , Al ₂ O ₃ and B ₂ O ₃ ), WO ₃ , at least one alkali metal oxide, and at least one Alkaline earth metal oxides. In some embodiments, the aluminoborosilicate glass includes from about 55 mol% to about 80 mol% SiO ₂ , from about 60 mol% to about 74 mol% SiO ₂ , or from about 64 mol% to About 70 mol% SiO ₂ . Furthermore, the aluminoborosilicate glass of the glass ceramic may include from about 2 mol% to about 40 mol% B ₂ O ₃ , from about 5 mol% to about 16 mol% B ₂ O ₃ , or from about 6 mol% mol% to about 12 mol% B ₂ O ₃ . Additionally, the aluminoborosilicate glass of the glass ceramic may include from about 0.5 mol% to about 16 mol% Al ₂ O ₃ , from about 2 mol% to about 20 mol% Al ₂ O ₃ , or from about 6 mol % % to about 14 mol% Al ₂ O ₃ .

The glass ceramic materials of the present disclosure include from about 0.7 mol% to about 15 mol% WO ₃ . In some embodiments, the glass ceramic material includes from about 1 mol% to about 6 mol% WO ₃ , or from about 1.5 mol% to about 5 mol% WO ₃ . In some implementations, the glass ceramic may further comprise from about 0% to about 50% MoO ₃ of WO ₃ present in the composition (ie, from about 0% to 5 mol% MoO ₃ ). In some embodiments, the glass ceramic further includes from about 0 mol% to about 3 mol%, or from about 0 mol% to about 2 mol% MoO ₃ .

The glass ceramic materials of the present disclosure include at least one alkali metal oxide. In specific embodiments, the glass ceramic material includes from about 0.2 mol% to about 15 mol% of at least one alkali metal oxide. The at least one alkali metal oxide may be selected from the group including Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O. In some implementations, the content difference of the Al ₂ O ₃ in the at least one alkali metal oxide and the aluminoborosilicate glass ranges from -6 mol% to +2 mol%.

The glass ceramic material of the present disclosure also includes at least one alkaline earth metal oxide. In specific embodiments, the glass ceramic includes from about 0.1 mol% to about 5 mol% of at least one alkaline earth metal oxide. At least one alkaline earth metal oxide may be selected from the group including MgO, SrO and BaO. In other embodiments, the glass ceramic material of the present disclosure includes 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%. SnO ₂ .

According to preferred practices, the glass ceramic materials of the present disclosure are substantially free of cadmium and substantially free of selenium. In specific implementations, the glass ceramic may further include at least one dopant selected from the following composition groups: F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi. In some embodiments, at least one dopant is present in the glass ceramic as an oxide in an amount from about 0 mol% to about 0.5 mol%.

Non-limiting compositions of glass ceramics in accordance with the principles of the present disclosure are set forth in Tables 1A (expressed in weight percent) and 1B (expressed in mol%) below.

Table 1A Table 1A – Continuation

Table 1B Table 1B – Continuation

According to specific implementation aspects, the glass ceramic material of the present disclosure can be produced by using a melt quenching process. The components can be mixed and blended in appropriate proportions by turbulent mixing and/or ball milling. Bulk materials may include, but are not limited to, one or more of sand, spodumene, phyllite, nepheline syenite, alumina, borax, boric acid, alkali gold and alkaline earth carbonates and nitrates, tungsten oxide and ammonium tungstate. The batch of material is then melted at a temperature ranging from about 1500°C to about 1700°C for a predetermined time. In some implementations, the predetermined time ranges from about 6 to about 12 hours, after which time the resulting melt may be cast or formed and then annealed, as is common knowledge in the art of this disclosure. understood by the person. In some implementations, the melt may be annealed between about 500°C and about 600°C to define an annealed melt.

At this stage of the process, the annealed melt is heat treated at about 500°C to about 1000°C for 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 develop one or more crystalline tungstate phases.

In some embodiments, the annealed melt is heat treated between about 600°C and about 800°C for about 5 minutes to about 24 hours to form the glass ceramic. According to some embodiments, the annealed melt is heat treated between about 650°C and about 725°C for about 45 minutes to about 3 hours to form a glass ceramic. In another implementation, the annealed melt is heat treated according to temperature and time to obtain special optical properties, such as at least 90% optical transmittance from 700 nm to 3000 nm and a sharp cutoff from about 320 nm to about 525 nm. wavelength. Furthermore, as outlined in the following examples, additional heat treatment temperatures and times may be used to obtain glass ceramic materials. Examples of illustrative applications

The following examples represent certain non-limiting examples of glass ceramic materials and articles of the present disclosure (including methods of making them).

