JP2021500299A - Glass ceramic and glass - Google Patents

Abstract

Glass ceramics include a silicate-containing glass phase and a crystalline phase, the crystalline phase containing tungsten and / or molybdenum, or a non-chemical suboxide of titanium, with pores occupied by dopant cations. Forming a "bronze" type solid defect structure.

Description

Description of related application

This application claims priority to US Provisional Patent Application No. 62/575763 filed on October 23, 2017, and US Patent Application No. 15/840040 filed on December 13, 2017. This is a partial continuation application of the issue, and the contents of both applications are all cited here.

The present disclosure relates broadly to articles comprising glass and / or glass ceramics, and more particularly to compositions and methods for forming such articles.

Metallic ultraviolet (“UV”) and near-infrared (“NIR”) -absorbing alkali-containing silicate glass-ceramics are a class of glass-ceramics that exhibit optical properties that depend on the wavelength of light incident on the glass-ceramic. Conventional UV / IR blocking glass (low or high visible transmittance) has certain cation species that bind to the network structure (eg, Fe2 + for absorbing NIR wavelengths and Fe23 + for absorbing UV wavelengths, as well as It is formed by introducing other dopants such as Co, Ni, and Se to change the visible transmittance. Since ancient times, these glass ceramics have been formed by melting the components together to form a glass, followed by the in-situ formation of submicron precipitates by post-formation heat treatment to form the glass ceramic. manufactured. These submicron precipitates (eg, tungstate and molybdate-containing crystals) absorb some wavelengths of light and give the glass ceramic optical properties. Such conventional glass-ceramics could be produced in both transparent and opalescent forms.

Traditional tungsten and molybdenum / alkali-containing silicate glasses have been thought to be constrained to a particular narrow composition range in order to produce transparent glass and glass ceramics at visible wavelengths. This considered composition range was based on the recognized dissolution limits of tungsten oxide in peralkali glass. For example, tungsten oxide, when batch-blended and melted in a conventional fashion, reacts with the alkali metal oxides in the batch and is cold and dense tungstic acid during the initial stages of melting immediately after being placed in the melting furnace. An alkaline liquid can be formed (eg, the reaction occurs at about 500 ° C.). Due to its high density, this phase segregates rapidly at the bottom of the crucible. The silicate component begins to melt at significantly higher temperatures (eg, above about 1000 ° C.) and remains on the tungstic acid alkaline liquid as its density is lower. Differences in the densities of these components result in stratification of different liquids, which gives those skilled in the art an appearance that is immiscible with each other. This effect is particularly effective when the value obtained by subtracting Al ₂ O ₃ from R ₂ O (for example, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O) is 0 mol% or more. It was observed. The apparent liquid immiscibility that appeared at the melting temperature resulted in segregation and crystallization of the tungsten-rich phase when cooled, which appeared as milky white opaque crystals. This problem was also present in molybdenum-containing melts.

Those skilled in the art observe a tungsten and / or molybdenum-rich phase separate from the silicate-rich phase and dissolve limits of tungsten and / or molybdenum within the silicate-rich phase (eg, about 2). .5 mol%) was recognized. The recognized dissolution limit always prevents the glass from becoming supersaturated with tungsten oxide or molybdenum, thereby both components post-formation heat treatment to produce a glass ceramic having a crystalline phase containing these elements. Prevented controllable precipitation. Therefore, the recognized solubility is a glass-ceramic composition that achieves a sufficient amount of dissolved tungsten and / or molybdenum by subsequent heat treatment to allow the formation of tungsten and / or molybdenum-containing wavelength-dependent submicron crystals. It hindered the development of things.

In view of these limitations, there is a need for new compositions and methods of making them that facilitate improved near-infrared and UV blocking (eg, due to the higher solubility of tungsten and molybdenum).

It has been found that the use of "bound" alkalis as described herein may result in uniform single-phase W or Mo-containing peralkali melts. Examples of binding alkalis are feldspar, nepheline, porcelain, spojumen, other albite or potash feldspars, alkali aluminosilicates and / or other natural containing alkali and one or more aluminum and / or silicon atoms. Generating and artificially produced minerals may be mentioned. By introducing the alkali in a bound form, the alkali will not react with the W or Mo present in the melt to form a dense alkali tungstate and / or alkaline molybdate liquid. In addition, this modification in the batch material results in a strong per-alkali composition (eg, R ₂ O-Al ₂ O ₃ = about) without forming any second phase of alkali tungstate and / or alkali molybdate. More than 2.0 mol%) will be possible to melt. This also allows for varying melting temperatures and mixing methods, yet single-phase uniform glass is produced.

