CN111511696A

CN111511696A - Glass-ceramic and glass

Info

Publication number: CN111511696A
Application number: CN201880083167.5A
Authority: CN
Inventors: M·J·德内卡; J·科尔
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2017-10-23
Filing date: 2018-10-23
Publication date: 2020-08-07
Also published as: EP3700871A4; JP2024010059A; JP2021500299A; JP7429189B2; NL2021858B1; CN113185129A; WO2019083937A3; TW201922660A; TWI811252B; CN113185129B; NL2021858A; KR20200062349A; WO2019083937A2; TW202346229A; EP3700871A2

Abstract

The glass-ceramic comprises: silicate-containing glass and a crystalline phase, wherein the crystalline phase comprises a non-stoichiometric suboxide of tungsten and/or molybdenum (or titanium), forming a 'bronze' type solid state defect structure in which vacancies are occupied by dopant cations.

Description

Glass-ceramic and glass

Cross referencing

This application claims priority from U.S. application No. 62/575,763 filed on day 10, 23, 2017 and is a continuation-in-part application No. 15/840,040 filed on day 13, 12, 2017, the contents of both of which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates generally to articles comprising glass and/or glass-ceramic, and more particularly, to compositions and methods of forming such articles.

Background

Alkali silicate glass-ceramics containing ultraviolet ("UV") and near infrared ("NIR") absorbance are glass-ceramics that exhibit optical properties depending on the wavelength of light impinging on the glass-ceramic. Conventional UV/IR blocking glasses (with low or high visible light transmittance) are formed by: certain cationic species (e.g., Fe2+ to absorb NIR wavelengths, Fe23+ to absorb UV wavelengths, and other dopants (e.g., Co, Ni, and Se) to modify visible light transmittance) are incorporated into the glass network. Generally, these glass-ceramics are produced by: the glass-ceramic is formed by melting the components together to form a glass, followed by in situ formation of submicron precipitates by post-forming heat treatment. These submicron sized precipitates (e.g., tungstate-and molybdate-containing crystals) are absorptive for the optical wavelength band, giving the glass-ceramic its own optical properties. Such conventional glass-ceramics may be produced in transparent form as well as in opalescent form.

It is believed that conventional tungsten-and molybdenum-containing alkali silicate glasses are limited to a particular and narrow compositional range in order to produce glasses and glass-ceramics that are transparent at visible wavelengths. The composition ranges believed are based on the perceived solubility limit of tungsten oxide in the overbased glass. For example, when batching and melting are carried out in a conventional manner, tungsten oxide may react with the alkali metal tungsten oxide in the batch at low temperatures during the initial phase of the melt immediately after being placed in the furnaceA dense alkaline tungstate liquid is formed (e.g., the reaction occurs at about 500 ℃). Due to this high density phase, it separates rapidly at the bottom of the crucible. At significantly higher temperatures (e.g., above about 1000 ℃), the silicate component begins to melt and, due to the lower density of the silicate component, it remains on top of the alkaline tungstate liquid. The difference in density of the components results in the layering of the different liquids, which makes them immiscible with each other as will be appreciated by those skilled in the art. Especially when R is₂O (e.g., L i)₂O、Na₂O、K₂O、Rb₂O、Cs₂O) minus Al₂O₃This effect is observed at about 0 mole% or greater. The apparent liquid immiscibility obtained at the melting temperature results in a phase separation of the tungsten rich phase and crystallization as it cools, which manifests itself as opalescent opaque crystals. This problem also exists with molybdenum-containing melts.

The skilled person observes that the tungsten-rich phase and/or the molybdenum-rich phase separates from the silicate-rich phase, they consider the solubility limit (e.g. about 2.5 mole%) of tungsten and/or molybdenum in the silicate-rich phase. The solubility limit is believed to prevent the glass from becoming supersaturated with tungsten or molybdenum oxides, thereby preventing the creation of glass-ceramics with crystalline phases containing these elements by way of shaped controlled-precipitation components after heat treatment. Thus, the solubility believed has hindered the development of glass-ceramic compositions that achieve sufficient amounts of soluble tungsten and/or molybdenum to achieve the formation of wavelength-dependent submicron crystals containing tungsten and/or molybdenum by subsequent thermal treatment.

In view of these limitations, new compositions and methods are needed such that they help improve near infrared and ultraviolet blocking (e.g., by higher tungsten and molybdenum solubility).

Disclosure of Invention

It has been found that a homogeneous single phase W-or Mo-containing overbased melt can be obtained by using a "bound" alkaline material as described herein. Exemplary bound alkaline agents may include: feldspar, nepheline, borax, spodumene, theirTanathlenite or potash feldspar, alkali-containing aluminosilicates and/or other naturally occurring or man-made alkali-containing materials, and one or more aluminum and/or silicon atom-containing minerals. By introducing the alkaline species in a bound form, the alkaline species may not react with W or Mo present in the melt to form a dense alkaline tungstate and/or alkaline molybdate liquid. In addition, such batch variations can achieve strongly overbased compositions (e.g., R)₂O-Al₂O₃About 2.0 mole percent or greater) without forming any alkaline tungstate and/or alkaline molybdate second phases. This also enables the melting temperature and mixing method to be varied and still produce a single phase homogeneous glass.

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

In some embodiments, the glass-ceramic comprises an amorphous phase and a crystalline phase comprising a compound of formula M_xWO₃And/or M_xMoO₃A plurality of precipitates of (A) wherein 0<x<1 and M are dopant cations. In some such embodiments, the length of the precipitate is from about 1nm to about 200nm, as measured by electron microscopy. The precipitates of the crystalline phase may be substantially uniformly distributed in the glass-ceramic.

In addition, the glass-ceramic may include an amorphous phase and a crystalline phase comprising a chemical formula of M_xTiO₂A plurality of precipitates of (A) wherein 0<x<1 and M are dopant cations. In some embodiments, the length of the precipitate is from about 1nm to about 200nm or from 1nm to about 300nm or from 1nm to about 500nm as measured by electron microscopy. The precipitates of the crystalline phase may be substantially uniformly distributed in the glass-ceramic.

In some embodiments, the glass-ceramic comprises a silicate-containing glass and crystals of non-stoichiometric tungsten and/or molybdenum suboxides inserted with dopant cations uniformly distributed In the silicate-containing glass over at least one 50nm wide wavelength band In the range of about 400nm to about 700nm, the glass-ceramic may have a transmission of about 5% or greater per mm.

In some embodiments, the glass-ceramic comprises a silicate-containing glass phase and a crystalline phase comprising a suboxide of tungsten and/or molybdenum forming a solid state defect structure in which holes are occupied by dopant cations. The volume fraction of crystalline phases in the glass-ceramic may be about 0.001% to about 20%.

In other embodiments, the glass-ceramic, the silicate-containing glass, and the crystals of non-stoichiometric titanium suboxide intercalated with dopant cations uniformly distributed in the silicate-containing glass; and/or a silicate-containing glass phase and a crystalline phase comprising a titanium suboxide forming a solid state defect structure in which holes are occupied by dopant cations.

In some embodiments, an article comprising at least one amorphous phase and one crystalline phase comprises from about 1 mol% to about 95 mol% SiO₂As a batch component. The crystalline phase includes an oxide of at least one of (about 0.1 mol% to about 100 mol% of the crystalline phase): (i) w, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation. The article may be substantially free of Cd and Se.

In other embodiments, the glass (e.g., a glass precursor of a glass-ceramic) comprises the following batch components: SiO 2₂About 25 mol% to about 99 mol%, Al₂O₃About 0 mol% to about 50 mol%, WO₃Adding MoO₃About 0.35 mol% to about 30 mol%, R₂O from about 0.1 mol% to about 50 mol%, wherein,R₂o is L i₂O、Na₂O、K₂O、Rb₂O and Cs₂One or more of O, and wherein R₂O minus Al₂O₃Is about-35 mol% to about 7 mol%. In some such embodiments, there is at least one of: (i) RO in the range of about 0.02 mol% to about 50 mol%, and (ii) SnO₂Is about 0.01 mol% to about 5 mol%, wherein RO is one or more of MgO, CaO, SrO, BaO, and ZnO. In some such embodiments, if WO₃From about 1 mol% to about 30 mol%, the glass further comprises about 0.9 mol% or less Fe₂O₃Or SiO₂Then from about 60 mole% to about 99 mole%. If WO₃From about 0.35 mol% to about 1 mol%, the glass may comprise from about 0.01 mol% to about 5.0 mol% SnO₂. If MoO₃About 1 mol% to about 30 mol%, SiO₂May range from about 61 mol% to about 99 mol%, or Fe₂O₃May be about 0.4 mole% or less and R₂O is greater than RO. If MoO₃Is about 0.9 mol% to about 30% and SiO₂Is from about 30 mole% to about 99 mole%, the glass may further comprise from about 0.01 mole% to about 5 mole% SnO₂。

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

In other embodiments, a method of forming a glass-ceramic comprises the steps of: melting silicon oxide together with tungsten and/or molybdenum to form a glass melt; solidifying the glass melt to form glass; and precipitating bronze type crystals comprising tungsten and/or molybdenum in the glass. Precipitation of the crystalline phase may include thermal processing of the glass. In at least some such embodiments, the method further comprises the step of growing the precipitate of crystalline phases to a length of at least about 1nm and no more than about 500 nm.

In other embodiments, the glass-ceramic comprises a silicate-containing glass phase; and a crystalline phase comprising a titanium suboxide including a solid state defect structure in which holes are occupied by dopant cations.

In other embodiments, the glass-ceramic comprises an amorphous phase; and a crystalline phase comprising a compound of formula M_xTiO₂A plurality of precipitates of (A) wherein 0<x<1 and M are dopant cations.

In other embodiments, the glass-ceramic comprises a silicate-containing glass; and a plurality of crystals uniformly distributed in the silicate-containing glass, wherein the crystals comprise a non-stoichiometric suboxide of titanium, and wherein the crystals are intercalated with dopant cations.

In other embodiments, the glass-ceramic article includes at least one amorphous phase and a crystalline phase; and about 1 mol% to about 95 mol% SiO₂(ii) a Wherein the crystalline phase comprises from about 0.1 mol% to about 100 mol% of a non-stoichiometric titanium suboxide of the crystalline phase, the oxide comprising at least one of: (i) ti, (ii) V and an alkali metal cation.

In other embodiments, a method of forming a glass-ceramic comprises: melting components comprising silica and titanium together to form a glass melt; solidifying the glass melt to form a glass, wherein the glass comprises a first average near-infrared 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 a ratio of the second average near infrared absorbance to the first average near infrared absorbance is about 1.5 or greater, and (b) an average optical density per mm of about 1.69 or less.

In other embodiments, the glass comprises, in the batch components: SiO 2₂About 1 molar% to about 90 molar%; al (Al)₂O₃About 0 molar% to about 30 molar%; TiO 2₂About 0.25 molar% to about 30 molar%; metal sulfide from about 0.25 molar% to about 30 molar%; r₂O from about 0 mol% to about 50 mol%, wherein R₂O is L i₂O、Na₂O、K₂O、Rb₂O and Cs₂One or more of O; and RO in a range from about 0 mol% to about 50 mol%, wherein RO is one or more of BeO, MgO, CaO, SrO, BaO, and ZnO, and wherein the glass is substantially free of Cd.

These and other features, advantages, and objects of the present disclosure will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings.

Drawings

The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the detailed description, serve to explain the principles and operations of the various embodiments. The disclosure, therefore, is best understood from the following detailed description when read in connection with the accompanying drawings, wherein:

fig. 1 is a cross-sectional view of an article including a substrate including a glass-ceramic composition according to at least one example of the present disclosure.

FIG. 2A is a graph of transmittance versus wavelength for a comparative CdSe glass and a heat-treated glass-ceramic according to at least one example of the present disclosure.

FIG. 2B is the image of FIG. 2A, rescaled to show the cut-off wavelengths of the comparative CdSe glass and heat-treated glass-ceramic samples.

FIG. 3A is a graph of transmittance versus wavelength for comparative example CdSe glasses and glass-ceramic samples heat treated according to various conditions from 525 ℃ to 700 ℃ according to examples of the present disclosure.

FIG. 3B is the image of FIG. 3A, rescaled to show the cut-off wavelengths of comparative example CdSe glasses and glass-ceramic samples heat treated according to various conditions.

FIG. 4A is a graph of transmittance versus wavelength for comparative example CdSe glasses and glass-ceramic samples heat treated at 700 deg.C and 800 deg.C according to various conditions in accordance with examples of the present disclosure.

FIG. 4B is the image of FIG. 4A, rescaled to show the cut-off wavelengths of comparative example CdSe glasses and glass-ceramic samples heat treated according to various conditions.

Fig. 4C is a graph of transmittance versus wavelength for the image in fig. 4A and comparative example CuInSe and CuInS glass samples, scaled to show the cutoff wavelengths for comparative example CdSe glass, glass ceramic samples heat treated according to various conditions, and CuInSe and CuInS samples.

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

Fig. 6A-6C are representative raman spectra of glass-ceramic samples heat treated at 650 ℃ and 700 ℃ according to various conditions and spray-quenched (splat-quenched) glass-ceramic samples according to examples of the present disclosure.

Fig. 7A &7B are raman spectra of glass-ceramic samples heat treated at 650 ℃ and 700 ℃ and spray-quenched (splat-quenched) according to various conditions, according to examples of the present disclosure.

FIG. 8 is a graph of residual stress versus substrate depth for two glass-ceramic samples having compressive stress regions derived from two representative ion-exchange processing conditions, in accordance with an example of the present disclosure.

Fig. 9 is a Scanning Electron Microscope (SEM) micrograph of a glass-ceramic according to an example embodiment.

Fig. 10A and 10B are microscope images of an SEM and a Transmission Electron Microscope (TEM), respectively, of a glass-ceramic according to another exemplary embodiment.

Fig. 11A and 11B are SEM and TEM micrographs, respectively, of a glass-ceramic according to another exemplary embodiment.

FIGS. 12A and 12B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889F L Z in the as-manufactured, unannealed state and in the heat-treated state (600 ℃ for 1 h).

FIGS. 13A and 13B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889FMB in as-manufactured, unannealed state and heat treated state (700 deg.C. for 1 h).

FIGS. 14A and 14B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889FMC in as-manufactured, unannealed state and heat treated state (500

deg.C

1h and 600 deg.C 1 h).

FIGS. 15A and 15B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889FMD in as-manufactured, unannealed state and heat treated state (500

deg.C

1h and 600 deg.C 1 h).

FIGS. 16A and 16B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889FME in as-manufactured, unannealed state and heat treated state (600 deg.C 1h and 700 deg.C 1 h).

FIGS. 17A and 17B are the transmission and absorption spectra of OD/mm collected 0.5mm polished plates of composition 889FMG in as-manufactured, unannealed state and heat treated state (700 deg.C. for 1h and 700 deg.C. for 2 h).

Figures 18A-18D are TEM micrographs at 4 different magnifications of titanium-containing crystals within a sample of heat treated composition 889FMC heat treated at 700 ℃ for 1 hour.

Figure 19A is a TEM micrograph of titanium-containing crystals within a sample of heat treated composition 889FMC heat treated at 700 ℃ for 1 hour.

FIG. 19B is an Electron Dispersive Spectroscopy (EDS) elemental view of titanium of the TEM micrograph of FIG. 19A.

Detailed Description

Before turning to the following detailed description and accompanying drawings, which set forth exemplary embodiments in detail, it is to be understood that the inventive technique is not limited to the details or methodology specifically described or illustrated in the drawings. For example, those skilled in the art will appreciate that features and attributes associated with one of the embodiments illustrated in the drawings or described in text relating to one of the embodiments may well apply to other embodiments illustrated in other drawings or described in other text.

As used herein, the term "and/or," when used in reference to two or more items, means that any one of the listed items can be taken alone, or any combination of two or more of the listed items can be taken. For example, if the composition is described as containing components A, B and/or C, the composition may contain a alone; only contains B; only contains C; a combination comprising A and B; a combination comprising A and C; a combination comprising B and C; or a combination comprising A, B and C.

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

Modifications of the disclosure will occur to those skilled in the art and to those who make and use the disclosure. Therefore, it is to be understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and are not intended to limit the scope of the disclosure, which is defined by the appended claims, as interpreted according to the principles of patent law, including the doctrine of equivalents.

Those skilled in the art will appreciate that the construction of the disclosure and other components is not limited to any particular materials. Other exemplary embodiments of the present disclosure disclosed herein may be formed from a wide variety of materials unless otherwise stated herein.

For the purposes of this disclosure, the term "coupled" (in all forms: connected, and the like) generally means that two components are joined (electrically or mechanically) to each other either directly or indirectly. Such engagement may naturally be static or may naturally be movable. Such joining may be achieved through the two components and any additional intermediate elements (electrically or mechanically) that are integrally formed as a single unitary piece with each other or with the two components. Such engagement may naturally be permanent, or may naturally be removable or disengagable, unless otherwise stated.