Referring now to Figures 2A and 2B, plots comparing transmittance versus wavelength of a CdSe glass ("Comparative Example 1") and a heat-treated glass ceramic ("Example 1") are provided. Note that Figure 2B is a plot of Figure 2A, resized to show a comparison of the cutoff wavelengths of CdSe glass and heat-treated glass-ceramic samples. In this example, a comparative CdSe glass, Comparative Example 1, has a conventional CdSe glass composition according to the following: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2 -1% S, and 0-1% Se; and the heat-treated glass-ceramic had the same composition as the Example 1 sample indicated in Tables 1A and 1B. Furthermore, the glass ceramics depicted in Figures 2A and 2B are prepared according to the previously noted method of producing glass ceramic materials in this disclosure, which includes a heat treatment step involving heating and annealing the melt at 700°C for about 1 hour. Additionally, the samples depicted in Figures 2A and 2B both have a normalized path length of 4 mm. What is evident from these figures is that, heat treated at 700°C for 1 hour, the glass ceramic sample (Example 1) and the CdSe glass sample (Comparative Example 1) exhibit sharp cutoffs in approximately the same wavelength range and sharpness.

Referring now to Figures 3A and 3B, plots comparing transmittance versus wavelength of CdSe glass ("Comparative Example 1") and heat-treated glass ceramics ("Examples 1A-1K") are provided. Note that Figure 3B is a plot of Figure 3A, resized to show a comparison of the cutoff wavelengths of CdSe glass and heat-treated glass-ceramic samples. In this example, a comparative CdSe glass, Comparative Example 1, has a conventional CdSe glass composition according to the following: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2 -1% S, and 0-1% Se; and the heat-treated glass ceramic each had the same composition as the Example 1 sample indicated in Tables 1A and 1B. Furthermore, the glass ceramics described in Figures 3A and 3B were prepared according to the method for making glass ceramic materials previously noted in this disclosure, which method includes 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 1B); 550°C for 3 hours and 10 minutes (Example 1C); 600°C for 6 hours and 24 minutes (Example 1D); 600°C for 15 hours and 20 minutes (Example 1E); 650°C for 2 hours (Example 1F); 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 1K). Additionally, all samples depicted in Figures 3A and 3B have a normalized path length of 4 mm. What is evident from these figures is that all glass ceramic samples (Examples 1A-1K) and the CdSe glass sample (Comparative Example 1) exhibit sharp cutoffs in approximately the same wavelength range and sharpness, subject to various conditions of heat treatment. Furthermore, it is apparent from these figures that various heat treatment temperature and time conditions can be used to change and adjust the cutoff wavelength and its sharpness in the range of about 320 nm to about 525 nm.

According to another example, 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 is a plot comparing transmittance versus wavelength of CdSe glass ("Comparative Example 1") and glass ceramic samples heat treated at 700°C and 800°C under various conditions (Examples 1K and 2A). Note that Figure 4B is a plot of Figure 4A, resized to show a comparison of the cut-off wavelengths of CdSe glass and glass-ceramic samples heat-treated under various conditions. In this example, a comparative CdSe glass, Comparative Example 1, has a conventional CdSe glass composition according to the following: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2-2.0 CdO, 0.2 -1% S, and 0-1% Se; a heat-treated glass-ceramic sample, Example 1K, having the same composition as the Example 1 sample indicated in Tables 1A and 1B; and a heat-treated glass-ceramic sample, Example 2A, had the same composition as the Example 2 sample indicated in Tables 1A and 1B. Furthermore, each of the glass ceramics described in Figures 4A and 4B was prepared according to the method for making glass ceramic materials previously noted in this disclosure, which method includes the following heat treatment steps after annealing: 700°C for 2 hours (Example 1K); and 800°C for 1 hour and 4 minutes (Example 2A). Additionally, all samples depicted in Figures 4A and 4B have a normalized path length of 4 mm. What is evident from these figures is that all glass ceramic samples (Examples 1K and 2A) and the CdSe glass sample (Comparative Example 1) exhibit sharp cutoffs in approximately the same wavelength range and sharpness, subject to various conditions of heat treatment. Furthermore, it is obvious from these figures and the individual compositions of these glass ceramics (see Tables 1A and 1B) that the composition of these magnesium tungsten glass ceramics can be used to change and adjust the cut-off wavelength and its wavelength at about 320 using special heat treatment conditions. nm to approximately 525 nm. It is also apparent that the higher magnesium content in the glass-ceramic of Example 2A (~3.84 mol%) compared to the magnesium content of the glass-ceramic of Example 1K (~0.95 mol%) may contribute to its lower cut-off wavelength, and perhaps Its higher penetration rate in the NIR range. Therefore, and without being bound by theory, changing the magnesium content in the composition of these glass ceramics and changing the heat treatment conditions can have the effect of changing the spectrum and cut-off wavelength of the glass ceramics.