According to aspects of the present disclosure, the glass ceramic comprises a silicate-containing glass phase and a crystalline phase, the crystalline phase having a "bronze" type solid defect structure in which the pores are occupied by dopant cations. Includes non-chemical suboxides of tungsten and / or molybdenum, or titanium that form.

In some embodiments, the glass ceramic comprises an amorphous phase and a crystalline phase comprising a plurality of precipitates of the formula M _x WO ₃ and / or M _x MoO ₃ , where 0 <x <1. , M are dopant cations. In some of such embodiments, the precipitate has a length of about 1 nm to about 200 nm as measured by electron microscopy. The precipitates of the crystalline phase may be substantially uniformly distributed within the glass ceramic.

Further, the glass-ceramic contains an amorphous phase and a crystalline phase containing a plurality of precipitates of the formula M _x TiO ₃ , where 0 <x <1 and M is a dopant cation. In some of such embodiments, the precipitate has a length of about 1 nm to about 200 nm, or about 1 nm to about 300 nm, or about 1 nm to about 500 nm, as measured by electron microscopy. The precipitates of the crystalline phase may be substantially uniformly distributed within the glass ceramic.

In some embodiments, the glass ceramic is a non-chemically quantitative tungsten and / or molybdenum suboxidation in which a silicate-containing glass and uniformly distributed dopant cations are inserted in the silicate-containing glass. Including crystals of things. The glass-ceramic may have a transmittance of about 5% per mm or more over at least one 50 nm wide wavelength range of light in the range of about 400 nm to about 700 nm. Dopant cations are H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd. , Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and / or Ce. Good. In some of such embodiments, at least some of the crystals are at a depth greater than about 10 μm from the outer surface of the glass ceramic. The crystals may have a rod-like morphology.

In some embodiments, the glass ceramic is a silicate-containing glass phase and a crystalline phase containing a suboxide of tungsten and / or molybdenum that forms a solid defect structure in which holes are occupied by dopant cations. And include. The volume fraction of the crystal phase in the glass ceramic may be from about 0.001% to about 20%.

In other embodiments, the glass ceramic is a silicate-containing glass and a crystal of non-chemical quantitative titanium hydroxide in which dopant cations uniformly distributed within the silicate-containing glass are inserted; and / Alternatively, it includes a silicate-containing glass phase and a crystal phase containing a suboxide of titanium that forms a solid defect structure in which holes are occupied by dopant cations.

In some embodiments, the article comprises at least one amorphous phase and one crystalline phase, which article comprises from about 1 mol% to about 95 mol% SiO ₂ as a batch component. The crystal phase is at least one of (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation: about 0. Contains 1 mol% to about 100 mol% oxide. The article may be substantially free of Cd and Se.

In yet another embodiment, the glass, such as the glass precursor of glass ceramic, has about 25 mol% to about 99 mol% SiO ₂ and about 0 mol% to about 50 mol% Al ₂ O in the batch component. _3. Containing about 0.35 mol% to about 30 mol% WO ₃ + MoO ₃ , and about 0.1 mol% to about 50 mol% R ₂ O, where R ₂ O is Li ₂ O, It is one or more of Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O, and R ₂ O-Al ₂ O ₃ is from about -35 mol% to about 7 mol%. In some of such embodiments, (i) RO is in the range of about 0.02 mol% to about 50 mol%, and (ii) SnO ₂ is from about 0.01 mol% to about. At least one of 5 mol%, where RO is one or more of MgO, CaO, SrO, BaO and ZnO. In some of such embodiments, if WO ₃ is from about 1 mol% to about 30 mol%, the glass thus contains less than about 0.9 mol% Fe ₂ O ₃ or As a result, SiO ₂ is about 60 mol% to about 99 mol%. If WO ₃ is from about 0.35 mol% to about 1 mol%, then the glass may contain from about 0.01 mol% to about 5.0 mol% SnO ₂ . If MoO ₃ is from about 1 mol% to about 30 mol%, thus SiO ₂ can range from about 61 mol% to about 99 mol%, or Fe ₂ O ₃ can be about 0.4. It may be less than or equal to mol%, and R ₂ O is higher than RO. If MoO ₃ is from about 0.9 mol% to about 30 mol% and SiO ₂ is from about 30 mol% to about 99 mol%, then the glass is from about 0.01 mol% to about 5 mol. May further contain% SnO ₂ .