As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other variables and characteristics are not and need not be exact, but may be approximate and/or larger or smaller as desired, reflecting tolerances, conversion factors, rounding off and measurement errors and the like, and other factors known to those of skill in the art. When the term "about" is used to describe a value or an endpoint of a range, it is to be understood that the disclosure includes the particular value or endpoint referenced. Whether or not the numerical values or range endpoints of the specification recite "about," the numerical values or range endpoints are intended to include two embodiments: one modified with "about" and one not. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

As used herein, the terms "substantially", "essentially" and variations thereof are intended to mean that the features described are equal or approximately the same as the numerical values or descriptions. For example, a "substantially planar" surface is intended to mean a planar or near-planar surface. Further, "substantially" is intended to mean that the two values are equal or approximately equal. In some embodiments, "substantially" may mean values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

Directional terminology used herein, such as upper, lower, left, right, front, rear, top, bottom, is for reference only to the accompanying drawings and is not intended to be absolute.

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

Unless otherwise indicated, all compositions are expressed as mole percent (mol%) of the furnish. One skilled in the art will appreciate that various melt components (e.g., fluorine, alkali metals, boron, etc.) may be subject to different levels of volatilization (e.g., as a function of vapor pressure, melting time, and/or melting temperature) during melting of the components. Thus, the term "about" in relation to such components is intended to include values within about 0.2 mole% as compared to the composition of the as-dosed materials provided herein when measured on the final article. In view of the above, substantial compositional equivalence between the final product and the batch composition is expected.

For the purposes of this disclosure, the terms "body," "bulk composition," and/or "bulk composition" are intended to include the bulk composition of the entire article, which may differ from the "local composition" or "localized composition," which may differ from the bulk composition by the formation of crystalline and/or ceramic phases.

Further, as used herein, the terms "article," "glass article," "ceramic article," "glass-ceramic," "glass element," "glass-ceramic article," and "glass-ceramic article" are used interchangeably and in their broadest scope include any object made, in whole or in part, from glass and/or glass-ceramic materials.

As used herein, "glassy state" refers to the inorganic amorphous phase material in the articles of the present disclosure, which is a fused product that cools to a rigid state without crystallization. As used herein, "glass-ceramic state" refers to the inorganic material in the articles of the present disclosure, which includes both the glass state as well as the "crystalline phase" and/or "crystalline precipitates" as described herein.

Coefficient of Thermal Expansion (CTE) has the unit of 10^-7And/c, represents values measured over a temperature range of about 0 ℃ to about 300 ℃, unless otherwise specified.

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

As used herein, in the present disclosureWhere "optical density units", "OD" and "OD units" are used interchangeably to refer to optical density units, this is generally understood to mean the measurement of the absorbance of a test material, measured with a spectrometer, to give an OD ═ log (I/I0), where I is₀Is the intensity of light incident on the sample, and I is the intensity of light transmitted through the sample. Further, as used in this disclosure, the term "OD/mm" or "OD/cm" is a normalized absorbance measurement determined by dividing the optical density units (i.e., as measured by an optical spectrometer) by the thickness of the sample (e.g., in millimeters or centimeters). Furthermore, any unit of optical density referred to over a particular wavelength range (e.g., 3.3 to 24.0OD/mm in UV wavelengths of 280 to 380 nm) is given as the average of the units of optical density over that particular wavelength range.

As used herein, the term "haze" means the percentage of transmitted light that is scattered outside a cone of about ± 2.5 ° measured in a sample having a transmission path of about 1mm according to ASTM method D1003.

Further, as used herein, the term "glass or glass-ceramic free of [ component ]" (e.g., cadmium-free and selenium-free glass-ceramic) means that the glass or glass-ceramic is completely free or substantially free (i.e., <500ppm) of the listed component(s), and that it is prepared without active, deliberate, or deliberate addition or compounding of the listed component(s) in the glass or glass-ceramic.

When referring to glass-ceramic and glass-ceramic materials and articles of the present disclosure, compressive stress and depth of compression ("DOC") are measured by using commercially available instruments, such as the scattering light polarizer SCA L P220 and the accompanying software version 5 manufactured by glass stress Limited (GlassStress, &lTtTtranslation = L "&gTtL &lTt/T &gTttd) or the FSM-6000 manufactured by Tokyo (Tokyo, Japan) Fangyuan Limited (Orihara Co., L t.), unless otherwise stated, both instruments measure optical retardation, which must be converted to stress by the stress optical coefficient (" SOC ") of the material being measuredA modified version of scheme C described in (1) (modified scheme C) to measure SOC, entitled "Standard Method for measuring Glass Stress-Optical Coefficient", the entire disclosure of which is incorporated herein by reference. Modification C included the use of glass or glass ceramic disks as test specimens, 5 to 10mm in thickness and 12.7mm in diameter. The disks are isotropic and uniform and, through the core, are polished and parallel on both sides. The improvement C further comprises calculating a maximum force F to be applied to the dish_{Maximum value}. The force should be sufficient to produce a compressive stress of at least 20 MPa. F is calculated using the following equation_{Maximum value}：

F_{Maximum value}＝7.854*D*h

In the formula, F_{Maximum value}Is the maximum force (N), D is the diameter of the disk (mm), and h is the thickness of the optical path (mm). For each force application, the stress was 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).

Further, as used herein, the terms "sharp cutoff wavelength" and "cutoff wavelength" are used interchangeably and refer to a cutoff wavelength in the range of about 350nm to 800nm, wherein above the cutoff wavelength (λ c) the glass-ceramic has a significantly higher transmittance than below the cutoff wavelength (λ c). The cutoff wavelength (λ c) is the wavelength at the midpoint between the "absorption limit wavelength" and the "high transmission limit wavelength" in a given spectrum of the glass-ceramic. The "absorption edge wavelength" is defined as a wavelength at which the transmittance is 5%; and in "high transmittance wavelength", defined as a wavelength having a transmittance of 72%. It will be understood that "sharp UV cut-off" as used herein may be the sharp cut-off wavelength of the cut-off wavelength described above that occurs in the ultraviolet band of the electromagnetic spectrum.

Articles of the present disclosure include glasses and/or glass-ceramics having one or more of the compositions listed herein. The article may be used in any number of applications. For example, the article may be used in the form of a substrate, element, lens, covering, and/or other element in any number of optically-relevant and/or aesthetic applications.

The article is formed from the batch composition and cast in a glassy state. The article may then be annealed and/or thermally processed (e.g., 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 readily crystallize and become glass-ceramic (e.g., cast substantially in the glass-ceramic state) without additional heat treatment. In instances where post-forming thermal processing is employed, a portion of the article, a majority of the article, substantially all of the article, or all of the article may be converted from a glassy state to a glassy ceramic state. Thus, while the composition of the article may be described in connection with the glassy state and/or the glassy ceramic state, the bulk composition of the article may remain substantially unchanged when transitioning between the glassy state and the glassy ceramic state, despite local portions of the article having different compositions (i.e., due to the formation of ceramic or crystalline precipitates).

According to various examples, an article may comprise: al (Al)₂O₃；SiO₂；B₂O₃；WO₃；MO₃；R₂O, wherein R₂O is L i₂O、Na₂O、K₂O、Rb₂O and Cs₂One or more of O, RO, wherein RO is one or more of MgO, CaO, SrO, BaO, and ZnO, and a plurality of dopants it will be appreciated that a variety of other components (e.g., F, As, Sb, Ti, P, Ce, Eu, L a, Cl, Br, etc.) do not depart from the teachings provided herein.

According to example 1, an article may comprise: SiO 2₂About 58.8 mol% to about 77.58 mol%, Al₂O₃About 0.66 mol% to about 13.69 mol%, B₂O₃About 4.42 mol% to about 27 mol%, R₂O from about 0 mol% to about 13.84 mol%, RO from about 0 mol% to about 0.98 mol%, WO₃About 1.0 mol% to about 13.24 mol%, and SnO₂From about 0 mol% to about 0.4 mol%. Such examples of articles may generally relate to embodiments 1-109 of table 1.

According to example 2, an article may comprise: SiO 2₂About 65.43 mol% to about 66.7 mol%, Al₂O₃About 9.6 mol% to about 9.98 mol%, B₂O₃About 9.41 mol% to about 10.56 mol%, R₂O from about 6.47 mol% to about 9.51 mol%, RO from about 0.96 mol% to about 3.85 mol%, WO₃About 1.92 mol% to about 3.85 mol%, MoO₃About 0 mol% to about 1.92 mol%, and SnO₂From about 0 mol% to about 0.1 mol%. Such examples of articles may generally relate to embodiments 110-122 of table 2.

According to example 3, an article may comprise: SiO 2₂About 60.15 mol% to about 67.29 mol%, Al₂O₃About 9.0 mol% to about 13.96 mol%, B₂O₃About 4.69 mol% to about 20 mol%, R₂O from about 2.99 mol% to about 12.15 mol%, RO from about 0.00 mol% to about 0.14 mol%, WO₃About 0 mol% to about 7.03 mol%, MoO₃About 0 mol% to about 8.18 mol%, SnO₂About 0.05 mol% to about 0.15 mol%, and V₂O₅From about 0 mol% to about 0.34 mol%. Such examples of articles may generally relate to embodiment 123-157 of table 3.

According to example 4, an article may comprise: SiO 2₂About 54.01 mol% to about 67.66 mol%, Al₂O₃About 9.55 mol% to about 11.42 mol%, B₂O₃About 9.36 mol% to about 15.34 mol%, R₂O from about 9.79 mol% to about 13.72 mol%, RO from about 0.00 mol% to about 0.22 mol%, WO₃About 1.74 mol% to about 4.48 mol%, MoO₃About 0 mol% to about 1.91 mol%, SnO₂About 0.0 mol% to about 0.21 mol%, V₂O₅About 0 mol% to about 0.03 mol%, Ag about 0 mol% to about 0.48 mol%, and Au about 0 mol% to about 0.01 mol%. Such examples of articles may generally relate to embodiments 158-311 of table 4.

According to example 5, an article may comprise: SiO 2₂About 60.01 mol% to about 77.94 mol%, Al₂O₃About 0.3 mol% to about 10.00 mol%, B₂O₃About 10 mol% to about 20 mol%, R₂O from about 0.66 mol% to about 10 mol%, WO₃About 1.0 mol% to about 6.6 mol%, and SnO₂From about 0.0 mol% to about 0.1 mol%. Such examples of articles may generally relate to embodiment 312 of table 5 and 328.

The article may have: about 1 mol% to about 99 mol% SiO₂Alternatively from about 1 mol% to about 95 mol% SiO₂Alternatively from about 45 mol% to about 80 mol% SiO₂Alternatively from about 60 mol% to about 99 mol% SiO₂Alternatively from about 61 mol% to about 99 mol% SiO₂Alternatively from about 30 mol% to about 99 mol% SiO₂Alternatively from about 58 mol% to about 78 mol% SiO₂Alternatively from about 55 mol% to about 75 mol% SiO₂Alternatively from about 50 mol% to about 75 mol% SiO₂Alternatively from about 54 mol% to about 68 mol% SiO₂Alternatively from about 60 mol% to about 78 mol% SiO₂Alternatively from about 65 mol% to about 67 mol% SiO₂Alternatively from about 60 mol% to about 68 mol% SiO₂Alternatively from about 56 mol% to about 72 mol% SiO₂Alternatively from about 60 mol% to about 70 mol% SiO₂. It will be appreciated that the SiO noted above is considered₂Any and all values and ranges between ranges. SiO 2₂May act as the primary glass-forming oxide and affect the stability, resistance to devitrification, and/or viscosity of the article.

The article may comprise: about 0 mol% to about 50 mol% Al₂O₃Alternatively from about 0.5 ml% to about 20 mol% Al₂O₃Alternatively from about 0.5 mol% to about 15 mol% Al₂O₃Alternatively from about 7 mol% to about 15 mol% Al₂O₃Alternatively from about 0.6 mol% to about 17 mol% Al₂O₃Alternatively from about 0.6 mol% to about 14 mol% Al₂O₃Alternatively from about 7 mol% to about 14 mol% Al₂O₃Alternatively from about 9.5 mol% to about 10 mol% Al₂O₃Alternatively from about 9 mol% to about 14 mol% Al₂O₃About 9.5 mol% to about 11.5 mol% Al₂O₃Alternatively from about 0.3 mol% to about 10 mol% Al₂O₃Alternatively from about 0.3 mol% to about 15 mol% Al₂O₃Alternatively from about 2 mol% to about 16 mol% Al₂O₃Alternatively from about 5 mol% to about 12 mol% Al₂O₃Alternatively from about 8 mol% to about 12 mol% Al₂O₃Alternatively from about 5 mol% to about 10 mol% Al₂O₃. It will be appreciated that the above noted Al is taken into account₂O₃Any and all values and ranges between ranges. Al (Al)₂O₃Can be used as a tunable network former and contribute to stable articles with low CTE, article rigidity, and facilitate melting and/or shaping.

The article may comprise WO₃And/or MoO₃. For example, WO₃Adding MoO₃And may be about 0.35 mole% to about 30 mole%. MoO₃May be about 0 mol% and WO₃Is about 1.0 mol% to about 20 mol%, or MoO₃May be about 0 mol% and WO₃Is about 1.0 mol% to about 14 mol%, or MoO₃Is about 0 mol% to about 8.2 mol% and WO₃Is about 0 mol% to about 16 mol%, or MoO₃Is about 0 mol% to about 8.2 mol% and WO₃Is about 0 mol% to about 9 mol%, or MoO₃Is about 1.9 mol% to about 12.1 mol% and WO₃Is about 1.7 mol% to about 12 mol%, or MoO₃Is about 0 mol% to about 8.2 mol% and WO₃Is about 0 mol% to about 7.1 mol%, or MoO₃Is about 1.9 mol% to about 12.1 mol% and WO₃Is about 1.7 mol% to about 4.5 mol%, or MoO₃Is about 0 mol% and WO₃Is about 1.0 mol% to about 7.0 mol%. For MoO₃The glass composition may have: about 0.35 mol% to about 30 mol% MoO₃Alternatively from about 1 mol% to about30 mol% MoO₃Alternatively from about 0.9 mol% to about 30% MoO₃Alternatively from about 0.9 mol% to about 20% MoO₃Alternatively from about 0 mol% to about 1.0 mol% MoO₃Alternatively from about 0 mol% to about 0.2 mol% MoO₃. For WO₃The glass composition may have: about 0.35 mol% to about 30 mol% WO₃Alternatively from about 1 mol% to about 30 mol% WO₃Alternatively from about 1 mol% to about 17 mol% WO₃Alternatively from about 1.9 mol% to about 10 mol% WO₃Alternatively from about 0.35 mol% to about 1 mol% WO₃Alternatively from about 1.9 mol% to about 3.9 mol% WO₃Alternatively from about 2 mol% to about 15 mol% WO₃Alternatively from about 4 mol% to about 10 mol% of WO₃Alternatively from about 5 mol% to about 7 mol% WO₃. It will be appreciated that the above noted WO is considered₃And/or MoO₃Any and all values and ranges between ranges.

The article may comprise: about 2 mol% to about 40 mol% B₂O₃Alternatively from about 4 mol% to about 40 mol% B₂O₃Alternatively from about 4.0 mol% to about 35 mol% B₂O₃Alternatively from about 4.0 mol% to about 27 mol% B₂O₃Alternatively from about 5.0 mol% to about 25 mol% B₂O₃Alternatively from about 9.4 mol% to about 10.6 mol% B₂O₃Alternatively from about 5 mol% to about 20 mol% B₂O₃Alternatively from about 4.6 mol% to about 20 mol% B₂O₃Alternatively from about 9.3 mol% to about 15.5 mol% B₂O₃Alternatively from about 10 mol% to about 20 mol% B₂O₃Alternatively from about 10 mol% to about 25 mol% B₂O₃. It will be appreciated that the above noted B is taken into account₂O₃Any and all values and ranges between ranges. B is₂O₃May be a glass-forming oxide that serves to reduce CTE, density and viscosity, making the article easier to melt and form at low temperatures.