Referring now to Figure 4C, the plot in Figure 4A is provided again, as well as the transmittance versus wavelength for comparative CuInSe and CuInS glass samples ("Comparative Example 2" and "Comparative Example 3" respectively). The spectra of Comparative Example 2 and Comparative Example 3 were obtained from the "Exemption Renewal Request) 13(b)" submitted to Oko-Institut e.V. on March 26, 2015, Spectaris e.V. Furthermore, Figure 4C is resized to show comparative CdSe glass (Comparative Example 1), glass ceramic samples heat-treated according to various conditions (Example 1K and Example 2A), and comparative CuInSe and CuInS samples (Comparative Example 2 and Comparative Example 3 ) cutoff wavelength. It is obvious from Figure 4C that the glass ceramic materials according to the present disclosure, Example 1K and Example 2A, outperform the comparative CuInSe and CuInS glasses in terms of approximate cut-off wavelength of the comparative CdSe glass. That is, compared to other semiconductor-doped glass substitutes, CuInSe and CuInS, these glass ceramics have optical properties that are more similar to the optical properties of CdSe glass.

Referring now to Figure 5, an x-ray diffraction ("XRD") pattern of a heat-treated glass ceramic, Example 1L (see Tables 1A and 1B), is provided in accordance with at least one example of the present disclosure. This sample was heat treated at 700°C for 17 hours and 16 minutes. It is apparent from the peak values listed for d-spacing (e.g., d=3.6127, d=3.2193, etc.) that the Example 1L glass-ceramic may contain a crystalline _MgWO tungsten oxide phase. Without being bound by theory, the XRD pattern in Figure 5 may also suggest that the glass ceramic contains a non-stoichiometric MgWO ₄ phase or a mixed alkali metal MgWO ₄ phase that can be described as M _x WO ₄ crystals, where M = Mg or M =Mg and one or more of the alkali metal group consisting of Li, Na, K, Rb and Cd, and 0<x<1.

Referring now to Figures 6A-6C, in accordance with an example of the present disclosure, a rapidly quenched glass ceramic sample is provided (i.e., Figure 6A, Example 1, without heat treatment after annealing) and heat treated at 650°C for 5 hours and 35 Raman light patterns of glass ceramic samples (Example 1H and Example 1L shown in Figures 6B and 6C, respectively) that were heat treated at 700°C for 17 hours and 16 minutes. As in the previous examples, all glass-ceramic materials subjected to Raman spectroscopy testing had glass-ceramic compositions according to Example 1 in Tables 1A and 1B. The special numerical symbols associated with the data sequences in Figures 6B and 6C (e.g., "#1", "#2-Orange", "#2-Gray", etc.) correspond to special numerical symbols on the samples undergoing Raman spectroscopy testing. Evaluate locations (including sample colors for those locations). Figure 6A demonstrates that samples quenched without further heat treatment (Example 1) exhibit various increasing intensity levels indicative of amorphous phases (e.g., network bending Si-O, Al-O, and BO at 470 cm ^-1 ) . In contrast, Figures 6B and 6C demonstrate that the lower intensity levels observed in the rapidly quenched sample (Example 1) correlate to the same Raman shift position in the heat-treated sample (Examples 1H and 1L) Have substantially higher intensity levels and positions indicating the presence of crystalline phases (e.g., WOW at 846 and 868 cm ^-1 related to MgW ₂ O ₇ ). In this way, it is evident from the signal peaks present at Raman shift positions including but not limited to 345, 376, 404, 464, 718, 846 and 868 cm ^-1 that the heat treatment conditions cause crystalline oxidation of MgW ₂ O ₇ Development of tungsten phase. Figures 6B and 6C also suggest that the heat treatment conditions result in a crystalline tungsten suboxide phase (i.e., a non-stoichiometric phase) that combines with or replaces the crystalline tungsten oxide phase (i.e., the M _x WO ₄ crystalline phase outlined previously). ) development.

Referring now to Figures 7A and 7B, according to examples of the present disclosure, heat treated at 650°C for 5 hours and 35 minutes and heat treated at 700°C for 17 hours and 16 minutes (Example 1H and Example 1L, respectively) and Raman spectrum of a glass ceramic sample as freshly quenched (i.e., Example 1, no heat treatment after annealing). As in the previous examples, all glass-ceramic materials subjected to Raman spectroscopy testing had glass-ceramic compositions according to Example 1 in Tables 1A and 1B. The special numerical symbols associated with the data sequences in these figures (e.g., "#1", "#2-Orange", "#2-Gray", etc.) correspond to special evaluation locations on the samples that were subjected to Raman spectroscopy testing ( including sample colors at those locations). First, Figures 7A and 7B demonstrate that the same Raman shift positions associated with high intensity levels observed in samples subjected to specific heat treatment conditions (Examples 1H and 1L), are substantially the same in the rapidly quenched sample (Example 1). to a lower intensity level. Thus, it is apparent that heat treatment conditions can result in a crystalline tungsten oxide phase (e.g., MgW ₂ O ₇ as shown in both Figures 7A and 7B) and/or a crystalline tungsten suboxide phase (i.e., non-chemical The development of the phase of measurement.