In some embodiments, the method of forming a glass ceramic is the step of melting (1) bound alkali, (2) silica, and (3) tungsten and / or molybdenum together to form a glass melt. It comprises a step of solidifying the glass melt into glass; and a step of precipitating a crystal phase in the glass to form a glass-ceramic article. The glass may be a single homogeneous solid phase. The crystalline phase may contain tungsten and / or molybdenum. Moreover, in some of such embodiments, the binding alkalis are (A) feldspar, (B) nepheline, (C) sodium borate, (D) spojumen, (E) albite, (F). Bonded to potash feldspar, (G) alkaline aluminosilicate, (H) alkaline silicate, and / or (I) (Ii) alumina, (I-ii) boria and / or (I-iii) silica Contains alkali.

In another embodiment, the method of forming a glass ceramic is a step of melting silica and tungsten and / or molybdenum together to form a glass melt, solidifying the glass melt to form glass. It comprises a step and a step of precipitating bronze-type crystals containing tungsten and / or molybdenum in the glass thereof. The step of precipitating the crystal phase may include a step of heat-processing the glass. In at least some of such embodiments, the method further comprises the step of growing the precipitate of the crystalline phase to a length of at least about 1 nm and no more than about 500 nm.

In another embodiment, the glass ceramic comprises a silicate-containing glass phase and a crystalline phase containing a titanium suboxide, in which the titanium suboxide has holes occupied by dopant cations. Includes solid defect structure.

In another embodiment, the glass ceramic comprises an amorphous phase and a crystalline phase containing a plurality of precipitates of formula M _x TiO ₂ , where 0 <x <1 and M is a dopant cation. Is.

In other embodiments, the glass ceramic comprises a silicate-containing glass and a plurality of crystals uniformly distributed within the silicate-containing glass, wherein the crystals are non-chemically sub-quantitative. It contains titanium oxide, and dopant cations are further inserted into the crystal.

In another embodiment, the glass-ceramic article comprises at least one amorphous phase and a crystalline phase, and about 1 mol% to about 95 mol% SiO ₂ , where the crystalline phase is about the crystalline phase. It contains from 0.1 mol% to about 100 mol% non-stoichiometric titanium suboxide, the suboxide containing at least one of (i) Ti, (ii) V and alkali metal cations. ..

In another embodiment, the method of forming a glass ceramic is the step of melting the components containing silica and titanium together to form a glass melt; the glass melt is solidified to near the first average. The step of forming a glass with infrared absorbance; and precipitating a crystalline phase in the glass, (a) a second average near-infrared absorbance, and (b) average optics per mm of about 1.69 or less. It is a step of forming a glass ceramic having a density, and includes a step in which the ratio of the second average near-infrared absorbance to the first average near-infrared absorbance is about 1.5 or more.

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

These and other features, advantages, and objectives of this disclosure will be further understood and recognized by those skilled in the art by reference to the following specification, claims, and accompanying drawings.

The accompanying drawings are included to give further understanding and are included in the specification and form a part thereof. The drawings of the drawings show one or more embodiments and serve to explain the principles and operations of the various embodiments, along with detailed description. Therefore, this disclosure will be better understood from the following detailed description when interpreted with the accompanying drawings.