The article may comprise at least one alkali metal oxide. Alkali goldThe metal oxide can be represented by the formula R₂O represents, wherein R is₂O is L i₂O、Na₂O、K₂O、Rb₂O、Cs₂One or more of O, and/or combinations thereof. The article may have the following alkali metal oxide composition: about 0.1 mol% to about 50 mol% R₂O, or from about 0 mol% to about 14 mol% R₂O, or from about 3 mol% to about 14 mol% R₂O, or from about 5 mol% to about 14 mol% R₂O, or from about 6.4 mol% to about 9.6 mol% R₂O, or from about 2.9 mol% to about 12.2 mol% R₂O, or from about 9.7 mol% to about 12.8 mol% R₂O, or from about 0.6 mol% to about 10 mol% R₂O, or from about 0 mol% to about 15 mol% R₂O, or from about 3 mol% to about 12 mol% R₂O, or from about 7 mol% to about 10 mol% R₂And O. It will be appreciated that the above noted R is taken into account₂Any and all values and ranges between the O ranges basic oxides (e.g., L i) may be incorporated in the article for a variety of reasons₂O、Na₂O、K₂O、Rb₂O and Cs₂O), including (i) lowering the melting temperature, (ii) increasing the formability, (iii) allowing chemical strengthening by ion exchange, and/or (iv) as a substance that partitions certain crystallites.

According to various examples, R₂O minus Al₂O₃The ranges of (A) are: from about-35 mol% to about 7 mol%, alternatively from about-12 mol% to about 2.5 mol%, alternatively from about-6 mol% to about 0.25%, alternatively from about-3.0 mol% to about 0 mol%. It will be appreciated that the above noted R is taken into account₂O minus Al₂O₃Any and all values and ranges between the ranges of (a).

The article may comprise at least one alkaline earth metal oxide. The alkaline earth metal oxide may be represented by the formula RO, wherein RO is one or more of MgO, CaO, SrO, BaO and ZnO. The product may comprise RO as follows: about 0.02 mol% to about 50 mol% RO, alternatively about 0.01 mol% to about 5 mol% RO, alternatively about 0.02 mol% to about 5 mol% RO, alternatively about0.05 mol% to about 10 mol% RO, alternatively about 0.10 mol% to about 5 mol% RO, alternatively about 0.15 mol% to about 5 mol% RO, alternatively about 0.05 mol% to about 1 mol% RO, alternatively about 0.5 mol% to about 4.5 mol% RO, alternatively about 0 mol% to about 1 mol% RO, alternatively about 0.96 mol% to about 3.9 mol% RO, alternatively about 0.2 mol% to about 2 mol% RO, alternatively about 0.01 mol% to about 0.5 mol% RO, alternatively about 0.02 mol% to about 0.22 mol% RO. It will be understood that any and all values and ranges between the above noted RO ranges are contemplated. According to various examples, R₂O may be greater than RO. In addition, the article may be RO free. Alkaline earth oxides (e.g., MgO, CaO, SrO, and BaO) and other divalent oxides (e.g., ZnO) may improve the melting behavior of the article, and may also function to increase the CTE, young's modulus, and shear modulus of the article.

The article may comprise: about 0.01 mol% to about 5 mol% SnO₂Alternatively from about 0.01 mol% to about 0.5 mol% SnO₂Alternatively from about 0.05 mol% to about 0.5 mol% SnO₂Alternatively from about 0.05 mol% to about 2 mol% SnO₂Alternatively from about 0.04 mol% to about 0.4 mol% SnO₂Alternatively from about 0.01 mol% to about 0.4 mol% SnO₂Alternatively from about 0.04 mol% to about 0.16 mol% SnO₂Alternatively from about 0.01 mol% to about 0.21 mol% SnO₂Alternatively from about 0 mol% to about 0.2 mol% SnO₂Alternatively from about 0 mol% to about 0.1 mol% SnO₂. It will be appreciated that the above noted SnO is contemplated₂Any and all values and ranges between ranges. The article may also contain a low concentration of SnO₂As a fining agent (e.g., other fining agents may include CeO)₂、As₂O₃、Sb₂O₅、Cl^-Or F^-Etc.) to help eliminate gaseous inclusions during the melting process. Certain clarifying agents may also function as redox couples, color centers and or nucleating or intercalating species in crystallites formed in the article.

The composition of certain components of the article may depend on the presence of other componentsAnd/or composition. For example, if WO₃From about 1 mol% to about 30 mol%, the article further comprises about 0.9 mol% or less Fe₂O₃Or SiO₂Is about 60 mole% to about 99 mole%. In another example, if WO₃From about 0.35 mol% to about 1 mol%, the article comprises from about 0.01 mol% to about 5.0 mol% SnO₂. In another example, if MoO₃About 1 mol% to about 30 mol%, SiO₂Is about 61 mol% to about 99 mol%, or Fe₂O₃Is about 0.4 mol% or less and R₂O is greater than RO. In another example, if MoO₃Is about 0.9 mol% to about 30% and SiO₂Is from about 30 mole% to about 99 mole%, the article comprises from about 0.01 mole% to about 5 mole% SnO₂。

The article may be substantially cadmium free and substantially selenium free. According to various examples, the article may further comprise at least one dopant selected from the group consisting of: ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, Se, Ta, Bi, Ag, Ce, Pr, Nd and Er for regulating the UV, visible, color and/or near-infrared absorption rate. The dopant concentration in the article can be from about 0.0001 mole% to about 1.0 mole%. For example, the article may include at least one of: ag is about 0.01 mol% to about 0.48 mol%, Au is about 0.01 mol% to about 0.13 mol%, V₂O₅Is about 0.01 mol% to about 0.03 mol%, Fe₂O₃Is about 0 mol% to about 0.2 mol%, Fe₂O₃Is about 0 mol% to about 0.2 mol%, and CuO is about 0.01 mol% to about 0.48 mol%. According to another example, the article may comprise at least one of: ag is about 0.01 mol% to about 0.75 mol%, Au is about 0.01 mol% to about 0.5 mol%, V₂O₅Is about 0.01 mol% to about 0.03 mol%, and CuO is about 0.01 mol% to about 0.75 mol%. The article may contain from about 0 mol% to about 5 mol% fluorine to soften the glass. The article may contain from about 0 mol% to about 5 mol% phosphorus to further adjust the physical properties of the article and to adjust the crystalsAnd (5) growing. The article may comprise Ga₂O₃、In₂O₃And/or GeO₂To further adjust the physical and optical properties (e.g., refractive index) of the article, trace amounts of impurities from about 0.001 to about 0.5 mole% may be present to further adjust the absorbance and/or make the article fluorescent of 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 L u, and further, small amounts of P may be added to certain compositions₂O₅To further adjust the physical properties and viscosity of the product.

It will be understood that SiO is recorded above₂、Al₂O3、WO₃、MoO₃、WO₃Adding MoO₃、B₂O₃、R₂O、RO、V₂O₅、Ag、Au、CuO、SnO₂And each composition and compositional range of dopants may be used for any other composition and/or compositional range of other components of the articles listed herein.

As explained above, conventional forming of tungsten-containing, molybdenum-containing, or mixed tungsten-molybdenum-containing alkali glasses is hindered by separation of melt components during the melting process. Separation of the glass components during the melting process results in a perceived solubility limit for the alkali tungstate salts in the molten glass and for articles cast from such melts. Generally, when the tungsten melt, molybdenum melt or mixed tungsten-molybdenum melt is even slightly overbased (e.g., R₂O-Al₂O₃About 0.25 mole percent or greater), the molten borosilicate glass simultaneously forms a glass and a dense liquid second phase. While the concentration of the alkaline tungstate secondary phase may be reduced by thorough mixing, high temperature melting, and using small batch sizes (about 1000g), the formation of deleterious secondary crystalline phases is not completely eliminated. It is believed that the formation of such an alkaline tungstate phase occurs during the initial stages of melting, wherein tungsten and/or molybdenumReacts with "free" or "unbound" alkaline carbonates. Due to the high density of the alkaline tungstate and/or alkaline molybdate relative to the borosilicate glass formed, it separates and/or delaminates rapidly, pools at the bottom of the crucible, and cannot dissolve rapidly in the glass due to the significant density difference. Due to R₂O can provide beneficial properties to the glass composition, so simply reducing the presence of R in the melt₂The O component may be undesirable.

The inventors of the present disclosure have found that a homogeneous single phase W-or Mo-containing overbased melt may be obtained by using a "bound" alkaline material. For purposes of this disclosure, a "bound" alkali species is an alkali element that is bound to alumina, boria, and/or silica, while a "free" or "unbound" alkali species is an alkali carbonate, alkali nitrate, and/or alkali sulfate, wherein the alkali species is not bound to silica, boria, and/or alumina. Exemplary bound alkaline agents may include: feldspar, nepheline, borax, spodumene, other albite or potash feldspar, alkali-containing aluminosilicates, alkali silicates and/or other naturally occurring or artificial alkali-containing substances as well as one or more minerals containing aluminum, boron and/or silicon atoms. By introducing the alkaline species in a bound form, the alkaline species may not react with W or Mo present in the melt to form a dense alkaline tungstate and/or alkaline molybdate liquid. In addition, such batch variations can achieve strongly overbased compositions (e.g., R)₂O-Al₂O₃About 2.0 mole percent or greater) without forming any alkaline tungstate and/or alkaline molybdate second phases. This also enables the melting temperature and mixing method to be varied and still produce a single phase homogeneous glass. It will be appreciated that since the alkali tungstate phase and the borosilicate glass are not completely immiscible, prolonged stirring may also effect mixing of the two phases to cast a single phase article.

Once the glass melt is cast and solidified to provide the article in a glassy state, the article may be annealed, heat treated, or otherwise thermally processed to form crystalline phases in the article. Thus, the article may be transformed from a glassy state to a glassy ceramic state. The crystalline phase in the glass-ceramic state can have various morphologies. According to various examples, the crystalline phase is formed as a plurality of precipitates in the heat treated region of the article. Thus, the precipitate may have a substantially crystalline structure.

As used herein, "crystalline phase" refers to an inorganic material in an article of the present disclosure that is a solid composed of atoms, ions, or molecules arranged in a pattern that is three-dimensional periodic. In addition, unless otherwise indicated, the presence of the "crystalline phase" referred to in this disclosure is determined using the following method. First, the presence of crystalline precipitates was detected using powder X-ray diffraction ("XRD"). Raman spectroscopy ("raman") is then used to detect the presence of crystalline precipitates in the event that XRD is unsuccessful (e.g., due to the size, mass, and/or chemistry of the precipitate). Optionally, the determination of the crystalline precipitate by XRD and/or raman techniques is verified visually or in any other way by transmission electron microscopy ("TEM"). In some cases, the mass and/or size of the precipitate may be low enough that visual verification of the precipitate is particularly difficult. Thus, XRD and raman of larger material samples may advantageously have larger sample sizes to determine the presence of precipitates.

The crystalline precipitate may have a generally rod-like or needle-like morphology. The precipitate may have the following longest length dimension: from about 1nm to about 500nm, alternatively from about 1nm to about 400nm, alternatively from about 1nm to about 300nm, alternatively from about 1nm to about 250nm, alternatively from about 1nm to about 200nm, alternatively from about 1nm to about 100nm, alternatively from about 1nm to about 75nm, alternatively from about 1nm to about 50nm, alternatively from about 1nm to about 25nm, alternatively from about 1nm to about 20nm, alternatively from about 1nm to about 10 nm. The size of the precipitate can be measured using an electron microscope. For the purposes of this disclosure, the term "electron microscope" means the first visual measurement of the longest length of the precipitate by scanning electron microscopy and, if the precipitate cannot be resolved, the subsequent use of transmission electron microscopy. Since crystalline precipitates may generally have rod-like or needle-like morphology, the width of the precipitates may be from about 2nm to about 30nm, alternatively from about 2nm to about 10nm, alternatively from about 2nm to about 7 nm. It will be appreciated that the size and/or morphology of the precipitates may be uniform, substantially uniform, or may vary. Generally, the peraluminum composition of the article can produce acicular shaped precipitates having a length of about 100nm to about 250nm and a width of about 5nm to about 30 nm. The overbased composition of the article may produce acicular precipitates having a length of about 10nm to about 30nm and a width of about 2nm to about 7 nm. The Ag-containing, Au-containing, and/or Cu-containing examples of the article can produce rod-like precipitates having a length of about 2nm to about 20nm and a width or diameter of about 2nm to about 10 nm. The volume fraction of the crystalline phase in the article may be from about 0.001% to about 20%, alternatively from about 0.001% to about 15%, alternatively from about 0.001% to about 10%, alternatively from about 0.001% to about 5%, alternatively from about 0.001% to about 1%.

The smaller size of the precipitates may be advantageous in reducing the amount of scattering of light by the precipitates, resulting in high optical clarity of the glass article when in the glass-ceramic state. As explained in more detail below, the size and/or mass of the precipitates in the article may vary, such that different portions of the article may have different optical properties. For example, the presence of precipitates in the article may result in a change in the absorbance, color, reflectance, and/or transmission of light and refractive index as compared to portions of the article having different (e.g., size and/or mass) precipitates and/or portions where no precipitates are present.

The precipitates may include oxides of tungsten and/or oxides of molybdenum. The crystalline phase includes an oxide of at least one of (about 0.1 mol% to about 100 mol% of the crystalline phase): (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 processing (e.g., heat treatment) of the article, tungsten and/or molybdenum cations aggregate to form crystalline precipitates, thereby transitioning from a glassy state to a glassy ceramic state. Molybdenum and/or tungsten present in the precipitate may be reduced or partially reduced. For example, molybdenum in the precipitateAnd/or tungsten may have an oxidation state of 0 to about + 6. According to various examples, the molybdenum and/or tungsten may have a +6 oxidation state. For example, the precipitate may have a general WO₃And/or MoO₃The chemical structure of (1). However, a significant portion of tungsten and or molybdenum in the +5 oxidation state may also be present, and the precipitate may be referred to as non-stoichiometric tungsten suboxide, non-stoichiometric molybdenum suboxide, "molybdenum bronze" and/or "tungsten bronze". One or more of the above alkali metals and/or dopants may be present in the precipitate to compensate for the +5 charge of W or Mo. The tungsten bronze and/or molybdenum bronze is of M_xWO₃Or M_xMoO₃A group of non-stoichiometric tungsten and/or molybdenum suboxides of the general chemical formula (I) wherein M is one or more of H, L i, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, L a, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, L U and/or U, and wherein 0<x<1。M_xWO₃And M_xMoO₃The structure is considered to be a solid state defect structure, in which the reduced WO₃Or MoO₃The pores (i.e., holes and/or channels in the lattice) in the network of (a) are randomly occupied by M atoms, which dissociate into M⁺A cation and a free electron. Depending on the concentration of "M", the material properties can range from metal to semiconductor, enabling the tuning of various optical absorption and electrical properties. The more W or Mo that is 5+, the more M + cations are needed to compensate and the larger the value of x.

Tungsten bronze is of the formula M_xWO₃Where M is a cationic dopant, such as some other metal, most commonly an alkali metal, and x is a variable less than 1. Although referred to as 'bronzes' for clarity, these compounds are structurally or chemically unrelated to metal bronzes, which are alloys of copper and tin. Tungsten bronze is a solid phase spectrum whose homogeneity varies with x. Depending on the dopant M and the corresponding concentration x, the material properties of tungsten bronzes can range from metals to semiconductors and exhibit adjustable optical absorption. The structure of these bronzes is a solid state defect structure, in which M is' cations are inserted into the pores or channels of the binary oxide matrix and are broken down into M + cations and free electrons.

For clarity, M_xWO₃Is a naming convention for complex systems of non-stoichiometric or 'sub-stoichiometric' compounds having varying crystal structures, which may be hexagonal, tetragonal, cubic or pyrochlore, wherein M may be one or a combination of certain elements of the periodic Table of the elements, and wherein x is from 0<x<1, where the oxidation state of the bronze-forming species (in this case, W) is in its highest oxidation state (W)⁶⁺) And lower oxidation state (e.g., W)⁵⁺) And wherein, WO₃The number three ("3") in (a) indicates that the number of oxygen anions may be between 2 and 3. Thus, instead, M_xWO₃Can be expressed as M_xWO_ZChemical form, wherein 0<x<1 and 2<z<3, or may be expressed as M_xWO_3-zIn the formula, 0<x<1 and 0<z<1. However, for convenience, for such non-stoichiometric crystals, M is used_xWO₃. Similarly, ' bronze ' generally applies to formula M '_xM”_yO_zWherein (i) M "is a transition metal, and (ii) M"_yO_zIs the highest binary oxide thereof, (iii) M' is some other metal, (iv) x falls within 0<x<1, or a pharmaceutically acceptable salt thereof.

A portion of the article, a majority of the article, substantially the entire article, or the entire article may be thermally processed to form a precipitate. Thermal processing techniques may include, but are not limited to: ovens (e.g., heat treatment ovens), microwaves, lasers, and/or other techniques for localized and/or bulk heating of an article. When subjected to thermal processing, the crystalline precipitates nucleate internally within the article in a homogeneous manner, wherein the article undergoes thermal processing to transition from a glass state to a glass-ceramic state. Thus, in some examples, the article may include both a glass state and a glass-ceramic state. In the case of thermal processing of the article body (e.g., placing the entire article in an oven), the precipitate may be formed uniformly throughout the article. In other words, there may be precipitates throughout the bulk of the article (i.e., more than about 10 μm from the surface) starting from the outer surface of the article. In the example of an article being locally heat-treated (e.g., by a laser), deposits may only be present where the heat treatment reaches a sufficient temperature (e.g., at the surface and into the body of the article near the heat source). It will be appreciated that the article may be subjected to more than one thermal process to produce a precipitate. Additionally or alternatively, thermal processing may be employed to remove and/or modify precipitates that have formed (e.g., as a result of prior thermal processing). For example, thermal processing can result in decomposition of the precipitate.