Referring now to Figure 8, a plot of residual stress (MPa) versus substrate depth (mm) is provided for glass ceramic samples (Example 10-IOXA and Example 10-IOXB) with compressive stress regions derived from two separate ion exchange process conditions. Drawing. In Figure 8, the y-axis is the residual substrate in the substrate, with positive values representing tensile residual stress and negative values representing compressive residual stress. Also in Figure 8, the x-axis is the depth in each substrate, with values at 0 mm and 1.1 mm representing the major surfaces of the substrate (e.g., major surfaces 12 and 14 of substrate 10, as shown in Figure 1) . Each of the glass ceramic samples in this example, Example 10-IOXA and Example 10-IOXB, had the same composition as indicated in the Example 10 samples in Tables 1A and 1B. Again, each sample was melted and cast onto a steel table to form optical cakes, consistent with the method outlined previously in this disclosure. Each sample was then annealed at 570°C for one hour and then cooled to ambient temperature at furnace rate. Samples with dimensions of 25 mm x 25 mm x ~1.1 mm were then ground and polished to form annealed optical cakes. Finally, the Example 10-IOXA sample was immersed in a 100% NaNO _molten salt bath at 390°C for eight (8) hours to create its compressive stress region. Similarly, the Example 10-10XB sample was immersed in a 100% NaNO _molten salt bath at 390°C for sixteen (16) hours to create its compressive stress zone. It should be noted that the actual thickness of the Example 10-IOXA and 10-IOXB samples was measured at 1.10 mm and 1.06 mm respectively.

It is obvious from Figure 8 that longer ion exchange duration tends to increase the DOC, stored strain energy, and peak tension (i.e., the maximum tensile stress in the central tensile region) of the glass-ceramic, while decreasing its Maximum compressive stress. In particular, the glass-ceramic sample with shorter ion exchange duration, Example 10-IOXA, exhibits a compressive stress region with a depth of compression (DOC) of 136.7 µm, a maximum compressive stress of approximately -320 MPa, and a peak tension centered at 57 MPa tensile (CT) region, and a stored strain energy of 16.6 J/ ^m2 . In comparison, a glass-ceramic sample with a longer ion exchange duration, Example 10-IOXB, exhibits a DOC of 168.0 µm, a maximum compressive stress of approximately -270 MPa, a CT region with a peak tension of 72 MPa, and 25 J/ m ² stored strain energy. Therefore, compared to Example 10-IOXA, which has a shorter ion exchange process duration, the longer ion exchange duration of the Example 10-IOXB sample resulted in a larger DOC, lower maximum compressive stress, and larger peak tension. CT area and larger stored strain energy.

Although it is apparent that the glass ceramic sample previously described in Figure 8 exhibits a region of compressive stress developed by immersion in a 100% NaNO _molten salt bath, other methods are also contemplated within this disclosure. For example, the glass-ceramics can also be ion-exchanged in a molten KNO ₃ bath (a mixture of NaNO ₃ and KNO ₃ ), or sequentially ion-exchanged first in a NaNO ₃ bath and then in KNO ₃ to increase the compressive stress potential. Aligned to the surface of the substrate, and close to the surface of the substrate. Therefore, sulfates, chlorides, and other salts of ion-exchanged metal ions (eg, Na ⁺ , K ^{+ ,} etc.) may also be used in these baths. Furthermore, the ion exchange temperature can vary from about 350°C to about 550°C, and a preferred range is from 370°C to about 450°C to prevent salt decomposition and stress relaxation.

With rough reference to Figures 9 to 11B, different size systems of crystals are found in the above-mentioned tungsten bronze and multi-color tungsten bronze glass ceramics. Crystal size depends on the base glass composition, but can also be slightly adjusted by heat treatment time and temperature. In addition, adding a small amount of calcium oxide (CaO) significantly increases the crystallization rate because it is believed to interact with tungsten oxide to form nanocrystals of scheelite that can serve as nucleation sites, or a non-stoichiometric scheelite-like structure. .