Sectional drawing of an article comprising a substrate made from a glass-ceramic composition according to at least one example of the present disclosure. Plot of transmittance for wavelength of comparative CdSe glass and heat treated glass ceramic according to at least one example of the present disclosure. Plot of FIG. 2A scaled to show cutoff wavelengths for comparative CdSe glass and heat treated glass ceramic samples. Plot of transmission over wavelength of comparative CdSe glass and glass ceramic samples heat treated at 525 ° C to 700 ° C according to various conditions according to the examples of the present disclosure. Plot of FIG. 3A scaled to show cutoff wavelengths of comparative CdSe glass and glass ceramic samples heat treated according to various conditions. Plot of transmittance over wavelength of comparative CdSe glass and glass ceramic samples heat treated at 700 ° C and 800 ° C according to various conditions according to the examples of the present disclosure. Plot of FIG. 4A scaled to show cutoff wavelengths of samples of comparative CdSe glass and glass ceramics heat treated according to various conditions. The scale was changed to show the cut-off wavelengths of the comparative CdSe glass samples, the glass ceramic samples heat-treated according to various conditions, and the CuInSe and CuInS samples, as well as the transmission of the comparative CuInSe and CuInS glass samples to wavelength. , Figure 4A plot X-ray diffraction (“XRD”) plot of heat treated glass ceramic according to at least one example of the present disclosure. Raman spectroscopy plots of splat-quenched glass-ceramic samples according to the examples of the present disclosure. Raman spectroscopy plots of splat-quenched glass-ceramic samples and glass-ceramic samples heat-treated at 650 ° C. according to various conditions according to the examples of the present disclosure. Raman spectroscopy plots of splat-quenched glass-ceramic samples and glass-ceramic samples heat-treated at 700 ° C. according to various conditions, according to the examples of the present disclosure. Raman spectroscopy plot of a glass-ceramic sample heat-treated at 650 ° C. according to various conditions and a glass-ceramic sample as splat-quenched according to the examples of the present disclosure. Raman spectroscopy plot of a glass-ceramic sample heat-treated at 700 ° C. according to various conditions and a glass-ceramic sample that remains splat-quenched according to the examples of the present disclosure. Plot of residual stress relative to substrate depth of two glass-ceramic samples with compressive stress regions resulting from each of the two ion exchange process conditions according to the examples of the present disclosure. Scanning electron microscope (SEM) photograph of glass ceramics according to an exemplary embodiment SEM photo of glass-ceramic according to another exemplary embodiment Transmission electron microscope (TEM) photography of glass ceramics according to another exemplary embodiment SEM photo of glass ceramic according to yet another exemplary embodiment TEM photograph of glass-ceramic according to yet another exemplary embodiment Transmittance spectrum of 0.5 mm polishing plane of composition 889FLZ under unslowly cooled and heat treated conditions (600 ° C., 1 hour) as manufactured Absorbance spectrum represented by OD / mm on a 0.5 mm polishing plane of the composition 889FLZ in the uncooled state as manufactured and under heat treatment conditions (600 ° C., 1 hour). Transmittance spectrum of 0.5 mm polishing plane of composition 889 FMB in uncooled and heat treated conditions (700 ° C., 1 hour) as manufactured Absorbance spectrum represented by OD / mm on a 0.5 mm polishing plane of the composition 889 FMB in the unslowly cooled state as manufactured and under heat treatment conditions (700 ° C., 1 hour). Transmittance spectrum of 0.5 mm polishing plane of composition 889 FMC in as-manufactured unslow-cooled and heat-treated conditions (500 ° C., 1 hour and 600 ° C., 1 hour) Absorbance spectrum expressed in OD / mm on a 0.5 mm polished plane of the composition 889 FMC in the uncooled state as manufactured and under heat treatment conditions (500 ° C., 1 hour and 600 ° C., 1 hour). Transmittance spectrum of 0.5 mm polishing plane of composition 889 FMD in as-manufactured unslow-cooled and heat-treated conditions (500 ° C., 1 hour and 600 ° C., 1 hour). Absorbance spectrum expressed in OD / mm on a 0.5 mm polished plane of the composition 889 FMD in the as-manufactured unslow-cooled state and heat treatment conditions (500 ° C., 1 hour and 600 ° C., 1 hour) Transmittance spectrum of 0.5 mm polishing plane of composition 889 FME in as-manufactured unslow-cooled and heat-treated conditions (600 ° C., 1 hour and 700 ° C., 1 hour). Absorbance spectrum expressed in OD / mm on a 0.5 mm polishing plane of the composition 889 FME in the uncooled state as manufactured and under heat treatment conditions (600 ° C., 1 hour and 700 ° C., 1 hour). Transmittance spectrum of 0.5 mm polishing plane of composition 889 FMG in as-manufactured unslow-cooled and heat-treated conditions (700 ° C., 1 hour and 700 ° C., 2 hours) Absorbance spectrum represented by OD / mm on a 0.5 mm polished plane of the composition 889 FMG in the as-manufactured unslow-cooled state and heat treatment conditions (700 ° C., 1 hour and 700 ° C., 2 hours). TEM photograph of a certain magnification of titanium-containing crystals in a heat-treated sample of composition 889FMC heat-treated at 700 ° C. for 1 hour. A TEM photograph of another magnification of the titanium-containing crystals in the heat-treated sample of the composition 889FMC heat-treated at 700 ° C. for 1 hour. Another magnification TEM photograph of the titanium-containing crystals in the heat-treated sample of the composition 889FMC heat-treated at 700 ° C. for 1 hour. A TEM photograph of the titanium-containing crystals in the heat-treated sample of the composition 889FMC heat-treated at 700 ° C. for 1 hour at yet another magnification. TEM photograph of titanium-containing crystals in a heat-treated sample of composition 889FMC heat-treated at 700 ° C. for 1 hour. Electron Dispersive Spectroscopy (EDS) Element Map of Titanium in TEM Photograph of FIG. 19A