According to various examples, the article may be optically transparent to the visible region of the electromagnetic spectrum (i.e., from about 400nm to about 700nm) for both the presence and absence of precipitates (i.e., in the portion that is in the glass or glass-ceramic state). As used herein, the term "optically transparent" refers to having greater than about 1% transmission (e.g., in%/mm) over a 1mm path length over at least one 50nm wide wavelength band of light in the range of about 400nm to about 700 nm. In some examples, the article has a transmittance over at least one 50nm wide wavelength band of light in the visible region of the spectrum of: about 5%/mm or greater, about 10%/mm or greater, about 15%/mm or greater, about 20%/mm or greater, about 25%/mm or greater, about 30%/mm or greater, about 40%/mm or greater, about 50%/mm or greater, about 60%/mm or greater, about 70%/mm or greater, about 80%/mm or greater, and above all lower limits between these values.

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

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

Various examples of the disclosure may provide various properties and advantages. It will be understood that while certain properties and advantages may be disclosed in connection with certain compositions, the various properties and advantages disclosed may be equally applicable to other compositions.

For the compositions of tables 1 and 5 below, articles made from the disclosed compositions may exhibit a low coefficient of thermal expansion ("CTE"). For example, the article may have a temperature range of about 10x10 over a temperature range of about 0 ℃ to about 300 ℃^-7℃^-1To about 60x10^-7℃^-1The coefficient of thermal expansion of (a). Such low CTE's may allow the article to withstand large and rapid fluctuations in temperature, making such articles suitable for operation in harsh environments. For optical properties, the article may exhibit: less than 1% transmittance at wavelengths of about 368nm or less, optical transparency in the visible region (e.g., about 500nm to about 700nm), and strong attenuation (e.g., blocking) of NIR wavelengths (e.g., about 700nm to about 1700 nm). Such articles may be advantageous over conventional NIR management solutions because the articles do not employ coatings or films (e.g., may be mechanically brittle, or sensitive to UV light and moisture). Since the article is impermeable to oxygen, moisture, and ultraviolet wavelengths (i.e., benefiting from its glass or glass-ceramic properties), NIR absorbing precipitates may be protected from harsh environmental conditions (e.g., moisture, caustic acids, alkalis, and gases) as well as rapidly changing temperatures. Further, the UV cut-off wavelength and the refractive index change of the glass ceramic state of the product can be adjusted by heat treatment after the molding. The glass-ceramic state of the article may exhibit a change in UV cut-off or refractive index as a result of its crystalline precipitates. The glass state of the article may have a refractive index of about 1.505 to about 1.508, while the glass-ceramic state of the article may have a refractive index of about 1.520 to about 1.522. The thermally adjustable UV cut and refractive index allows for the ability to conform to a variety of UV cut glass specifications with a single glass can by varying the post-forming thermal processing conditions of the article. The refractive index adjusted thermally can produce a large refractive index delta (10)^-2). Due to high viscosity(e.g., 10)⁸To 10¹²Poise) to complete the heat treatment required to adjust the UV absorbance, the final article can be thermally processed without damaging the surface or causing deformation.

For the compositions of tables 1 and 2, articles made from these compositions can provide a new class of non-toxic cadmium and selenium-free articles that exhibit optical extinction with sharp and tunable cutoff wavelengths. Unlike the Cd-free alternatives as Se-containing CdSe filter glasses, these articles do not contain resource and recovery process ("RCRA") metals or other hazardous agents. Furthermore, unlike Cd-free alternatives containing indium and or gallium, the article may be composed of lower cost elements. For optical properties, articles made from these compositions can provide high transparency in the NIR (e.g., greater than about 90%) for the out to 2.7 micron case. In addition, the article may exhibit a sharp visible cut-off wavelength of about 320nm to about 525nm, which may be tuned by thermal processing conditions (e.g., time and temperature) as well as by composition.

For 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, articles made from these compositions can be thermally processed into a glass-ceramic state, which provides various optical properties. For example, for a thickness of about 0.5mm, the transmittance of an article of such composition may be: a visible spectrum (e.g., about 400nm to about 700nm) from about 4% to about 30%, a NIR (e.g., about 700nm to about 1500nm) from about 5% to about 15%, a UV transmittance at wavelengths less than about 370nm of about 1% or less or a UV transmittance at wavelengths from 370nm to about 390nm of about 5% or less. According to some examples, the mixed molybdenum-tungsten example of the article is capable of absorbing 92.3% of the solar spectrum. Such optical properties may be visually perceived as the color of the article. Similar to other compositions, optical properties are produced by the growth of precipitates, and thus, upon thermal processing, color may change on the article. Such thermally variable colors may be used to create a color gradient within an article, such as a shaded edge or border (boarder) in a windshield or sunroof of the article. Such features may be advantageous for eliminating frits baked onto conventional windshield and sunroof surfaces. This thermally tunable color can be used to create a gradient absorption across the article. In addition, articles produced from these compositions can be bleached and patterned by laser (e.g., operating at 355nm, 810nm, and 10.6 μm wavelengths). Upon exposure to laser light at these wavelengths, the exposed portion of the article may change from a blue or gray color (e.g., due to the color of the precipitate) to a clear water white or light yellow color due to thermal decomposition of the UV and NIR absorbing precipitates. A pattern may be created in the article by selective bleaching of desired areas by rastering along the surface of the article with a laser. When the article is bleached, the resulting glassy state is not as absorptive of NIR and the bleaching process is self-limiting (i.e., because the NIR-absorbing precipitate has already decomposed). Furthermore, selective laser exposure may not only produce patterns, but may also produce variable UV & NIR absorbance on the article. According to other examples, the article may be ground to a sufficiently small size and functionalized for use as a photothermally susceptible agent for cancer treatment (i.e., due to its NIR absorbing optical properties).

For the compositions of table 4, articles made from these compositions may be capable of being heat treated (e.g., formed into a glass-ceramic state) after forming, thereby simultaneously adjusting optical absorption and producing a wide range of colors from a single composition. Further, such examples may be fusion formable and/or ion exchangeable. Conventional colored glass compositions employing Ag, Au, and/or Cu typically rely on the formation of nanosized metal precipitates to produce color. The inventors of the present disclosure found that Ag¹⁺Cations may be inserted into the oxides of tungsten and molybdenum to form silver tungsten bronze and/or silver molybdenum bronze, which may provide the article with multi-color characteristics. Unexpectedly, M is composed to the article_xWO₃Or M_xMoO₃Adding low concentration of AgO or AgNO₃Various colors (e.g., red, orange, yellow, green, blue) can be produced by thermally processing the article for different times and temperaturesColor, various brown colors, and/or combinations thereof). It will be appreciated that Au and/or Cu may be used in a similar manner. Analysis confirmed that color tunability was not due to the formation of a crystalline phase (e.g., M)_xWO₃Or M_xMoO₃) The result of templated (patterned) metal nanoparticle ensemble (ensemble) was obtained. Conversely, it is believed that the color tunability in these multi-colored articles results from the variation in band gap energy of the doped tungsten and/or molybdenum oxide precipitates from the insertion of basic ions and Ag into the precipitates¹⁺The concentration of Au and/or Cu cations forms pure basic, pure metal and/or mixed alkali metal, tungsten and/or molybdenum bronzes in different stoichiometric ratios. The band gap energy of the precipitates varies due to their stoichiometry and thus is largely independent of precipitate size and/or shape. Thus, M is doped_xWO₃Or M_xMoO₃The precipitates may remain the same size and/or shape, but may still have many different colors depending on the identity and concentration "x" of the dopant "M". Heat treatment of such articles can produce nearly complete color red in a single article. Further, the color gradient may be stretched or compressed over some physical distance by a thermal gradient applied to the article. In other examples, the article may be subjected to a laser patterning process to locally adjust the color of the article. Such articles may be advantageous for producing colored sunglass lens blanks, cell phone and/or flat plate covers and/or other products that may be constructed of glass-ceramics and that may have aesthetic colors. Since the precipitates are located within the glass-ceramic, scratch resistance and environmental durability are higher than when conventional metallic and polymeric color layers are applied to provide color. Since the color of the article can be changed based on the heat treatment, a can of glass melt can be used to continuously produce a body that can be heat treated to have a specific color as indicated by the consumer's needs. In addition, articles made from these glass compositions may absorb UV and/or IR radiation, similar to other compositions disclosed herein.

According to various examples of the present disclosure, the article may be suitable for use in various fusion forming processes. For example, various compositions of the present disclosure may be used in a single fused laminate or a double fused laminate where transparent tungsten, molybdenum, mixed tungsten molybdenum, and/or titanium glasses are used as cladding materials around a substrate to form a laminate article. After application as a cladding, the cladding in the glass state may be converted to the glass-ceramic state. The glass-ceramic state cladding of the fused laminate may have a thickness of about 50 μm to about 200 μm and may have strong UV and IR attenuation and high average visible light transmission (e.g., about 75% to about 85% for automotive windshields and/or architectural glazings), strong UV and IR attenuation and low visible light transmission (e.g., about 5% to about 30% for automotive side lights, automotive roof panels, and privacy glazings), and/or the laminate may have visible and infrared absorbance adjusted by treatment in a gradient furnace, localized heating, and/or localized bleaching. Furthermore, using the composition as a cladding to form an article provides a new process to fully achieve the purpose of tunable optical properties while producing a strengthened monolithic glass sheet.

According to various examples, the articles resulting from the compositions of the present disclosure may be powdered or granulated and added to various materials. For example, the powdered article can be added to a coating, a binder, a polymeric material (e.g., polyvinyl butyral), a sol gel, and/or combinations thereof. Such features may be advantageous for imparting one or more properties of the article to the materials described above.

According to various examples, the article may comprise TiO₂. The article may contain TiO in the following concentrations₂: 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 1.0 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 17.09.0 mole%, or about 20.0 mole%, or about 21.0 mole%, or about 22.0 mole%, or about 23.0 mole%, or about 24.0 mole%, or about 25.0 mole%, or about 26.0 mole%, or about 27.0 mole%, or about 28.0 mole%, or about 29.0 mole%, or about 30.0 mole%, or any and all values and ranges therebetween. For example, the article may contain TiO at the following concentrations₂: about 0.25 mol% to about 30 mol%, or about 1 mol% to about 30 mol% TiO₂Alternatively from about 1.0 mol% to about 15 mol% TiO₂Alternatively from about 2.0 mol% to about 15 mol% TiO₂Alternatively from about 2.0 mol% to about 15.0 mol% TiO₂. It will be appreciated that the above noted TiO is contemplated₂Any and all values and ranges between ranges.

According to various examples, the article may comprise one or more metal sulfides. For example, the metal sulfide may include MgS, Na₂S and/or ZnS. According to various examples, the article may comprise one or more metal sulfides. For example, the metal sulfide may include MgS, Na₂S and/or ZnS. The article may comprise the metal sulfide at the following concentrations: 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 28.0 mol%, or about 29.0 mol%, or about 28.0 mol%, or any and all values and ranges therebetween. For example, the article may comprise a metal sulfide at a concentration as followsAn object: from about 0.25 mol% to about 30 mol%, alternatively from about 1.0 mol% to about 15 mol%, alternatively from about 1.5 mol% to about 5 mol%.

Similar to the oxides of tungsten and molybdenum described above, examples of articles comprising titanium may also produce crystalline phases that include precipitates of oxides of titanium. The crystalline phase includes Ti and an oxide of an alkali metal cation (about 0.1 mol% to about 100 mol% of the crystalline phase). Without being bound by theory, it is believed that during thermal processing (e.g., heat treatment) of the article, titanium cations accumulate to form crystalline precipitates near and/or on the metal sulfide, thereby transitioning from a glassy state to a glassy ceramic state. The metal sulfide may play a dual role, both as a nucleating agent (i.e., because the metal sulfide may have a higher melting temperature than the melt to act as a seed on which titanium may accumulate) and as a reducing agent (i.e., the metal sulfide is a high reducing agent and thus may reduce the accumulated titanium to a 3+ state). Thus, the titanium present in the precipitate can be reduced or partially reduced due to the metal sulfide. For example, the titanium in the precipitate may have an oxidation state of 0 to about + 4. For example, the precipitate may have substantially TiO₂The chemical structure of (1). However, a significant portion of titanium in the +3 oxidation state may also be present, and in some cases, these Ti³⁺The cations may be stabilized by the charge of species inserted into the channels in the titanium oxide lattice to form compounds known as non-stoichiometric titanium suboxides, "titanium bronzes," or "bronze-type" titanium crystals. One or more of the above-mentioned alkali metals and/or dopants may be present in the precipitate to compensate for the +3 charge of Ti. The titanium bronze is of M_xTiO₂A group of non-stoichiometric titanium suboxides of the general chemical formula (I) wherein M ═ H, L i, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, L a, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, L U, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi and Ce, and wherein 0<x<1。M_xTiO₂The structure is considered to be solidA state defect structure of, among others, reduced TiO₂The pores (i.e., holes or channels in the lattice) in the network of (a) are randomly occupied by M atoms, which dissociate into M⁺A cation and a free electron. Depending on the concentration of "M", the material properties can range from metal to semiconductor, enabling the tuning of various optical absorption and electrical properties. The more Ti that is 3+, the more M + cations are needed to compensate and the larger the value of x.

Consistent with the disclosure above, titanium bronzes are of the formula M_xTiO₂Where M is a cationic dopant, such as some other metal, most commonly an alkali metal, and x is a variable less than 1. Although referred to as 'bronzes' for clarity, these compounds are structurally or chemically unrelated to metal bronzes, which are alloys of copper and tin. Titanium bronze is a solid phase spectrum whose homogeneity varies with x. Depending on the dopant M and the corresponding concentration x, the material properties of titanium bronzes can range from metals to semiconductors and exhibit tunable optical absorption. The structure of these bronzes is a solid state defect structure in which the M' dopant cations are inserted into (i.e., occupy) the pores or channels of the binary oxide matrix and are broken down into M + cations and free electrons.

For clarity, M_xTiO₂Is a naming convention for complex systems of non-stoichiometric or 'sub-stoichiometric' compounds having varying crystal structures, which may be monoclinic, hexagonal, tetragonal, cubic or pyrochlore, wherein M may be one or a combination of certain elements of the periodic Table of the elements, and wherein x is from 0<x<1, wherein the oxidation state of the bronze-forming species (in this case, Ti) is in its highest oxidation state (Ti)⁴⁺) And lower oxidation state (e.g., Ti)³⁺) And wherein TiO₂The number di ("2") in (a) indicates that the number of oxyanions may be between 1 and 2. Thus, instead, M_xTiO₂Can be expressed as M_xTiO_ZChemical form, wherein 0<x<1 and 1<z<2, or may be expressed as M_xTiO_2-zIn the formula, 0<x<1 and 0<z<1. However, for convenience, for such non-stoichiometric crystals, M is used_xTiO₂. Similarly, ' bronze ' generally applies to formula M '_xM”_yO_zWherein (i) M "is a transition metal, and (ii) M"_yO_zIs the highest binary oxide thereof, (iii) M' is some other metal, (iv) x falls within 0<x<1, or a pharmaceutically acceptable salt thereof.

According to various examples, the glass-ceramic article comprising titanium may be substantially free of W, Mo and rare earth elements. As noted above, the ability of titanium to form its own suboxides may eliminate the need for tungsten and molybdenum, and the suboxides of titanium may not require rare earth elements.

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

For example, the article may comprise L i at about 1 mol% or less, or L i at about 0.5 mol% or less, or L i at about 0.1 mol% or less, or L i at about 0.0 mol%, or any and all values and ranges therebetween.

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

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

The formation of titanium suboxides in the titanium-containing example of the article can result in different absorptance and transmittance of different light wavelength bands. The article in the glass state may have an average UV transmission of about 18% to about 30% in the Ultraviolet (UV) band of light (e.g., about 200nm to about 400nm) prior to precipitation of titanium suboxides. For example, the average UV transmittance of the article in the 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. The article in the glass-ceramic state may have an average UV transmittance of about 0.4% to about 18% after the titanium suboxide is formed or precipitated. For example, the average UV transmittance of an article in the glass-ceramic state 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 appreciated that the transmittance values described above may be present in an article having a thickness or optical path length of from about 0.4mm to about 1.25 mm.