Referring now to Figure 9, relatively large crystals were found in the aforementioned highly peraluminous tungsten bronze melt (eg, _MxWO3 glass ceramic) _and are shown in Figure 9. These crystals are needle-like in shape, with a length of 100-250 nm and a width of 5-30 nm. In the freshly quenched state, after rapid quenching (i.e., rapid quenching) between two iron plates, these glass-ceramic materials were x-ray amorphous and scanned electron microscopy (SEM) analysis showed no precipitates ( crystals, grains) exist. After heat treatment of quenched glass at 700ºC for 30 minutes or more and cooling to room temperature at 10ºC per minute, tungsten bronze precipitates and alumina-rich needles form. Increase the heat treatment time and temperature to increase the precipitate concentration, for example, after heat treatment at 700ºC for 1 hour and 40 minutes and cooling to room temperature at 10ºC/minute. Energy dispersive x-ray spectrometer (EDS) x-ray images of the grains formed after heat treatment showed that they contained tungsten, oxygen and potassium.

Referring to Figures 10A and 10B, for at least some overbased tungsten bronze melts (R ₂ O-AL ₂ O ₃ > 0), the grain size is smaller than that in the peraluminous melt (Figure 9) , and no alumina-rich needles are formed. Like a peraluminous melt, the perbased material is x-ray amorphous when quenched (i.e., rapidly quenched) between two iron plates. Micrographs show that no grains were present in the material prior to heat treatment. After heat treatment at 550ºC and rapid quenching for a time between 15 and 30 hours, followed by cooling to 475ºC at 1ºC/min, and then cooling to room temperature at the furnace rate, TEM analysis revealed high aspect ratio acicular tungsten bronze grains. Formed, as shown in Figures 10A and 10B. The most obtained needles have diameters between 2 and 7 nm and lengths between 10 and 30 nm. X-ray EDS of the heat-treated and flash-quenched sample showed that the grains contained tungsten.

Referring to Figures 11A and 11B, the silver tungsten bronze glass ceramic includes crystal grains, the shape of the crystal grains is generally rod-shaped, has an aspect ratio between 2 and 4, most of the length is about 2-20 nm, and most of the grains are rod-shaped. The diameter is about 2-10 nm, and is about 11 to 14.8 volume percent of the material glass ceramic. The samples shown in Figures 11A and 11B were heat treated at 550ºC for 4 hours, cooled to 475ºC at 1ºC/minute, and then cooled to room temperature at furnace rate. The rod was then placed in the gradient oven for five minutes so that one end of the rod was at room temperature and the other end of the rod was at 650ºC. The area between each end is exposed to an approximately uniform gradient of temperatures between 25º and 650ºC. In areas with temperatures above about 575ºC, the color begins to change from blue to green, to yellow, to orange, and finally to red. All colors are highly transparent.

As disclosed above, according to some exemplary embodiments, the glass-ceramic has a wavelength band of light of at least 50 nm wide in the range from about 400 nm to about 700 nm, with a thickness of about 5%/mm or greater. The penetration rate. However, in other embodiments, the glass ceramic has lower transmittance, such as being opaque. According to at least some of these embodiments, these glass ceramics are unique in that they strongly absorb but do not scatter light and have very low haze. According to various such embodiments, the glass-ceramic has an optical density per millimeter (OD/mm) of at least 0.07 for at least some (e.g., at most, >90%) of light having wavelengths of 200-400 nm, and at most the same wavelength A haze of 25 OD/mm, and/or less than 10%, where optical density is calculated using optical absorbance measurements obtained with a spectrophotometer, and haze is measured using a hazemeter wide-angle scattering test. According to various such embodiments, the glass-ceramic has an optical density per millimeter (OD/mm) of at least 0.022 for at least some (e.g., at most, >90%) of light having wavelengths of 400-750 nm, and at most the same wavelength 10 OD/mm, and/or less than 10% haze. According to various such embodiments, the glass-ceramic has an optical density per millimeter (OD/mm) of at least 0.04 for at least some (e.g., at most, >90%) of light having wavelengths from 750 to 2000 nm, and at most the same wavelength 15 OD/mm, and/or less than 10% haze. Examples containing titanium

Referring now to Tables 8A and 8B, a list of exemplary glass ceramic compositions for articles including titanium is provided.

Table 8A

Table 8B

With reference now to Table 8C and Figures 12A-17B, optical data are provided for samples of the compositions from Tables 8A and 8B.

Table 8C

Prepared by weighing the batch ingredients, mixing the batch ingredients by shaker-mixer or ball mill, and melting in a fused silica crucible at a temperature between 1300 ^° -1650 ^° C for 4-32 hours Various compositions of Table 8C and Figures 12A-17B. Cast the glass onto a metal table to create 0.5 mm thick glass cakes. Some of the melt is cast onto a steel table and rolled into sheets using steel rollers. To develop and control optical transmission and absorbance, the samples were heat treated in an atmospheric electric oven over a time range from 5-500 min at a temperature range from 425-850 ^° C. The sample cakes were then polished to a thickness of 0.5 mm and tested.