Before embarking on drawings detailing the following detailed description and exemplary embodiments, it is understood that the art of the invention is not limited to the details or methodologies described in the detailed description or shown in the drawings. Should. For example, the features and attributes described in the text relating to an embodiment shown in one of the drawings or related to one of the embodiments are shown in another of the drawings. , Or other embodiments described elsewhere in the text, may be appreciated by those skilled in the art.

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

In this document, related terms such as first and second, top and bottom are used only to distinguish one entity or action from another, and which substance between such entities or actions is used. Such relationships or sequences of are not necessarily required or implied.

Modifications of this disclosure will be recalled to those skilled in the art and those who use the disclosure. Accordingly, the embodiments shown in the drawings and described above are for explanatory purposes only and are intended to limit the scope of the present disclosure, as interpreted in accordance with the principles of patent law, including the doctrine of equivalents. Instead, it will be understood that the scope of the present disclosure is defined by the following claims.

It will be appreciated by those skilled in the art that the constituents of the disclosures described, and other ingredients, are not limited to any particular material. Other exemplary embodiments of the disclosures disclosed herein may be formed from a wide variety of materials, unless otherwise stated.

For the purposes of the present disclosure, the term "bound" (in all its forms: binding, binding, binding, etc.) broadly refers to the connection of two components, either directly or indirectly to each other (in all its forms: binding, binding, binding, etc.) Means electrical or mechanical). Such a connection may be virtually stationary or virtually movable. Such a connection may be made by the two components (electrically or mechanically) and any additional intermediate members integrally molded with each other, or by the two components. Unless otherwise stated, such connections may be virtually permanent or virtually removable or releasable.

As used herein, the term "about" does not require the quantity, size, formulation, parameters, and other quantities and features to be accurate, but tolerable, conversion factors, rounding. , Measurement error, and other factors known to those of skill in the art, meaning that they may be approximated and / or larger or smaller, as desired. When the term "about" is used in describing the endpoints of a value or range, the disclosure should be understood to include that particular value or endpoint mentioned. Whether or not the endpoints of a number or range in the specification are "approx.", The endpoints of the number or range are modified by the following two embodiments: "approx." And "approx." It is intended to include those that are not modified with. It will be further understood that each endpoint of those ranges is significant both with respect to the other endpoint and regardless of the other endpoint.

Terms such as "substantial" and "substantially", as used herein, and variants thereof are intended to point out that the described features are equal to or nearly equal to a value or description. .. For example, a "substantially flat" surface is intended to mean a surface that is flat or nearly flat. Further, "substantially" is intended to mean that the two values are equal or nearly 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.

Orientation terms such as those used herein-for example, top, bottom, right, left, front, back, top, bottom-are used only for the drawings drawn and are intended to imply absolute orientation. There is no.

As used herein, a noun refers to "at least one" object and should not be limited to "only one" object unless explicitly indicated to be the opposite. Thus, for example, reference to "ingredients" includes embodiments having more than one such ingredient, unless the context clearly indicates otherwise.

Unless otherwise stated, all compositions are expressed in mole percent (mol%) as they are in batch. As will be appreciated by those skilled in the art, the components of various melts (eg, fluorine, alkali metals, boron, etc.) will volatilize at different levels during the melting of the components (eg, vapor pressure, melting time and / Or it may be exposed to (as a function of melting temperature). Thus, the term "about" for such ingredients has a value within about 0.2 mol% when the final article is measured, as compared to the as-batch-blended composition given herein. Intended to include. With the above in mind, substantial compositional equivalence is expected between the final product and the as-batch composition.