The article in the glassy state may have an average visible light transmission of about 60% to about 85% in the visible band of light (e.g., about 400nm to about 750nm) prior to precipitation of the titanium suboxide. For example, the average visible light transmission of an article in the 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 and all values and ranges therebetween. The article in the glass-ceramic state may have an average visible light transmission of about 4% to about 85% after the titanium suboxide is formed or precipitated. For example, the average UV transmittance of the article in the glass-ceramic state may 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 appreciated that the transmittance values described above may be present in an article having a thickness or optical path length of from about 0.4mm to about 1.25 mm.

The article in the glass state may have an average NIR transmittance of about 80% to about 90% prior to precipitation of titanium suboxides in the Near Infrared (NIR) band of light (e.g., about 750nm to about 1500 nm). For example, the average NIR transmittance of an article in the glass 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. The article in the glass-ceramic state may have an average NIR transmittance of about 0.1% to about 10% after the suboxide of titanium is formed or precipitated. For example, the average UV transmittance of the article in the glass-ceramic state may 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 appreciated that the transmittance values described above may be present in an article having a thickness or optical path length of from about 0.4mm to about 1.25 mm.

In the NIR band of light, the article in the glass state, free of titanium suboxides, may have an average optical density per mm (i.e., first near infrared absorbance) as follows: about 0.4 or less, or about 0.35 or less, or about 0.3 or less, or about 0.25 or less, or about 0.2 or less, or about 0.15 or less, or about 0.1 or less, or about 0.05 or less, or any and all values and ranges therebetween. After precipitation of the titanium suboxide, the article in the glass-ceramic state having the titanium suboxide may have an optical density per mm (i.e., a second near infrared absorption) as follows: about 6.0 or less, or about 5.5 or less, or about 5.0 or less, or about 4.5 or less, or about 4.0 or less, or about 3.5 or less, or about 3.0 or less, or about 2.5 or less, or about 2.0 or less, or about 1.5 or less, or about 1.0 or less, or about 0.5 or less, or any and all values and ranges therebetween. Thus, in some cases, the ratio of the second average near infrared absorbance to the first average near infrared absorbance 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 10.1 or greater. In such examples, the article in the glass-ceramic state having a suboxide of titanium may have an average optical density per mm of visible light wavelength of 1.69 or less.

According to various examples, the article may exhibit a haze of about 20% or less, or about 15% or less, or about 12% or less, or about 11% or less, or about 10.5% or less, or about 10% or less, or about 9.5% or less, or about 9% or less, or about 8.5% or less, or about 8% or less, or about 7.5% or less, or about 7% or less, or about 6.5% or less, or about 6% or less, or about 5.5% or less, or about 5% or less, or about 4.5% or less, or about 4% or less, or about 3.5% or less, or about 3% or less, or about 2.5% or less, or about 2% or less, or about 1.5% or less, or about 3.5% or less, or about 3% or less, or about 2.5% or less, or about 0.5% or less, or about 0% or less, or about 0.5% or less, as measured with respect to the haze of a glass ceramic article, or a conventional glass or a glass article, or a glass article that is less than a glass or a glass article that is less than a glass or a glass article that is less than a glass article that.

Using titanium-containing suboxides of the formula M_XTiO₂The crystalline or non-stoichiometric titanium bronze articles of (a) can provide a number of advantages.

First, the thermal processing time to produce titanium suboxides can be shorter than for the production of other glass-ceramics. In addition, the thermal processing temperature may be below the softening point of the article. Such features may be advantageous for reducing manufacturing complexity and cost.

Second, it is possible to provide a wide range of melt compositions (including those having detachable properties)Those of sub-switching capability) incorporate color packing (e.g., TiO)₂+ ZnS). In addition, such color packing may have less impact on chemical durability and other related properties of the article due to the lower concentration of color packing required.

Third, the use of titanium-containing suboxide glass-ceramics may provide fusion formable and chemically strengthenable materials for ultraviolet and/or infrared blocking materials that may not have melting difficulties due to radiation trapping. For example, for an article comprising titanium suboxide, it is highly transparent at visible and NIR wavelengths when molten or in the as-cast state (i.e., green state prior to heat treatment), as opposed to Fe, which has a strong absorption in the near infrared even when molten²⁺Doped glass.

Examples

The following examples represent non-limiting examples of the composition of the articles of the present disclosure.

Referring now to table 1, an article may have: SiO 2₂About 58.8 mol% to about 77.58 mol%, Al₂O₃About 0.66 mol% to about 13.69 mol%, B₂O₃About 4.42 mol% to about 27 mol%, R₂O from about 0 mol% to about 13.84 mol%, RO from about 0 mol% to about 0.98 mol%, WO₃About 1.0 mol% to about 13.24 mol%, and SnO₂From about 0 mol% to about 0.4 mol%. It will be understood that any of the exemplary compositions of table 1 may comprise: MnO₂About 0 mol% to about 0.2 mol%, Fe₂O₃About 0 mol% to about 0.1 mol%, TiO₂About 0 mol% to about 0.01 mol%, As₂O₅About 0 mol% to about 0.17 mol%, and/or Eu₂O₃From about 0 mol% to about 0.1 mol%. The compositions of table 1 are provided in the as-dosed state in the crucible.

Table 1:

referring now to table 2, an article may have: SiO 2₂About 65.43 mol% to about 66.7 mol%, Al₂O₃About 9.6 mol% to about 9.98 mol%, B₂O₃About 9.41 mol% to about 10.56 mol%, R₂O from about 6.47 mol% to about 9.51 mol%, RO from about 0.96 mol% to about 3.85 mol%, WO₃About 1.92 mol% to about 3.85 mol%, MoO₃About 0 mol% to about 1.92 mol%, and SnO₂From about 0 mol% to about 0.1 mol%. The compositions of table 2 are provided in the as-dosed state in the crucible.

TABLE 2

Referring now to table 3, an article may have: SiO 2₂About 60.15 mol% to about 67.29 mol%, Al₂O₃About 9.0 mol% to about 13.96 mol%, B₂O₃About 4.69 mol% to about 20 mol%, R₂O from about 2.99 mol% to about 12.15 mol%, RO from about 0.00 mol% to about 0.14 mol%, WO₃About 0 mol% to about 7.03 mol%, MoO₃About 0 mol% to about 8.18 mol%, SnO₂About 0.05 mol% to about 0.15 mol% and V₂O₅From about 0 mol% to about 0.34 mol%. It will be understood that any of the exemplary compositions of table 3 may comprise Fe₂O₃From about 0 mol% to about 0.0025 mol%. The compositions of table 3 are provided in the as-dosed state in the crucible.

TABLE 3

Referring now to table 4, an article may have: SiO 2₂About 54.01 mol% to about 67.66 mol%, Al₂O₃About 9.55 mol% to about 11.42 mol%, B₂O₃About 9.36 mol% to about 15.34 mol%, R₂O from about 9.79 mol% to about 13.72 mol%, RO from about 0.00 mol% to about 0.22 mol%, WO₃About 1.74 mol% to about 4.48 mol%, MoO₃About 0 mol% to about 1.91 mol%, SnO₂About 0.0 mol% to about 0.21 mol%, V₂O₅About 0 mol% to about 0.03 mol%, Ag about 0 mol% to about 0.48 mol%, and Au about 0 mol% to about 0.01 mol%. It will be understood that any of the exemplary compositions of table 4 may comprise: CeO (CeO)₂About 0 mol% to about 0.19 mol%, CuO about 0 mol% to about 0.48 mol%, Br-about 0 mol% to about 0.52 mol%, Cl-about 0 mol% to about 0.2 mol%, TiO%₂About 0 mol% to about 0.96 mol%, and/or Sb₂O₃From about 0 mol% to about 0.29 mol%. The compositions of table 4 are provided in the as-dosed state in the crucible.

TABLE 4

Referring now to table 5, an article may have: SiO 2₂About 60.01 mol% to about 77.94 mol%, Al₂O₃About 0.3 mol% to about 10.00 mol%, B₂O₃About 10 mol% to about 20 mol%, R₂O from about 0.66 mol% to about 10 mol%, WO₃About 1.0 mol% to about 6.6 mol%, and SnO₂From about 0.0 mol% to about 0.1 mol%. It will be understood that any of the exemplary compositions of table 5 may comprise Sb₂O₃From about 0 mol% to about 0.09 mol%. The compositions of table 5 are provided in the as-dosed state in the crucible.

TABLE 5

Referring now to table 6, a list of comparative example exemplary glass compositions is provided that when melted with unbound alkaline batch materials (e.g., alkaline carbonates) in place of bound alkaline species (e.g., nepheline), form liquid alkaline tungstates that separate during the melting process. As explained above, the second liquid alkaline tungstate phase may solidify as separate crystals, which may cause the substrate made therefrom to be opalescent.

TABLE 6

Exemplary applications

In this context, cadmium and selenium containing glasses ("CdSe glasses") can be characterized by their toxicity because they have appreciable amounts of cadmium and selenium. Some efforts have been made to develop non-toxic or low-toxic alternatives to CdSe glasses. For example, some conventional alternatives include a Cd-free glass composition. However, these compositions still contain selenium and other expensive dopants, such as indium and gallium. Furthermore, conventional Cd-free selenium-containing glasses are characterized by poor cut-off wavelength and/or viewing angle dependence relative to CdSe glasses. Thus, applicants believe that there is a need for cadmium and selenium free materials having comparable or improved optical properties relative to conventional CdSe glasses. Preferably, these materials have adjustable bandgaps and sharp cut-offs as non-toxic alternatives to CdSe glasses. For the target applications of these materials, there is also a need for a non-toxic CdSe glass substitute having the following characteristics: low Coefficient of Thermal Expansion (CTE), durability, resistance to thermal stress, and/or simpler and lower cost manufacturing and processing requirements.

According to some aspects of the present disclosure, glass-ceramics are provided that include an aluminoborosilicate glass; WO₃About 0.7 to about 15 molar%; at least one alkali metal oxide, about 0.2 to about 15 mole%; and at least one alkaline earth metal oxide, from about 0.1 to about 5 mole%.

According to some aspects of the present disclosure, glass-ceramics are provided that include an aluminoborosilicate glass; WO₃About 0.7 to about 15 molar%; at least one alkali metal oxide, about 0.2 to about 15 mole%; and at least one alkaline earth metal oxide, from about 0.1 to about 5 mole%. Furthermore, glassThe ceramic includes: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm.

According to other aspects of the present disclosure, glass-ceramics are provided that include aluminoborosilicate glass; WO₃About 0.7 to about 15 molar%; at least one alkali metal oxide, about 0.2 to about 15 mole%; and at least one alkaline earth metal oxide, from about 0.1 to about 5 mole%. Further, the glass-ceramic comprises at least one of: alkaline earth, alkaline and mixed alkaline earth-alkaline tungstate crystalline phases, either in stoichiometric or non-stoichiometric form.

In some implementations of the foregoing aspects of the glass-ceramic, the aluminoborosilicate glass comprises: SiO 2₂About 55 to about 80 mol% Al₂O₃About 2 to about 20 mole%, and B₂O₃About 5 to about 40 mole percent SiO₂68 to 72 mol% Al₂O₃8 to 12 mol%, and B₂O₃5 to 20 mol%. Further, the at least one alkaline earth metal oxide may include MgO of 0.1 to 5 mol%. The at least one alkali metal oxide may comprise Na₂O5 to 15 mol%. Further, the at least one alkali metal oxide and Al in the aluminoborosilicate glass₂O₃The amount of (b) may vary from-6 mol% to +2 mol%.

In other practices of the foregoing 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 comprise at least one dopant selected from the group consisting of: F. p, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi. In other practices of the foregoing aspects of the glass-ceramic, the glass-ceramic may further comprise MoO₃Which is WO present in the glass-ceramic₃From 0% to about 50%.

In accordance with another aspect of the present disclosure, an article is provided that includes a substrate including a major surface and a glass-ceramic composition, including: aluminoborosilicate glass; WO₃About 0.7 to about 15 molar%; at least one alkali metal oxide, about 0.2 to about 15 molar%; and at least one alkaline earth metal oxide, from about 0.1 to about 5 mole%. Further, in some practices of this aspect, the substrate further includes a compressively stressed region extending from the major surface to a first selected depth in the substrate and originating from the ion exchange process. Further, in some embodiments of this aspect, the substrate can comprise: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm.

According to another aspect of the present disclosure, there is provided a method of manufacturing a glass-ceramic, including: mixing a batch comprising an aluminoborosilicate glass, WO₃About 0.7 to about 15 mole%, at least one alkali metal oxide about 0.2 to about 15 mole%, and at least one alkaline earth metal oxide about 0.1 to about 5 mole%; melting the batch at about 1500 ℃ to about 1700 ℃ to form a melt; annealing the melt at about 500 ℃ to about 600 ℃ to define an annealed melt; and heat treating the annealed melt at about 500 ℃ to about 1000 ℃ for about 5 minutes to about 48 hours to form the glass-ceramic.

In some practices of the foregoing methods of making glass-ceramics, the heat treating comprises heat treating the annealed melt at about 600 ℃ to about 800 ℃ for about 5 minutes to about 24 hours to form the glass-ceramic. Further, the heat treating comprises heat treating the annealed melt at about 650 ℃ to about 725 ℃ for about 45 minutes to about 3 hours to form the glass-ceramic. In some embodiments of the method, the glass-ceramic may comprise: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm.

As described in detail in this disclosure, cadmium and selenium free glass-ceramic materials are provided that have comparable or improved optical properties compared to conventional CdSe glasses. In embodiments, these materials have adjustable bandgaps and sharp cut-offs as non-toxic alternatives to CdSe glasses. Embodiments of these materials may also be characterized by a low Coefficient of Thermal Expansion (CTE), durability, resistance to thermal stress, and/or simpler and lower cost manufacturing and processing requirements.

More generally, the glass-ceramic materials disclosed herein, and articles containing them, include a balance of aluminoborosilicate glass, tungsten oxide, at least one alkali metal oxide, and at least one alkaline earth metal oxide. These glass-ceramic materials can be characterized as: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm. Further, these materials may include at least one alkaline earth tungstate crystalline phase established, for example, via certain heat treatment conditions after the glass-ceramic is formed. Furthermore, embodiments of these glass-ceramic materials are characterized in that the cut-off can be adjusted by selecting specific heat treatment conditions. Thus, these glass-ceramic materials provide non-toxic cadmium and selenium free glass-ceramics as a replacement for conventional CdSe glasses.

Various embodiments of the glass-ceramic material of the present disclosure may be used in the form of substrates, components, covers, and other components in any of the following applications: a security and surveillance filter configured to suppress visible light for infrared illumination; airport runway lights; laser eye protection glasses; a grating for motion control of the motor; a bar code reader; an atomic force microscope; a nano-imprinting machine; laser interferometer metrology solutions; a laser-based dynamic calibration system; lithographic solutions for integrated circuit manufacturing; a photon error rate test solution; a photon digital communication analyzer; a photon dither generation and analysis system; an optical modulation analyzer; an optical power meter; an optical attenuator; a light source; a light wave component analyzer; a gas chromatograph; a spectrometer; a fluorescence microscope; a traffic surveillance camera; environmental waste, water and exhaust monitoring equipment; a spectral filter of the camera; a radiation thermometer; an imaging brightness colorimeter; processing an industrial image; a controllable wavelength light source for counterfeit detection; a scanner for digitizing the color image; an astronomical filter; a hanflei site analyzer in a medical diagnostic device; and filters for ultrashort pulse lasers. These embodiments of glass-ceramic materials are also suitable for various artistic endeavors and applications utilizing colored glasses, glass-ceramics and ceramics, such as glass blowers, firemen, colored glass artists, and the like.

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

Referring now to fig. 1, a display article 100 includes a substrate 10, the substrate 10 including a glass-ceramic composition according to the present disclosure. These articles may be used for any of the applications listed above (e.g., filters, airport runway lights, barcode readers, etc.). Thus, in some embodiments, the substrate 10 may be characterized as: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm. The substrate 10 includes a pair of opposed

major surfaces

12, 14. In some embodiments of the article 100, the substrate 10 includes a compressive stress region 50. As shown in fig. 1, the compressive stress region 50 of the article 110 is exemplary and extends from the major surface 12 to a first selected depth 52 within the substrate. Some embodiments of article 100 (not shown) include a comparable additional compressive stress region 50 extending from major surface 14 to a second selected depth (not shown). In addition, some embodiments of the article 100 (not shown) include a plurality of compressive stress regions 50 extending from the

major surfaces

12, 14 of the substrate 10. Further, some embodiments of article 100 (not shown) include: a plurality of compressive stress regions 50 extending from the respective

major surfaces

12, 14, and also extending from short edges of the substrate 10 (i.e., edges orthogonal to the major surfaces 12, 14). As will be appreciated by those skilled in the art of the present disclosure, various combinations of compressive stress regions 50 may be incorporated into the article 100 depending on the processing conditions used to create these compressive stress regions 50 (e.g., fully immersing the substrate 10 in the molten salt ion exchange bath, partially immersing the substrate 10 in the molten salt ion exchange bath, fully immersing the substrate 10 with certain edges and/or surfaces masked, etc.).