It is obvious from the data in Table 8C and Figures 12A-17B that the titanium-containing glass is highly transparent in the NIR system as it is made, and is mostly transparent at visible light wavelengths. Upon thermal treatment in the temperature range from about 500°C to about 700°C, a crystalline phase (ie, titanium suboxide) precipitates and the optical transmittance of these samples decreases and some become strongly absorbing in the NIR.

Powder X-ray diffraction was performed on each composition of Table 8C and powder X-ray diffraction indicated that all compositions were X-ray amorphous in the as-fabricated and unannealed state. The heat-treated samples showed some evidence of titanium oxide crystalline phases, including anatase (889FLY) and rutile (889FMC and 889FMD). The sample exhibits low haze (ie, 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 both the as-fabricated and post-heat-treated states is due to the relatively small size of the grains (i.e., about 100 nm or less) and low abundance (i.e., due to the introduction of only The fact that about 2 mol% TiO ₂ ). Therefore, based on conventional powder XRD, it is believed that the species formed in these materials are below the detection limit (in size and abundance). This hypothesis was confirmed by TEM microscopy.

Referring now to Figures 18A-D, four different magnification TEM micrographs of titanium oxide in a sample of glass code 889FMC that was heat treated at 700°C for one hour are provided. These crystals are rod-shaped in appearance and have an average width of approximately 5 nm and an average length of approximately 25 nm.

Referring to Figures 19A and 19B, the TEM micrograph (Figure 19A) and the corresponding EDS elemental diagram (Figure 19B) of the heat-treated sample composed of glass code 889FMC are provided. As can be seen in Figure 19A, the sample includes a plurality of grains. Set up EDS graph to detect titanium. As can be seen, the results of the EDS titanium mapping closely track the grains, indicating that the grains are rich in titanium. In this diagram, light or "white" areas indicate the presence of Ti.

Referring now to Table 9A, exemplary glass compositions without titanium are provided.

Table 9A

Table 9B provides solar performance metrics for a variety of glasses. In Table 9B, composition 196KGA is incorporated as the cladding layer of a dual-fusion laminate (i.e., total clad glass ceramic thickness = 0.2 mm) where the core composition of the laminate is chemically strengthened from Corning Incorporated ^{® Gorilla®} glass. Composition 196KGA is 1 mm thick and heat treated at 550°C for 30 minutes and allowed to cool to 475°C at 1°C per minute. The 889FMD specimen was 5 mm thick and heat treated at 600°C for 1 hour. 889FMG samples were 0.5 mm thick and heat treated at 700°C for 2 hours. The VG10 sample refers to the glass sold under the trade name SGG VENUS (VG 10) by Saint-Gobain ^® and has different thicknesses.

Table 9B

In Table 9B, T_L is the total visible light transmittance (which is the weighted average transmittance of light passing through the mosaic glass in the wavelength range 380 nm to 780 nm and tested according to ISO 9050 paragraph 3.3). T_TS is the total transmitted solar energy (also known as the solar penetration factor ("SF") or the total solar heat penetration ("TSHT"), which is T_DS (total direct solar energy) plus the total solar energy transmitted by ISO 13837-2008 Annex B and ISO 9050-2003, paragraph 3.5, of the total fraction of solar energy absorbed by the glazing and then reradiated into the interior of the vehicle. In this case, for a parked vehicle with a wind speed of 4 m/s (14 km/hr)% Conditions calculate T_TS, and T_TS is equal to (%T_DS) + 0.276*(% solar absorption rate). T_DS is the total direct solar penetration (also known as "solar transmittance" ("Ts") or "energy transfer", which It is the weighted average transmittance of light passing through the mosaic glass in the wavelength range from 300 nm to 2500 nm as measured in ISO 13837 paragraph 6.3.2)). R_DS is the reflected solar component (i.e., has a nominal 4% Friel reflection). T_E is the direct solar penetration rate. T_UV is the UV transmittance measured according to ISO 9050 and ISO 13837 A. T_IR is the infrared transmittance measured by Volkswagen standard TL957.

It is self-evident from the data in Table 9B that glass code 196KGA has the best optical performance and is able to produce the lowest UV, VIS, and NIR transmission at very short path lengths (0.2 mm). Compared to VG10 glass, 0.5 mm thick titanium-containing compositions 889FMD and 889FMG produce excellent optical performance at path lengths of 3.85 mm or less. In other words, titanium-containing compositions 889FMD and 889FMG outperform VG10 glass despite having shorter path lengths.