For the purposes of the present disclosure, the terms "bulk", "bulk composition" and / or "overall composition" are intended to include the overall composition of the entire article, which is the bulk due to the formation of crystalline and / or ceramic phases. It may be distinguished from "local composition" or "local composition" which may differ from the composition.

Also, as used herein, the terms "article", "glass article", "ceramic article", "glass ceramic", "glass element", and "glass ceramic article" are interchangeably the broadest. In the sense, it may be used to include any object made entirely or partially from glass and / or glass-ceramic material.

As used herein, "glass state" refers to the inorganic amorphous phase material in the article of the present disclosure, which is the product of melting that has been cooled to a rigid state without crystallization. As used herein, the "glass-ceramic state" of the present disclosure comprises both the glass state and the "crystalline phase" and / or "crystalline precipitate" as described herein. Refers to the inorganic material in the article.

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

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

As used herein, "optical density unit", "OD" and "OD unit" are I ₀ being the intensity of light incident on the sample and I being the intensity of light transmitted through the sample. Interchangeable in the present disclosure to refer to optical density units, as commonly understood as a measure of the absorbance of the material being tested, measured by a spectrometer, given by OD = -log (I / I ₀ ). Is used for. In addition, the terms "OD / mm" or "OD / cm" as used in the present disclosure are measured in optical density units (ie, in optical spectrometers) in sample thickness (eg, in millimeters or centimeters). Is a normalized measure of absorbance, determined by dividing the optics. In addition, any optical density unit referenced over a particular wavelength range (eg, 3.3 OD / mm to 24.0 OD / mm at UV wavelengths from 280 nm to 380 nm) is an optical density unit over a defined wavelength range. Given as an average value.

As used herein, the term "haze" refers to transmitted light scattered outside a cone at an angle of ± 2.5 ° in a sample with a transmission path of approximately 1 mm, measured according to ASTM procedure D1003. Refers to the percentage of.

Also, as used herein, the term "[ingredient] -free [glass or glass-ceramic]" (eg, "cadmium- and selenium-free glass-ceramic") completely includes the listed ingredients. Glass prepared to be free or substantially free (ie, <500 ppm) and not actively, intentionally or purposefully added or batch-blended into the glass or glass ceramic. Or represents glass ceramic.

As with the glass ceramics and glass ceramic materials and articles of the present disclosure, compressive stresses and compressive depths (“DOC”) are defined in GlassStress, Ltd., unless otherwise specified. Commercially available products such as the scattered light polarizing device SCALP220 manufactured by (Tallinn, Estonia) and its accompanying software version 5, or FSM-6000 manufactured by Orihara Seisakusho Co., Ltd. (Tokyo, Japan). Measured by assessing surface stress using an instrument. Both devices measure the optical delay that must be converted to stress by the stress optical coefficient (“SOC”) of the material being tested. Thus, stress measurements rely on precise measurements of SOC related to birefringence of glass. The SOC is then measured according to an improved version of Procedure C, which is the ASTM Standard C770-98, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", all of which is cited herein. 2013) (“Improvement Procedure C”). This modification procedure C involves using glass or glass ceramic discs as test pieces with a thickness of 5 to 10 mm and a diameter of 12.7 mm. The disc is isotropic and uniform, with a hole in the core and both sides polished and parallel. This improvement procedure C also includes a step of calculating the maximum force Fmax to be applied to the disk. This force should be sufficient to generate a compressive stress of at least 20 MPa. Fmax is the formula:
Fmax = 7.854 ^* D ^* h
In the equation, Fmax is the maximum force (N), D is the diameter of the disc (mm), and h is the thickness of the optical path (mm). For each applied force, the stress is:
σ (MPa) = 8F / (π ^* D ^* h)
In the equation, F is the force (N), D is the diameter of the disc (mm), and h is the thickness of the optical path (mm).

Also, as used herein, the terms "sudden cutoff wavelength" and "cutoff wavelength" are used interchangeably and are cutoff wavelengths in the range of about 350 nm to 800 nm, which are glass ceramics. Refers to a cutoff wavelength having a transmittance above the cutoff wavelength (λc), which is substantially higher than the transmittance below the cutoff wavelength (λc). The cutoff wavelength (λc) is the wavelength at the midpoint between the “absorption limit wavelength” and the “high transmittance limit wavelength” in the predetermined spectrum of the glass ceramic. The "absorption limit wavelength" is specified as a wavelength having a transmittance of 5%, and the "high transmittance limit wavelength" is defined as a wavelength having a transmittance of 72%. It will be appreciated that the "steep UV cutoff" used herein may be the steep cutoff wavelength of the cutoff wavelength as described above, which occurs within the ultraviolet band of the electromagnetic spectrum.