As used herein, "selected depth" (e.g., selected depth 52), "depth of compression" and "DOC" may be used interchangeably to define the depth of the stress change in the substrate 10 from compression to tension as described herein, depending on the ion exchange process, DOC may be measured by a surface stress meter (e.g., FSM-6000) or a diffuse light polarizer (SCA L P.) when stress is generated in a substrate 10 having a glass or glass-ceramic composition by exchanging potassium ions into the glass substrate, DOC is measured using a surface stress meter. when stress is generated in a glass article by exchanging sodium ions into the glass article, DOC is measured using SCA L P. when stress is generated in a substrate 10 having a glass or glass-ceramic composition by exchanging both potassium and sodium ions into the glass, DOC is measured by SCA L P because it is believed that the depth of exchange of sodium represents DOC, and the depth of exchange of potassium ions represents the change in magnitude of compressive stress (rather than the change from compression to tension), and in this type of glass, the maximum compressive stress is measured by the exchange depth of potassium ions in the region of the substrate 10 as defined by the maximum compressive stress, or compressive stress region 50, as defined by the maximum compressive stress region of the compressive stress in the other embodiments 12.

Referring again to fig. 1, the substrate 10 of the article 100 may be characterized by a glass-ceramic composition. In an embodiment, the glass-ceramic composition of the substrate 10 has: WO₃Is 0.7 to 15 mole percent, at least one alkali metal oxide is 0.2 to 15 mole percent, at least one alkaline earth metal oxide is 0.1 to 5 mole percent, and the balance silicate-containing glass. These silicate-containing glasses include: aluminoborosilicate glasses, borosilicate glasses, aluminosilicate glasses, soda lime glasses, and chemically strengthened versions of these silicate-containing glasses.

Further, in the embodiment of article 100 shown in fig. 1, substrate 10 may have a length and width or diameter selected to define its surface area. The substrate 10 may have at least one edge defined by its length and width or by its diameter between the

major surfaces

12, 14 of the substrate 10. The substrate 10 may also have a selected thickness. In some embodiments, the substrate has a thickness as follows: about 0.2mm to about 1.5mm, about 0.2mm to about 1.3mm, and about 0.2mm to about 1.0 mm. In other embodiments, the substrate has a thickness as follows: from about 0.1mm to about 1.5mm, from about 0.1mm to about 1.3mm, or from about 0.1mm to about 1.0 mm.

In some embodiments of the article 100, as shown in the exemplary form of FIG. 1, the substrate 10 is selected from chemically strengthened aluminoborosilicate glasses. For example, the substrate 10 may be selected from a chemically strengthened aluminoborosilicate glass having a compressive stress region 50 extending to a first selected depth 52 of greater than 10 μm, with a maximum compressive stress of greater than 150 MPa. In other embodiments, the substrate 10 is selected from a chemically strengthened aluminoborosilicate glass having a compressive stress region 50 extending to a first selected depth 52 greater than 25 μm, 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), the maximum compressive stress being greater than about 150MPa, greater than 200MPa, greater than 250MPa, greater than 300MPa, greater than 350MPa, greater than 400MPa, greater than 450MPa, greater than 500MPa, greater than 550MPa, greater than 600MPa, greater than 650MPa, greater than 700MPa, greater than 750MPa, greater than 800MPa, greater than 850MPa, greater than 900MPa, greater than 950MPa, greater than 1000MPa, and all maximum compressive stress levels between these values. In some embodiments, the maximum compressive stress is 2000MPa or less. Further, 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, 25 μm or greater, 30 μm or greater, 35 μm or greater, and even higher depending on the thickness of the substrate 10 and the processing conditions associated with creating the compressive stress region 50. In some embodiments, the DOC is less than or equal to 0.3 times the thickness (t) of the substrate 10, e.g., 0.3t, 0.28t, 0.26t, 0.25t, 0.24t, 0.23t, 0.22t, 0.21t, 0.20t, 0.19t, 0.18t, 0.15t, or 0.1 t.

As described above, the glass-ceramic material of the present disclosure (including the substrate 10 for the article 100, see fig. 1) is characterized by the following glass-ceramic composition: WO₃0.7 to 15 mole%; 0.2 to 15 mole% of at least one alkali metal oxide; 0.1 to 5 mole% of at least one alkaline earth metal oxide; and the balance silicate-containing glass, such as aluminoborosilicate glass. In embodiments, the glass-ceramic material may be characterized as: an optical transmission of at least 90% from 700nm to 3000nm, and a sharp cutoff wavelength from about 320nm to about 525 nm. In some implementations, the glass-ceramic material can also be characterized by the presence of at least one alkaline earth tungstate crystalline phase and/or at least one alkali tungstate crystalline phase. For example, the alkaline earth tungstate crystal phase may be M_xWO₃Wherein M is at least one of Be, Mg, Ca, Sr, Ba and Ra, and wherein 0<x<1. In embodiments of the glass-ceramics of the present disclosure, the at least one alkaline earth tungstate crystalline phase is one or both of: MgWO₄Crystalline phases (see, e.g., fig. 5 and its corresponding description) and MgW₂O₇Crystalline phases (see, e.g., FIGS. 6A-6C, 7A)&7B and their corresponding descriptions). As another example, the alkaline tungstate crystal phase may be M_xWO₃Wherein M is L i, Na, K, Cs, or a salt thereof,At least one of Rb, and wherein 0<x<1. As another example, the tungstate crystal phase may be M_xWO₃Wherein M is a combination of an alkaline earth material selected from Be, Mg, Ca, Sr, Ba and Ra and an alkali metal selected from L i, Na, K, Cs and Rb, and wherein 0<x<1。

In embodiments, the glass-ceramics of the present disclosure are optically transparent in the visible region of the spectrum (i.e., about 400nm to about 700 nm). As used herein, the term "optically transparent" refers to having greater than about 1% transmission (e.g., in%/mm) over a 1mm path length over at least one 50nm wide wavelength band of light in the range of about 400nm to about 700 nm. In some embodiments, the glass-ceramic has a transmittance over at least one 50nm wide wavelength band of light in the visible region of the spectrum of: at least greater than about 5%/mm, greater than about 10%/mm, greater than about 15%/mm, greater than about 20%/mm, greater than about 25%/mm, greater than about 30%/mm, greater than about 40%/mm, greater than about 50%/mm, greater than about 60%/mm, greater than about 70%/mm, and all lower values therebetween.

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

Embodiments of the glass-ceramic materials of the present disclosure include aluminoborosilicate glasses (e.g., containing SiO)₂、Al₂O₃And B₂O₃)、WO₃At least one alkali metal oxide and at least one alkaline earth metal oxide. In some embodiments, an aluminoborosilicate glass comprises: about 55 mol% to about 80 mol% SiO₂About 60 mol% to about 74 mol% SiO₂Or about 64 mol% to about 70 mol% SiO₂. Furthermore, the aluminoborosilicate glass of the glass-ceramic may comprise: about 2 mol% to about 40 mol% B₂O₃About 5 mol% to about 16 mol% B₂O₃Or from about 6 mol% to about 12 mol% B₂O₃. Furthermore, the aluminoborosilicate glass of the glass-ceramic may comprise: about 0.5 mol% to about 16 mol% Al₂O₃About 2 mol% to about 20 mol% Al₂O₃Or from about 6 mol% to about 14 mol% Al₂O₃。

The glass-ceramic material of the present disclosure comprises from about 0.7 mol% to about 15 mol% WO₃. In some embodiments, the glass-ceramic material comprises about 1 mol% to about 6 mol% WO₃Or from about 1.5 mol% to about 5 mol% WO₃. In some embodiments, the glass-ceramic may further comprise WO present in the composition₃About 0% to about 50% MoO₃(i.e., MoO)₃About 0% to 5 mol%). In some embodiments, the glass-ceramic further comprises from about 0 mol% to about 3 mol% or from about 0 mol% to about 2 mol%Mol% MoO₃。

In embodiments, the glass-ceramic material comprises 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 consisting of L i₂O、Na₂O、K₂O、Rb₂O and Cs₂And O. In some implementations, the at least one alkali metal oxide and Al in the aluminoborosilicate glass are₂O₃The amount of (b) is different in the range of-6 mol% to +2 mol%.

The glass-ceramic material of the present disclosure also includes at least one alkaline earth metal oxide. In an embodiment, the glass-ceramic comprises about 0.1 mol% to about 5 mol% of the at least one alkaline earth oxide. The at least one alkaline earth metal oxide may be selected from the group consisting of: MgO, SrO and BaO. In other embodiments, the glass-ceramic material of the present disclosure comprises from about 0 mol% to about 0.5 mol%, from about 0 mol% to about 0.25 mol%, or from about 0 mol% to about 0.15 mol% SnO₂。

According to a preferred mode of practice, the glass-ceramic material of the present disclosure is substantially free of cadmium and substantially free of selenium. In embodiments, the glass-ceramic may further comprise at least one dopant selected from the group consisting of: F. p, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi. In some embodiments, the at least one dopant is present in the glass-ceramic in an amount of from about 0 mol% to about 0.5 mol%, calculated as oxide.

Non-limiting compositions of glass-ceramics according to the principles of the present disclosure are shown in tables 1A (reported as weight%) and 1B (reported as mole%) below.

TABLE 1A

TABLE 1A (continuation)

TABLE 1B

TABLE 1B (continuation)

According to embodiments, the glass-ceramic material of the present disclosure may be manufactured by employing a melt quench process. The components may be mixed and blended in the appropriate proportions by turbulent mixing and/or ball milling. Batch materials may include, but are not limited to, one or more of the following: gravel, spodumene, petalite, nepheline, syenite, alumina, borax, boric acid, carbonates and nitrates of alkali metals and alkaline earth metals, tungsten oxides and ammonium tungstate. The dosed material is then melted at a temperature of about 1500 ℃ to about 1700 ℃ for a predetermined time. In some implementations, the predetermined time ranges from about 6 to about 12 hours, after which time the resulting melt can be cast or formed and then annealed as will be understood by those skilled in the art of the present disclosure. In some embodiments, the melt may be annealed at about 500 ℃ to about 600 ℃ to define an annealed melt.

At this stage of the process, the annealed melt is heat treated at about 500 ℃ to about 1000 ℃ 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 and below the softening point of the glass-ceramic to establish one or more crystalline tungstate phases.

In some embodiments, the annealed melt is heat treated at about 600 ℃ to about 800 ℃ for about 5 minutes to about 24 hours to form a glass-ceramic. According to some embodiments, the annealed melt is heat treated at about 650 ℃ to about 725 ℃ for about 45 minutes to about 3 hours to form a glass-ceramic. In another practice, the annealed melt is heat treated according to the temperature and time to achieve specific optical properties, such as an optical transmission of at least 90% from 700nm to 3000nm and a sharp cutoff wavelength of about 320nm to about 525 nm. In addition, as described in the examples below, other heat treatment temperatures and times may be employed to obtain the glass-ceramic material.

Example of an exemplary application

The following examples represent certain non-limiting examples of glass-ceramic materials and articles of the present disclosure, including methods for their manufacture.

Referring now to fig. 2A and 2B, transmittance versus wavelength plots for comparative CdSe glass ("comparative example 1") and heat-treated glass-ceramic ("example 1") are provided. Note that fig. 2B is the image of fig. 2A, rescaled to show the cut-off wavelengths of the comparative CdSe glass and heat treated glass-ceramic samples. In this example, a comparative example CdSe glass (comparative example 1) has a conventional CdSe glass composition according to: 40-60% SiO₂，5-20％B₂O₃，0-8％P₂O₅，1.5-6％Al₂O₃，4-8％Na₂O，6-14％K₂O, 4-12% ZnO, 0-6% BaO, 0.2-2.0CdO, 0.2-1% S, and 0-1% Se; while the heat-treated glass-ceramics had the same composition as the sample of example 1 shown in tables 1A and 1B. Furthermore, the glass-ceramic shown in FIGS. 2A and 2B is prepared according to the methods of making glass-ceramic materials described above in the present disclosure, including a heat treatment step comprising heating the annealed melt at 700 ℃ for about 1 hour. In addition, both samples shown in FIGS. 2A and 2B have a normalized path length of 4 mm. From these figures, it was confirmed that the glass ceramic sample (example 1) heat-treated at 700 ℃ for 1 hour exhibited an approximate phase to the CdSe glass sample (comparative example 1)Sharp cut-off and sharpness in the same wavelength range.

Referring now to FIGS. 3A and 3B, graphs of transmittance versus wavelength are provided for comparative CdSe glasses ("comparative example 1") and heat-treated glass-ceramics ("examples 1A-1K"). Note that fig. 3B is the image of fig. 3A, rescaled to show the cut-off wavelengths of the comparative CdSe glass and heat treated glass-ceramic samples. In this example, a comparative example CdSe glass (comparative example 1) has a conventional CdSe glass composition according to: 40-60% SiO₂，5-20％B₂O₃，0-8％P₂O₅，1.5-6％Al₂O₃，4-8％Na₂O，6-14％K₂O, 4-12% ZnO, 0-6% BaO, 0.2-2.0CdO, 0.2-1% S, and 0-1% Se; while the heat-treated glass ceramic samples had the same compositions as the samples of example 1 shown in tables 1A and 1B, respectively. Further, the glass-ceramics shown in fig. 3A and 3B are respectively prepared according to the manufacturing method of the glass-ceramic material described above in the present disclosure, and include the following heat treatment steps after annealing: 525 ℃ for 1 hour 40 minutes (example 1A); 525 ℃ for 10 hours 39 minutes (example 1B); 550 ℃ for 3 hours 10 minutes (example 1C); 600 ℃ for 6 hours and 24 minutes (example 1D); 600 ℃ for 15 hours and 20 minutes (example 1E); 650 ℃ for 2 hours (example 1F); 650 ℃ for 3 hours (example 1G); 650 ℃ for 5 hours 35 minutes (example 1H); 650 ℃ for 23 hours 10 minutes (example 1I); 700 ℃ for 1 hour (example 1J); and 700 ℃ for 2 hours (example 1K). Furthermore, all samples shown in fig. 3A and 3B have a normalized path length of 4 mm. From these figures, it was confirmed that all glass ceramic samples (examples 1A to 1K) heat-treated according to various conditions exhibited sharp cutoff and sharpness in approximately the same wavelength range as CdSe glass (comparative example 1). Furthermore, it is evident from these figures that various heat treatment temperature and time conditions can be employed to vary and adjust the cutoff wavelength and its sharpness in the range of about 320nm to about 525 nm.

According to another example, the CdSe glasses of the comparative examples and the glass-ceramic samples heat-treated at 700 ℃ and 800 ℃ according to various conditions were preparedAnd their optical properties were evaluated. FIG. 4A is a graph of transmittance versus wavelength for comparative example CdSe glass ("comparative example 1") and glass-ceramic samples heat treated at 700 ℃ and 800 ℃ according to various conditions (examples 1K and 2A). Note that fig. 4B is the image of fig. 4A, rescaled to show the cutoff wavelengths of the comparative CdSe glass and the glass-ceramic samples heat-treated according to various conditions. In this example, a comparative example CdSe glass (comparative example 1) has a conventional CdSe glass composition according to: 40-60% SiO₂，5-20％B₂O₃，0-8％P₂O₅，1.5-6％Al₂O₃，4-8％Na₂O，6-14％K₂O, 4-12% ZnO, 0-6% BaO, 0.2-2.0CdO, 0.2-1% S, and 0-1% Se; the heat treated glass-ceramic sample (example 1K) had the same composition as the sample of example 1 shown in tables 1A and 1B; and the heat treated glass-ceramic sample (example 2A) had the same composition as the example 2 sample shown in tables 1A and 1B. Further, the glass-ceramics shown in fig. 4A and 4B are respectively prepared according to the manufacturing method of the glass-ceramic material described above in the present disclosure, and include the following heat treatment steps after annealing: 700 ℃ for 2 hours (example 1K); and 800 ℃ for 1 hour 4 minutes (example 2A). Furthermore, all samples shown in fig. 4A and 4B have a normalized path length of 4 mm. From these figures, it is confirmed that all glass ceramic samples heat-treated according to various conditions (examples 1K and 2A) exhibit sharp cutoff and sharpness in approximately the same wavelength range as CdSe glass (comparative example 1). Furthermore, it is also evident from these figures and the respective compositions of the glass-ceramics (see tables 1A and 1B) that these magnesium-tungsten glass-ceramic compositions can be used to vary and adjust the cutoff wavelength and its sharpness in the range of about 320nm to about 525nm by specific heat treatment conditions. It is also apparent that the higher magnesium content (about 3.84 mole%) in the example 2A glass-ceramic may contribute to its lower cutoff wavelength and may contribute to its higher transmittance in the NIR range compared to the example 1K glass-ceramic (about 0.95 mole%). Thus, and without being bound by theory, varying the magnesium content in these glass-ceramic compositionsAnd changing the heat treatment conditions will have an effect on changing the spectrum and cut-off wavelength of the glass-ceramic.