The architecture and configuration of methods and products as shown in various illustrative implementations are illustrative only. Although only some specific implementation aspects are described in detail in this disclosure, many modifications (such as changes in size, scale, structure, shape, and proportions of various components, parameter values, installation configurations, use of materials, colors, and directions) may be made. without materially departing from the novel teachings and advantages of the subject matter described herein. Some elements shown as integrally formed may be constructed as multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of separate elements or positions may be altered or varied. The order or order of any processes, logic algorithms, or method steps may be changed or reordered according to alternative implementations. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and configurations of the various exemplary embodiments without departing from the scope of the technology of the present invention.

10‧‧‧Substrate 12‧‧‧Main surface 14‧‧‧Main surface 50‧‧‧Compressive stress zone 52‧‧‧Depth 100‧‧‧Object

The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings of the accompanying drawings illustrate one or more embodiments and, together with the embodiments, serve to explain the principles and operations of the various embodiments. In this way, the present disclosure will be more comprehensively understood from the following embodiments together with the accompanying drawings, in which:

Figure 1 is a cross-sectional view of an object according to at least one example of the present disclosure. The object includes a substrate, and the substrate includes a glass ceramic composition.

Figure 2A is a plot of transmittance versus wavelength comparing CdSe glass and heat-treated glass ceramics in accordance with at least one example of the present disclosure.

Figure 2B is a plot of Figure 2A, resized to show a comparison of the cutoff wavelengths of CdSe glass and heat-treated glass ceramic samples.

Figure 3A is a plot of transmittance versus wavelength comparing CdSe glass and glass ceramic samples heat treated from 525°C to 700°C under various conditions, in accordance with examples of the present disclosure.

Figure 3B is a plot from Figure 3A, resized to show the cutoff wavelengths comparing CdSe glass and glass ceramic samples heat treated under various conditions.

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 under various conditions, in accordance with examples of the present disclosure.

Figure 4B is a plot of Figure 4A, resized to show the cutoff wavelengths comparing CdSe glass and glass ceramic samples heat treated under various conditions.

Figure 4C is a plot of Figure 4A, along with a comparison of transmittance versus wavelength for CuInSe and CuInS glass samples, scaled to show cutoffs for comparison of CdSe glass, glass ceramic samples heat treated under various conditions, and CuInSe and CuInS samples. wavelength.

Figure 5 is an x-ray diffraction ("XRD") pattern of a heat-treated glass ceramic according to at least one example of the present disclosure.

Figures 6A-6C are respective Raman spectra of glass-ceramic samples that were splat-quenched according to examples of the present disclosure and glass-ceramic samples that were heat-treated at 650°C and 700°C according to various conditions.

Figures 7A and 7B are Raman spectra of glass-ceramic samples heat-treated at 650°C and 700°C under various conditions and glass-ceramic samples freshly quenched according to examples of the present disclosure.

Figure 8 is a plot of residual stress versus substrate depth for two glass ceramic samples with compressive stress regions derived from two separate ion exchange process conditions, in accordance with examples of the present disclosure.

Figure 9 is a scanning electron microscope (SEM) micrograph of a glass ceramic according to an exemplary embodiment.

Figures 10A and 10B are respectively SEM and transmission electron microscope (TEM) micrographs of glass ceramics according to another exemplary embodiment.

Figures 11A and 11B are respectively SEM and TEM micrographs of glass ceramics according to yet another exemplary embodiment.

Figures 12A and 12B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from the 0.5 mm polished flat plate composed of 889FLZ in the unannealed state and heat treatment conditions (600°C, 1h).

Figures 13A and 13B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from the 0.5 mm polished flat plate composed of 889FMB in the unannealed state and heat treatment conditions (700°C, 1h).

Figures 14A and 14B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from 0.5 mm polished flat plates composed of 889FMC in the unannealed state and heat treatment conditions (500°C, 1h and 600°C, 1h). ).

Figures 15A and 15B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from 0.5 mm polished flat plates composed of 889FMD in the unannealed state and heat treatment conditions (500°C, 1h and 600°C, 1h). ).

Figures 16A and 16B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from 0.5 mm polished flat plates composed of 889FME in the unannealed state and heat treatment conditions (600°C, 1h and 700°C, 1h). ).

Figures 17A and 17B show the transmittance spectrum and absorbance spectrum (OD/mm) collected from the 0.5 mm polished flat plate composed of 889FMG in the unannealed state and heat treatment conditions (700°C, 1h and 700°C, 2h). ).

Figures 18A-18D are TEM micrographs at different magnifications of titanium-containing crystals in a heat-treated sample composed of 889FMC that was heat-treated at 700°C for one hour.

Figure 19A is a TEM micrograph of titanium-containing crystals in a heat-treated sample composed of 889FMC that was heat-treated at 700°C for one hour.

Figure 19B shows the electron dispersion spectrum (EDS) elemental diagram of titanium in the TEM micrograph of Figure 19A.