The articles of the present disclosure consist of glass and / or glass ceramic having one of the compositions outlined herein. The article can be used for any number of purposes. For example, the article may be used in the form of substrates, elements, lenses, covers and / or other elements in any optical and / or aesthetic application.

This article is formed from a batch-blended composition and cast in a glassy state. The article may later be slowly cooled and / or heat treated (eg, heat treated) to form a glass-ceramic state with multiple ceramics or crystalline particles. Depending on the casting technique used, the article will easily crystallize into a glass-ceramic (eg, essentially cast into a glass-ceramic state) without the need for additional heat treatment. Will be understood. In examples where post-formation thermal processing is used, some, most, substantially all or all of the article may be converted from a glass state to a glass ceramic state. Thus, while the composition of the article may be described with respect to the glassy and / or glass-ceramic state, the bulk composition of the article has a composition in which the localized portion of the article is different (ie, ceramic or crystalline precipitation). Despite this (due to the formation of objects), it may remain substantially unchanged when converted between the glassy and glass-ceramic states.

According to various examples, the article may contain Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , WO ₃ , MO ₃ , R ₂ O, RO, and a large number of dopants, in the formula R ₂ O is one or more of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O, and RO is one or more of MgO, CaO, SrO, BaO and ZnO. is there. Many other components (eg, F, As, Sb, Ti, P, Ce, Eu, La, Cl, Br, etc.) will be understood without departing from the teachings given herein.

According to the first example, the article is about 58.8 mol% to about 77.58 mol% SiO ₂ , about 0.66 mol% to about 13.69 mol% Al ₂ O ₃ , about 4. 42 mol% to about 27 mol% B ₂ O ₃ , about 0 mol% to about 13.84 mol% R ₂ O, about 0 mol% to about 0.98 mol% RO, about 1.0 mol% May contain from about 13.24 mol% WO ₃ and from about 0 mol% to about 0.4 mol% SnO ₂ . Such examples of articles would generally be relevant to Examples 1-109 of Table 1.

According to the second example, the article is about 65.43 mol% to about 66.7 mol% SiO ₂ , about 9.6 mol% to about 9.98 mol% Al ₂ O ₃ , about 9. 41 mol% to about 10.56 mol% B ₂ O ₃ , about 6.47 mol% to about 9.51 mol% R ₂ O, about 0.96 mol% to about 3.85 mol% RO, Containing about 1.92 mol% to about 3.85 mol% WO ₃ , about 0 mol% to about 1.92 mol% MoO ₃ , and about 0 mol% to about 0.1 mol% SnO _2. There is. Such examples of articles would generally be relevant to Examples 110-122 in Table 2.

According to the third example, the article is about 60.15 mol% to about 67.29 mol% SiO ₂ , about 9.0 mol% to about 13.96 mol% Al ₂ O ₃ , about 4. 69 mol% to about 20 mol% B ₂ O ₃ , about 2.99 mol% to about 12.15 mol% R ₂ O, about 0.00 mol% to about 0.14 mol% RO, about 0 WO ₃ from mol% to about 7.03 mol%, MoO ₃ from about 0 mol% to about 8.18 mol%, SnO ₂ from about 0.05 mol% to about 0.15 mol%, and about 0 mol%. _May contain from about 0.34 mol% V ₂ O ₅ . Such examples of articles would generally be relevant to Examples 123-157 in Table 3.

According to the fourth example, the article is about 54.01 mol% to about 67.66 mol% SiO ₂ , about 9.55 mol% to about 11.42 mol% Al ₂ O ₃ , about 9. 36 mol% to about 15.34 mol% B ₂ O ₃ , about 9.79 mol% to about 13.72 mol% R ₂ O, about 0.00 mol% to about 0.22 mol% RO, About 1.74 mol% to about 4.48 mol% WO ₃ , about 0 mol% to about 1.91 mol% MoO ₃ , about 0.0 mol% to about 0.21 mol% SnO ₂ , about. It may contain from 0 mol% to about 0.03 mol% V ₂ O ₅ , from about 0 mol% to about 0.48 mol% Ag, and from about 0 mol% to about 0.01 mol% Au. Such examples of articles would generally be relevant to Examples 158-311 in Table 4.