Referring now to fig. 4C, the image of fig. 4A is again provided along with a graph of transmittance versus wavelength for comparative example CuInSe and CuInS glass samples ("comparative example 2" and "comparative example 3", respectively). The spectra of comparative examples 2 and 3 were obtained from "exempt renewal request 13 (b)" submitted to the austrian institute (Oko-institute.v.) on 26.3.2015 from Spectaris e.v. Further, fig. 4 is enlarged to show the cutoff wavelengths of the CdSe glass of comparative example (comparative example 1), the glass ceramic samples heat-treated according to various conditions (examples 1K and 2A), and the CuInSe and CuInS samples of comparative examples (comparative examples 2 and 3). From fig. 4C, it is confirmed that the glass-ceramic materials according to the present disclosure (example 1K and example 2A) are superior to the comparative examples CuInSe and CuInS glasses in approaching the cutoff wavelength of the comparative example CdSe glass. That is, the optical properties of these glass-ceramics are closer to CdSe glasses than other semiconductor-doped glass substitutes (CuInSe and CuInS).

Referring now to fig. 5, an X-ray diffraction ("XRD") pattern is provided for a heat-treated glass-ceramic (example 1L, see tables 1A and 1B) according to at least one example of the present disclosure, this sample is heat-treated at 700 ℃ for 17 hours and 16 minutes as can be seen from the peak evidence for the listed d-spacing (e.g., d-3.6127, d-3.2193, etc.), example 1L glass-ceramic will include crystalline MgWO₄A tungsten oxide phase. Without being bound by theory, the XRD pattern of FIG. 5 also suggests that the glass-ceramic comprises a non-stoichiometric ratio of MgWO₄Phase or mixed alkaline-MgWO₄Phase, which can be described as M_xWO₄Crystals of formula (I) wherein M ═ Mg or M ═ Mg and one or more of alkali metals selected from L i, Na, K, Rb and Cd, and 0<x<1。

Referring now to FIGS. 6A-6C, a spray-quenched (splat-quenched) glass-ceramic sample (i.e., FIG. 6A, example 1, no heat treatment after annealing) is provided along with glass-ceramic samples according to examples of the present disclosure (example 1H and example 1L, respectively) heat treated at 650 deg.C for 5 hours 35 minutes and at 700 deg.C for 17 hours 16 minutes, as shown in FIGS. 6B and 6CShown) in the drawing. As with the previous examples, all glass-ceramic materials subjected to raman microscopy tests had a glass-ceramic composition according to example 1 in tables 1A and 1B. And FIG. 6B&The particular numerical designation associated with the data series in 6C (e.g., "# 1", "# 2-orange", "# 2-gray", etc.) corresponds to the particular evaluation location on the sample undergoing raman spectroscopy testing (including the color of the sample at those locations). FIG. 6A demonstrates that the spray quenched sample without further heat treatment (example 1) exhibits various increased strength levels (e.g., 470 cm) indicating no crystalline phase^-1Network bonds Si-O, Al-O and B-O) in contrast, fig. 6B and 6C demonstrate that the heat treated samples (examples 1H and 1L) have significantly higher intensity levels at the same raman shift location associated with the lower intensity level observed in the quench-sprayed sample (example 1), which indicates the presence of a crystalline phase (e.g., 846)&868cm^-1And MgW₂O₇The relevant W-O-W). Thus, it appears that the heat treatment conditions resulted in the establishment of a crystalline tungsten oxide phase (e.g., MgW)₂O₇) Evidence is at Raman-shifted positions (including but not limited to 345, 376, 404, 464, 718, 846, and 868 cm)^-1) There is a signal peak. Fig. 6B and 6C also suggest that the heat treatment conditions result in the establishment of a crystalline tungsten suboxide phase (i.e., non-stoichiometric ratio) as the crystalline tungsten oxide phase (i.e., M as described above)_xWO₄Crystalline phase) or combinations or substitutions.

Referring now to FIGS. 7A and 7B, Raman spectra are provided for glass-ceramic samples heat treated at 650 deg.C for 5 hours and 35 minutes and heat treated at 700 deg.C for 17 hours and 16 minutes according to examples of the present disclosure (example 1H and example 1L, respectively) and for glass-ceramic samples just after quenching (i.e., example 1, no heat treatment after annealing.) As with the previous examples, all glass-ceramic materials subjected to Raman microscopy testing all have glass-ceramic compositions according to example 1 in tables 1A and 1B, the specific numerical designations (e.g., "# 1", "# 2-orange", etc.) associated with the series of data in these figures correspond to those on samples subjected to Raman spectroscopy testingMost importantly, fig. 7A and 7B demonstrate that the spray quenched sample (example 1) has a significantly lower intensity level at the same raman shift location associated with the high intensity level associated with the sample subjected to the particular heat treatment conditions (examples 1H and 1L.) thus, demonstrating that the heat treatment conditions result in the establishment of a crystalline tungsten oxide phase (e.g., MgW as shown in both fig. 7A and 7B)₂O₇) And/or a crystalline tungsten suboxide phase (i.e., non-stoichiometric ratio).

Referring now to fig. 8, a graph of residual stress (MPa) versus substrate depth (mm) for two glass-ceramic samples (example 10-IOXA and example 10-IOXB) having compressive stress regions derived from two corresponding ion exchange process conditions is provided. In fig. 8, the y-axis is the residual stress in the substrate, positive values refer to tensile residual stress and negative values refer to compressive residual stress. Further, in fig. 8, the x-axis is the depth in each substrate, and the values at 0mm and 1.1mm represent the major surfaces of the substrate (e.g.,

major surfaces

12 and 14 of substrate 10 as shown in fig. 1). Each of the glass ceramic samples in this example (example 10-IOXA and example 10-IOXB) had the same composition as the example 10 sample shown in tables 1A and 1B. In addition, each sample was melted and poured onto a steel table to form an optical cake, consistent with the method described above in this disclosure. Each sample was then annealed at 570 ℃ for one hour and then cooled to ambient temperature at the furnace rate. Samples with dimensions of 25mm x 25mm x 1.1mm were then ground and polished to form an annealed optical cake. Finally, example 10-IOXA samples were immersed in 100% NaNO at 390 deg.C₃The molten salt bath was continued for eight hours (8 hours) to form a compressive stress region thereof. Similarly, example 10-IOXB immersion in 100% NaNO at 390 deg.C₃The molten salt bath was continued for sixteen hours (16 hours) to form its compressive stress region. It is noted that the actual thicknesses measured for examples 10-IOXA and 10-IOXB were 1.10mm and 1.06mm, respectively.

As demonstrated by FIG. 8, longer ion exchange durations tend to increase the DOC, stored strain energy, and magnitude of peak tension (i.e., central tension zone) of the glass-ceramicMaximum tensile stress in the domain) while reducing its maximum compressive stress. Specifically, the glass-ceramic sample with shorter ion exchange duration (example 10-IOXA) exhibited a compressive stress region with a depth of compression (DOC) of 136.7 μm, a maximum compressive stress of about-320 MPa, a Central Tension (CT) region given by a peak tension of 57MPa, and 16.6J/m²Stored strain energy. In contrast, the glass-ceramic sample with longer ion exchange duration (example 10-IOXB) exhibited 168.0 μm DOC, a maximum compressive stress of about-270 MPa, a CT region given by a peak tension of 72MPa, and 25J/m²Stored strain energy. Thus, the longer ion exchange duration of example 10-IOXB resulted in a larger DOC, lower maximum compressive stress, CT region given by the larger peak tension, and larger stored strain energy than example 10-IOXA with a shorter ion exchange process duration.

Although it was confirmed that the above-described glass-ceramic sample shown in FIG. 8 exhibited a structure due to immersion in 100% NaNO₃The established compressive stress region in the molten salt bath, but other approaches are contemplated by the present disclosure. For example, the glass-ceramic may be melted KNO₃、NaNO₃With KNO₃In a bath of the mixture of (a), or first in NaNO₃In the bath, the next step is in KNO₃In turn, ion exchange to increase the level of compressive stress on and near the surface of the substrate. Thus, ion exchange metal ions (e.g., Na) may also be employed in these baths⁺、K⁺Etc.) sulfates, chlorides, and other salts. Further, the ion exchange temperature may vary from about 350 ℃ to 550 ℃, with a preferred range of 370 ℃ to about 450 ℃ to prevent salt decomposition and stress relaxation.

Referring generally to fig. 9 through 11B, different sized crystalline regions are found in the tungsten bronze and multi-colored tungsten bronze glass-ceramics described above. The crystal size depends on the base glass composition, but can also be adjusted slightly by the heat treatment time and temperature. Furthermore, with the addition of small amounts of calcium oxide (CaO), the crystallization rate is significantly increased, which is believed to interact with tungsten oxide to form nanocrystals or non-stoichiometric barite-like structures of barite (scheelite) that can act as nucleation sites.

Referring now to FIG. 9, the highly super-aluminum tungsten bronze melt (e.g., M) described above_xWO₃Glass-ceramic) and as shown in fig. 9. These crystals had a needle-like shape, a length of 100-250nm and a width of 5-30 nm. In the as-quenched state (rapid quenching between two iron plates, i.e. spray quenching), these glass-ceramic materials are X-ray amorphous and Scanning Electron Microscope (SEM) analysis confirms the absence of precipitates (crystals, crystallites). After heat treatment of the quenched glass at 700 ℃ for 30 minutes or more and cooling to room temperature at 10 ℃ per minute, tungsten bronze precipitates and alumina-rich needles were formed. The precipitate concentration increases with increasing heat treatment time and temperature, for example after heat treatment at 700 ℃ for 1 hour 40 minutes and cooling to room temperature at 10 ℃/minute. X-ray energy dispersive X-ray spectroscopy (EDS) images of the crystallites formed after heat treatment show that they comprise tungsten, oxygen and potassium.

Referring to FIGS. 10A and 10B, for at least some of the overbased tungsten bronze melts (R)₂O-AL₂O₃>0) The crystallite size was smaller than in the superpure melt (figure 9) and no alumina rich needles were formed. Similar to a peraluminum melt, such an overbased material is X-ray amorphous when quenched (i.e., spray quenched) between two iron plates. The microscopic picture shows that no crystallites are present in the material before the heat treatment. TEM analysis showed the formation of high aspect ratio acicular tungsten bronze crystallites after a heat treatment of spray quenching at 550 ℃ for 15 to 30 hours, followed by cooling to 475 ℃ at 1 ℃/minute and then cooling to room temperature at the furnace rate, as shown in figures 10A to 10B. Most of the resulting needles were 2 to 7nm in diameter and 10 to 30nm in length. X-ray EDS of the heat treated quenched samples showed that the crystallites contained tungsten.

Referring to fig. 11A and 11B, the silver tungsten bronze glass-ceramic comprises crystallites that are generally rod-shaped in shape with an aspect ratio of 2 to 4, most commonly about 2-20nm in length, about 2-10nm in diameter, and about 11 to 14.8% by volume of the material glass-ceramic. The samples shown in fig. 11A and 11B were heat treated at 550 ℃ for 4 hours, cooled to 475 ℃ at 1 ℃/minute, and then cooled to room temperature at the furnace rate. The rod was then placed in a gradient furnace for 5 minutes so that one end of the rod was maintained at room temperature and the other end of the rod was 650 ℃. The area between each end is exposed to an approximately uniform gradient between temperatures of 25 ℃ to 650 ℃. In the region where the temperature is above about 575 ℃, the color begins to shift 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 transmittance of about 5%/mm or greater over at least one 50nm wide wavelength band in the range of about 400nm to about 700 nm. However, in other embodiments, the glass-ceramic has a lower transmittance, such as those that are opaque. In accordance with at least some such embodiments, these glass-ceramics are unique in that they are strongly absorbing, 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., most, > 90%) of light at 200-400nm wavelengths, up to 25OD/mm for the same wavelength, and/or a haze of less than 10%, wherein the optical density is calculated by measuring the optical absorbance with a spectrophotometer and the haze is measured by a haze meter 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., most (> 90%) light at 400-750nm wavelength, up to 10OD/mm for the same wavelength, and/or has a haze of less than 10%. 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., most (> 90%) of light at wavelengths of 750-2000 nm), up to 15OD/mm for the same wavelengths, and/or has a haze of less than 10%.

Examples of titanium

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

TABLE 8A

TABLE 8B

Referring now to table 8C and fig. 12A-17B, optical data for the compositional samples of tables 8A and 8B are provided.

TABLE 8C

Various compositions of table 8C and fig. 12A-17B were prepared as follows: the batch components are weighed, mixed by a vibratory mixer or ball mill, and melted in a fused silica crucible at a temperature of 1300 ℃ to 1650 ℃ for 4 to 32 hours. Glass was poured onto a metal table to produce a 0.5mm thick glass cake. Some of the melt was poured onto a steel table and then rolled into sheet using steel rolls. To establish and control the optical transmittance and absorbance, the samples were heat treated in an ambient air electric oven at a temperature of 425 ℃ to 850 ℃ for 5 to 500 minutes. The sample cake was then polished to a thickness of 0.5mm and tested.

From the data in Table 8C and FIGS. 12A-17B, it is confirmed that the as-manufactured state of the titanium-containing glass is highly transparent in the NIR region and is largely transparent at visible wavelengths. After heat treatment at temperatures of about 500 ℃ to about 700 ℃, the crystalline phase (i.e., titanium suboxide) precipitates, and the optical transmission of these samples decreases and some becomes strongly absorbing in the NIR.

The heat treated samples show evidence of some titania-containing crystalline phases, including anatase (889F L Y) and rutile (889FMC and 889 FMD). the samples exhibit low haze (i.e., about 10% or less, or about 889FMD)<5% or less, or about 1% or less, or about 0.1% or less). Without being bound by theory, the low haze exhibited by these compositions in the as-manufactured and post-heat treated state is a result of the fact that: the crystallites are very small (i.e., about 100nm or less) and are low in abundance (i.e., due to the incorporated TiO)₂The fact that only about 2 mole percent). Thus, it is believed that the species formed in these materials are below the detection limits of conventional powder XRD. This hypothesis was confirmed by TEM microscopy.

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

Referring now to fig. 19A and 19B, a TEM micrograph (fig. 19A) and a corresponding EDS elemental map (fig. 19B) of a heat treated sample of glass number composition 889FMC are provided. As can be seen from fig. 19A, the sample includes a plurality of crystallites. The EDS plot was set to detect titanium. It can be seen that the EDS plotted the results for titanium closely followed the crystallite traces, indicating that the crystallites are enriched in titanium. In this figure, the bright or 'white' regions indicate the presence of Ti.

Referring now to fig. 9A, an exemplary glass composition that is free of titanium is provided.

TABLE 9A

Table 9B provides solar performance measurements for various glasses. In Table 9B, a composition of 196KGA was combined as the clad layer (i.e., total clad glass-ceramic thickness of 0.2mm) of a dual fusion laminate, where the core composition of the laminate was from Corning, Inc. (Corning)

) Chemical strengthening of

And (3) glass. The composition 196KGA is 1mm thick, heat treated at 550 ℃ for 30 minutes and cooled to 475 ℃ at 1 ℃ per minute. 889FMD samples were 5mm thick and were heat processed at 600 ℃ for 1 hour. 889FMG samples were 0.5mm thick and were heat processed at 700 deg.C for 2 hours. The VG10 sample is referred to as Saint-

) Glasses sold under the name SGG VENUS (VG 10) and differing in thickness from each other.

TABLE 9B

In Table 9B, T _ L is the total visible transmission (this is the weight average transmission of light through the glazing in the wavelength range of 380nm to 780nm and is measured in accordance with ISO 9050 section 3.3.) T _ TS is the total transmitted solar energy (also known as the solar factor ("SF") or the total solar thermal transmission ("TSHT"), which is the sum of T _ DS (total direct solar energy) plus the fraction that is absorbed by the glazing and then re-radiated into the vehicle interior, calculated in accordance with ISO13837 appendix 2008B & ISO 9050 section 3.5.) in this case T _ TS is calculated for a parking condition with a wind speed of 4m/s (14 km/h), "T _ DS) +0.276 (% solar energy absorption),. T _ DS is the total direct solar energy transmission (also known as" solar energy transmission "(" Ts ") or" energy transmission 2500 ") measured in accordance with ISO 9037 nm to the weight average transmission of light through the glazing in the wavelength range of 300nm to 780nm, measured in accordance with ISO 1386. UV reflectance measured in accordance with ISO 9037. UV reflectance standards T _ DS, UV 1387, R..