Domestic storage information (please note in order of storage institution, date and number) None

Overseas deposit information (please note in order of deposit country, institution, date and number) None

Claims (20)

A glass ceramic, comprising: a silicate-containing glass phase; and a crystalline phase, the crystalline phase comprising titanium suboxides, the titanium suboxides comprising solid defect structures, in which pores are formed by Occupied by dopant cations, wherein the crystalline phase is uniformly distributed within the glass-ceramic such that the titanium suboxides are present from an outer surface of the glass-ceramic throughout an entirety of the glass-ceramic, wherein the glass phase and the crystalline The phase makes the glass-ceramics optically transparent and has strong attenuation of near-infrared rays, which has: in a wavelength band of at least 50nm wide in a wavelength range from 400nm to 700nm, the glass-ceramics have a 1%/mm or For greater transmittance, and at least a 50 nm wide wavelength band of light in a wavelength range from 700 nm to 1700 nm, the glass ceramic has an absorption rate of at least 90%/mm. The glass ceramic as claimed in claim 1, wherein the glass ceramic is substantially free of W, Mo, and rare earth elements. The glass ceramic according to claim 1, wherein the glass ceramic further contains 0.1 mol% or less Fe. The glass ceramic as claimed in claim 1, wherein the titanium suboxides have the general formula M _x TiO ₂ , where 0<x<1 and M is a dopant cation. The glass ceramic as claimed in claim 1, wherein the glass ceramic contains a haze of 10% or less at a thickness of 1 mm. A glass ceramic, comprising: an _amorphous phase; and a crystalline phase, the crystalline phase comprising a plurality of precipitates of the _formula M The precipitates are uniformly distributed in the glass ceramic, so that the precipitates of the formula M _x TiO ₂ exist from an outer surface of the glass ceramic throughout the whole of the glass ceramic, and the crystalline phase and the amorphous phase are The glass-ceramic exhibits a haze of 20% or less, where the haze refers to the percentage of transmitted light that traverses a transmission path of 1 mm of the glass-ceramic and is scattered outside a ±2.5° angle cone. The glass ceramic according to claim 6, wherein the plurality of precipitates comprise a length from 1 nm to 300 nm as measured by an electron microscope. The glass ceramic as claimed in claim 6 or 7, wherein the plurality of precipitates of the crystalline phase are substantially homogeneously distributed within the glass ceramic. The glass ceramic according to claim 6, wherein the dopant cations include 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, At least one of Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce. The glass ceramic as claimed in claim 6, wherein the plurality of crystals comprise a volume fraction of from 0.001% to 15% in the glass ceramic. A glass ceramic, comprising: a silicate-containing glass; and a plurality of crystals homogeneously distributed in the silicate-containing glass, wherein the crystals comprise non-stoichiometric titanium inserted with doped cations Suboxide comprising non-stoichiometric titanium suboxide with intercalated dopant cations present from an outer surface of the glass-ceramic throughout an entirety of the glass-ceramic, and wherein the crystals and the silicate glass are structured The glass ceramic is optically transparent and can absorb ultraviolet rays, and it has: in a wavelength band of light of at least 50 nm wide in a range from 400 nm to 700 nm, the glass ceramic has a 1%/mm or greater A transmittance, and light in a wavelength band of light having a wavelength less than 400 nm that is at least 50 nm wide, the glass ceramic has to Less than 90%/mm absorption rate. The glass ceramic as claimed in claim 11, wherein the dopant cations include 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 one or more of Ce. The glass ceramic as claimed in claim 11, wherein the glass ceramic does not contain β-quartz. The glass ceramic of claim 11, wherein at least a portion of the crystals are located at a depth greater than 10 μm from an outer surface of the glass ceramic. The glass ceramic as claimed in claim 11, wherein the plurality of crystals comprise a volume fraction of from 0.001% to 15% in the glass ceramic. A glass ceramic object, comprising: at least one amorphous phase and one crystalline phase; and from 1 mol% to 95 mol% SiO ₂ ; wherein the crystalline phase includes a non-stoichiometric amount of from 0.1 mol% to 100 mol% of the crystalline phase Titanium suboxide, the oxide contains at least one of the following: (i) Ti, (ii) V and an alkali metal cation. A glass ceramic article as claimed in claim 16, wherein the The crystalline phase is distributed substantially homogeneously within the glass ceramic object as a plurality of precipitates. The glass ceramic object of claim 17, wherein at least some of the precipitates are located at a depth greater than 10 μm from an outer surface of the object. The glass ceramic object of claim 16, wherein the crystalline phase includes a plurality of precipitates, and the plurality of precipitates have a length from 1 nm to 500 nm as measured by an electron microscope. The glass ceramic object as claimed in claim 16, wherein the object is substantially free of Cd and Se.