As self-evident from the data in table 9B, glass number 196KGA has the best optical performance and is capable of producing the lowest UV, visible and NIR transmittance over a very short path length (0.2 mm). At 0.5mm thickness, the titanium-containing compositions 889FMD and 889FMG produced optical performance superior to VG10 glass for path lengths of 3.85mm or less than 3.85 mm. In other words, the titanium-containing compositions 889FMD and 889FMG performed better than VG10 glass despite the shorter path length.

Further, with reference to at least some of the glass-ceramics disclosed or contemplated herein, the glass-ceramics include an amorphous phase and a crystalline phase, wherein the crystalline phase includes (e.g., includes, is predominantly) a bronze structure as disclosed herein, e.g., having a formula M_xTiO₂、M_xWO₃And the like, as disclosed herein. The volume fraction of the crystalline phase may be from about 0.001% to about 20%, alternatively from about 1% to about 20%, alternatively from about 5% to about 20%, alternatively from about 10% to about 30%, alternatively from about 0.001% to about 50%. In other embodiments, the volume fraction of the crystalline phase may be from about 0.001% to about 20%, alternatively from about 0.001% to about 15%, alternatively from about 0.001% to about 10%, alternatively from about 0.001% to about 5%, alternatively from about 0.001% to about 1%. In other contemplated embodiments, the volume fraction of crystalline phases in the glass-ceramic may be greater than 50%.

With further reference to at least some of the glass-ceramics disclosed or contemplated herein, the glass-ceramics comprise an amorphous phase and a crystalline phase, wherein the crystalline phase comprises (e.g., comprises, is predominantly) a bronze structure as disclosed herein, e.g., having a formula M_xTiO₂、M_xWO₃Etc., as disclosed herein, wherein M represents asThe dopant cations, and precipitates (e.g., crystals) disclosed herein are suboxides, where 0<x<1, e.g. wherein 0<x<1，0<x<0.9, e.g. wherein 0<x<0.75, e.g. wherein, 0<x<0.5, e.g. wherein 0<x<0.2, and/or for example, wherein, 0.01<x<1, e.g. wherein, 0.01<x<1, e.g. wherein, 0.1<x<1, e.g. wherein, 0.2<x<1, and/or wherein, 0.5<x<1, e.g. wherein, 0.001<x<0.999, e.g. wherein, 0.01<x<0.99, e.g. wherein, 0.1<x<0.9, e.g. wherein, 0.2<x<0.9, or wherein, 0.1<x<0.8。

The construction and arrangement of the methods and products shown in the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, many modifications are possible (e.g., to the sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations) without materially departing from the novel teachings and advantages of the subject matter recited herein. Some elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or modified. The order or sequence of any process, logical algorithm, or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the technical scope of the present invention.

Claims

1. A glass-ceramic, comprising:

an amorphous phase; and

a crystalline phase comprising a plurality of precipitates, said precipitates comprising M_xWO₃And/or M_xMoO₃In the formula, 0<x<1 and M are dopant cations.

2. The glass ceramic of claim 1, wherein the length of the precipitate is from about 1nm to about 200nm as measured by electron microscopy.

3. The glass-ceramic of claim 1 or 2, wherein the precipitates of the crystalline phase are substantially homogeneously distributed in the glass-ceramic.

4. A glass-ceramic, comprising:

silicate glass; and

crystals homogeneously distributed in the silicate-containing glass, wherein the crystals comprise non-stoichiometric amounts of tungsten and/or molybdenum suboxides, and dopant cations are inserted into the crystals.

5. The glass-ceramic of claim 4, wherein the glass-ceramic comprises a transmittance of about 5%/mm or greater over at least one 50nm wide optical wavelength band in the range of about 400nm to about 700 nm.

6. The glass-ceramic of claim 4 wherein the dopant cation comprises at least one of H, L i, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, L a, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, L U, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce.

7. The glass-ceramic of claim 4 wherein the crystals have a rod-like morphology.

8. The glass ceramic of claim 4, wherein a portion of the crystals are located at a depth greater than about 10 μm from the outer surface of the glass ceramic.

9. A glass-ceramic, comprising:

a glassy phase; and

a crystalline phase comprising a suboxide of tungsten and/or molybdenum, the suboxide of tungsten and/or molybdenum comprising a solid state defect structure in which pores are occupied by dopant cations.

10. The glass-ceramic of claim 9, wherein the crystalline phase occupies a volume fraction of the glass-ceramic of about 0.001% to about 20%.

11. An article of manufacture, comprising:

at least one amorphous phase and a crystalline phase; and

SiO₂about 1 molar% to about 95 molar%;

wherein the crystalline phase comprises from about 0.1 mol% to about 100 mol% of an oxide of the crystalline phase, wherein the oxide comprises at least one of: (i) w, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.

12. The article of claim 11, wherein the crystalline phase is substantially uniformly distributed in the article as a plurality of precipitates.

13. The article of claim 12, wherein at least a portion of the precipitates are located at a depth greater than about 10 μ ι η from an outer surface of the article.

14. The article of claim 11, wherein the crystalline phase comprises a plurality of precipitates comprising a length of about 1nm to about 500nm as measured by electron microscopy.

15. The article of claim 11, wherein the article is substantially free of Cd and Se.

16. A glass comprising, in batch components:

SiO₂about 25 molar% to about 99 molar%;

Al₂O₃about 0 molar% to about 50 molar%;

WO₃adding MoO₃About 0.35 molar% to about 30 molar%;

R₂o from about 0.1 mol% to about50 mol%, wherein R₂O is L i₂O、Na₂O、K₂O、Rb₂O and Cs₂One or more of O, and wherein R₂O minus Al₂O₃Is about-35 mole% to about 7 mole%; and

at least one of: (i) RO about 0.02 mol% to about 50 mol%, and (ii) SnO₂About 0.01 mol% to about 5 mol%, wherein RO is one or more of MgO, CaO, SrO, BaO, and ZnO;

wherein, if WO₃From about 1 mol% to about 30 mol%, the glass further comprises about 0.9 mol% or less Fe₂O₃Or SiO₂Then from about 60 mole% to about 99 mole%;

wherein, if WO₃From about 0.35 mol% to about 1 mol%, the glass comprises from about 0.01 mol% to about 5.0 mol% SnO₂；

Wherein, if MoO₃About 1 mol% to about 30 mol%, SiO₂Is about 61 mol% to about 99 mol%, or Fe₂O₃Is about 0.4 mol% or less and R₂O is greater than RO;

wherein, if MoO₃Is about 0.9 mol% to about 30% and SiO₂Is from about 30 mole% to about 99 mole%, the glass further comprises from about 0.01 mole% to about 5 mole% SnO₂。

17. The glass of claim 16, further comprising B₂O₃About 2.0 mol% to about 40 mol%, wherein, SiO₂Is about 45 mol% to about 80 mol%, and Al₂O₃Is about 0.5 mol% to about 15 mol%, wherein R₂O is about 0 mol% to about 14 mol% and RO is about 0 mol% to about 1 mol%, and wherein at least one of: (1) MoO₃Is about 0 mol% and WO₃Is about 1.0 molar% to about 17 molar%; (2) SnO₂Is about 0.01 molar% to about 0.4 molar%; and/or (3) Fe₂O₃Is about 0 mol% to about 0.2 mol%.

18. The glass of claim 16, further comprising B₂O₃About 5 mol% to about 20 mol%, wherein, SiO₂Is about 55 mol% to about 75 mol%, and Al₂O₃Is about 8 mol% to about 12 mol%, wherein R₂O is about 3 to about 14 mole% and RO is about 0.5 to about 4.5 mole%, wherein, WO₃Is about 1.9 mol% to about 10 mol%, and wherein, MoO₃Is about 0 mol% to about 1.0 mol%.

19. The glass of claim 16, further comprising B₂O₃About 4 mol% to about 35 mol%, wherein, SiO₂Is about 55 mol% to about 75 mol%, Al₂O₃Is about 9 mol% to about 14 mol%, wherein R₂O is about 2.9 mol% to about 12.2 mol% and RO is about 0.01 mol% to about 0.5 mol%, wherein MoO₃Is about 0 mol% to about 8.2 mol% and WO₃Is about 0 mol% to about 9 mol%, and wherein at least one of: (1) SnO₂Is about 0.04 mol% to about 0.4 mol%, (2) Fe₂O₃Is about 0 mol% to about 0.2 mol%, and/or (3) V₂O₅Is about 0 mol% to about 0.4 mol%.

20. The glass of claim 16, further comprising B₂O₃About 5 mol% to about 25 mol%, wherein, SiO₂Is about 50 mol% to about 75 mol% and Al₂O₃Is about 7 mol% to about 14 mol%, wherein R₂O is about 5 mol% to about 14 mol% and RO is about 0.02 mol% to about 0.5 mol%, wherein MoO₃Is about 1.9 mol% to about 12.1 mol% and WO₃Is about 1.7 mole% to about 12 mole%, and wherein at least one of: (1) the glass further comprises about 0.01 mol% to about 0.75 mol% Ag, about 0.01 mol% to about 0.5 mol% Au, and V₂O₅From about 0.01 mole% to about 0.03 mole%,and CuO from about 0.01 mol% to about 0.75 mol%; and/or (2) SnO₂Is about 0.01 mole% to about 0.5 mole%.

21. The glass of claim 16, further comprising B₂O₃About 10 mol% to about 20 mol%, wherein, SiO₂Is about 60 mol% to about 78 mol%, Al₂O₃Is about 0.3 mol% to about 10 mol%, wherein R₂O is about 0.6 mol% to about 10 mol% and RO is about 0.02 mol%, and wherein WO₃Is about 0 mol% and MoO₃Is about 1.0 mol% to about 7.0 mol%.

22. A method of forming a glass-ceramic article, comprising:

melting together to form a glass melt, components comprising (1) bound alkali species, (2) silica, and (3) tungsten and/or molybdenum;

solidifying the glass melt into glass; and

a crystalline phase is precipitated in the glass to form the glass-ceramic article.

23. The method of claim 22, wherein the glass is a homogeneous single phase.

24. The method of claim 22 or 23, wherein a crystalline phase comprises the tungsten and/or molybdenum.

25. The method of any one of claims 22 to 24, wherein the bound alkaline substance comprises: (A) feldspar, (B) nepheline, (C) sodium borate, (D) spodumene, (E) albite, (F) potash feldspar, (G) alkali-containing aluminosilicate, (H) alkali-containing silicate, and/or (I): (I-I) an alkaline substance bound to alumina, (I-ii) an alkaline substance bound to boria, and/or (I-iii) an alkaline substance bound to silica.

26. A method of forming a glass-ceramic article, comprising:

melting together components comprising silica and tungsten and/or molybdenum to form a glass melt;

solidifying the glass melt to form glass; and

precipitating a plurality of bronze type crystals comprising said tungsten and/or molybdenum in the glass.

27. The method of claim 26, wherein the precipitating of the plurality of bronze crystals comprises hot working the glass.

28. The method of claim 26 or 27, further comprising growing a plurality of bronze type crystals to a length of at least about 1nm and no more than about 500 nm.

29. A glass-ceramic, comprising:

an amorphous phase; and

a crystalline phase comprising a compound of formula M_xTiO₂A precipitate of (A), wherein 0<x<1 and M are dopant cations.

30. The glass-ceramic of claim 29, wherein the glass-ceramic exhibits a transmittance of about 1%/mm or greater over at least one 50nm wide optical wavelength band in the range of about 400nm to about 700 nm.

31. The glass ceramic of claim 29, wherein at least some of the precipitates are at least 1nm in length and no more than 300nm in length.

32. The glass-ceramic of claim 31 wherein the precipitates of crystalline phases are uniformly distributed in the glass-ceramic.

33. The glass-ceramic of claim 31 wherein the formula is M_xTiO₂The volume fraction of precipitates in the glass-ceramic is at least 0.001% and not more than 20%.

34. The glass ceramic of claim 33, wherein the formula is M_xTiO₂The volume fraction of precipitates in the glass-ceramic is at least 5%.

35. The glass-ceramic of claim 34 wherein the dopant cation comprises H, L i, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, L a, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, L U, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and/or Ce.

36. A glass-ceramic, comprising:

silicate glass; and

crystals homogeneously distributed in the silicate glass, wherein the crystals comprise titanium suboxide intercalated with dopant cations.

37. The glass-ceramic of claim 36, wherein the glass-ceramic exhibits a transmittance of about 1%/mm or greater over at least one 50nm wide optical wavelength band in the range of about 400nm to about 700 nm.

38. The glass ceramic of claim 36, wherein the crystals are at least 1nm in length and no more than 300nm in length.

39. The glass-ceramic of claim 38 wherein the crystals are uniformly distributed in the glass-ceramic.

40. The glass-ceramic of claim 38 wherein the volume fraction of crystals in the glass-ceramic is at least 0.001% and no more than 20%.

41. The glass ceramic of claim 40, wherein the volume fraction of crystals in the glass ceramic is at least 5%.

42. The glass-ceramic of claim 41 wherein the dopant cations comprise H, L i, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, L a, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, L U, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and/or Ce.

43. A glass-ceramic, comprising:

a glassy phase; and

a crystalline phase of titanium-containing suboxide that forms a solid state defect structure in which pores are occupied by dopant cations.

44. The glass-ceramic of claim 43, wherein the glass-ceramic has a transmittance of about 1%/mm or greater over at least one 50nm wide optical wavelength band in the range of about 400nm to about 700 nm.

45. A glass-ceramic article, comprising:

at least one amorphous phase and a crystalline phase; and

SiO₂about 1 molar% to about 95 molar%;

wherein the crystalline phase comprises from about 0.1 mol% to about 100 mol% of the crystalline phase of a non-stoichiometric titanium suboxide comprising at least one of: (i) ti, (ii) V and an alkali metal cation.

46. The glass-ceramic article of claim 45, wherein the crystalline phase is substantially uniformly distributed in the glass-ceramic article as a plurality of precipitates.

47. The glass-ceramic article of claim 46, wherein at least some of the precipitates are located at a depth greater than about 10 μm from the outer surface of the article.

48. The glass-ceramic article of claim 45, wherein the crystalline phase comprises a plurality of precipitates comprising a length of about 1nm to about 500nm as measured by electron microscopy.

49. The glass-ceramic article of claim 45, wherein the article is substantially free of Cd and Se.

50. A method of forming a glass-ceramic article, comprising:

melting components comprising silica and titanium together to form a glass melt;

solidifying the glass melt to form a glass, wherein the glass comprises a first average near-infrared absorbance; and

precipitating a crystalline phase in a glass to form a glass-ceramic, the glass-ceramic comprising: (a) a second average near infrared absorbance, wherein a ratio of the second average near infrared absorbance to the first average near infrared absorbance is about 1.5 or greater, and (b) an average optical density per mm of about 1.69 or less.

51. The method of claim 50, wherein the precipitation of the crystalline phase is performed at a temperature of about 450 ℃ to about 850 ℃.

52. The method of claim 50, wherein the precipitation of the crystalline phase is performed at a temperature of about 500 ℃ to about 700 ℃.

53. The method of claim 50, wherein the precipitation of the crystalline phase is carried out for a period of time from about 15 minutes to about 240 minutes.

54. The method of claim 50, wherein the precipitation of the crystalline phase is carried out for a period of time from about 60 minutes to about 90 minutes.

55. A glass comprising, in batch components:

SiO₂about 1 molar% to about 90 molar%;

Al₂O₃about 0 molar% to about 30 molar%;

TiO₂about 0.25 molar% to about 30 molar%;

metal sulfide from about 0.25 molar% to about 30 molar%;

R₂o from about 0 mol% to about 50 mol%, wherein R₂O is L i₂O、Na₂O、K₂O、Rb₂O and Cs₂One or more of O; and

RO is about 0 mol% to about 50 mol%, wherein RO is one or more of BeO, MgO, CaO, SrO, BaO, and ZnO, wherein the glass is substantially free of Cd.

56. The glass of claim 55, wherein the TiO is₂Is about 1.0 mol% to about 15 mol%.

57. The glass of claim 55, wherein the TiO is₂Is about 2.0 mol% to about 10 mol%.

58. The glass of claim 55, wherein the metal sulfide is about 1.0 mol% to about 15 mol%.

59. The glass of claim 58, wherein the metal sulfide is about 1.5 mol% to about 5 mol%.

60. The glass of any one of claims 55-59, wherein the metal sulfide comprises MgS, Na₂At least one of S and ZnS.

61. The glass of claim 55, wherein the glass is substantially free of L i.

62. The glass of claim 55, wherein the glass is substantially free of Zr.