According to a fifth example, the article is about 60.01 mol% to about 77.94 mol% SiO ₂ , about 0.3 mol% to about 10.00 mol% Al ₂ O ₃ , about 10 mol. % To about 20 mol% B ₂ O ₃ , about 0.66 mol% to about 10 mol% R ₂ O, about 1.0 mol% to about 6.6 mol% WO ₃ , and about 0.0 It may contain from mol% to about 0.1 mol% SnO ₂ . Such examples of articles would generally be relevant to Examples 312-328 in Table 5.

Articles are from about 1 mol% to about 99 mol% SiO ₂ , or from about 1 mol% to about 95 mol% SiO ₂ , or from about 45 mol% to about 80 mol% SiO ₂ , or from about 60 mol%. About 99 mol% SiO ₂ , or about 61 mol% to about 99 mol% SiO ₂ , or about 30 mol% to about 99 mol% SiO ₂ , or about 58 mol% to about 78 mol% SiO ₂ , Or about 55 mol% to about 75 mol% SiO ₂ , or about 50 mol% to about 75 mol% SiO ₂ , or about 54 mol% to about 68 mol% SiO ₂ , or about 60 mol% to about 78. Mol% SiO ₂ , or about 65 mol% to about 67 mol% SiO ₂ , or about 60 mol% to about 68 mol% SiO ₂ , or about 65 mol% to about 72 mol% SiO ₂ , or about It may have 60 mol% to about 70 mol% SiO ₂ . It will be appreciated that any and all values and ranges between the above ranges of SiO ₂ are possible. SiO ₂ acts as a major glass-forming oxide and can affect the stability, devitrification and / or viscosity of the article.

The article is about 0 mol% to about 50 mol% Al ₂ O ₃ , or about 0.5 mol% to about 20 mol% Al ₂ O ₃ , or about 0.5 mol% to about 15 mol% Al. ₂ O ₃ , or about 7 mol% to about 15 mol% Al ₂ O ₃ , or about 0.6 mol% to about 17 mol% Al ₂ O ₃ , or about 0.6 mol% to about 14 mol% Al ₂ O ₃ , or about 7 mol% to about 14 mol% Al ₂ O ₃ , or about 9.5 mol% to about 10 mol% Al ₂ O ₃ , or about 9 mol% to about 14 mol%. Al ₂ O ₃ , or about 9.5 mol% to about 11.5 mol% Al ₂ O ₃ , or about 0.3 mol% to about 10 mol% Al ₂ O ₃ , or about 0.3 mol. From% to about 15 mol% Al ₂ O ₃ , or from about 2 mol% to about 16 mol% Al ₂ O ₃ , or from about 5 mol% to about 12 mol% Al ₂ O ₃ , or from about 8 mol% It may contain about 12 mol% Al ₂ O ₃ , or about 5 mol% to about 10 mol% Al ₂ O ₃ . It will be appreciated that any and all values and ranges between the above ranges of Al ₂ O ₃ are possible. Al ₂ O ₃ may function as a conventional reticulated structure forming material and contributes to stable articles with low CTE, stiffness of articles, and promotion of melting and / or molding.

Articles may include WO ₃ and / or MoO ₃ . For example, the sum of WO ₃ and MoO ₃ can be from about 0.35 mol% to about 30 mol%. MoO ₃ can be about 0 mol%, WO ₃ can be from about 1.0 mol% to about 20 mol%, or MoO ₃ can be about 0 mol%, WO ₃ can be about 1. 0 mol% to about 14 mol%, or MoO ₃ from about 0 mol% to about 8.2 mol%, WO ₃ from about 0 mol% to about 16 mol%, or MoO ₃ from about 0 From mol% to about 8.2 mol%, WO ₃ is from about 0 mol% to about 9 mol%, or MoO ₃ is from about 1.9 mol% to about 12.1 mol%, WO ₃ is It is from about 1.7 mol% to about 12 mol%, or MoO ₃ is from about 0 mol% to about 8.2 mol%, WO ₃ is from about 0 mol% to about 7.1 mol%, or MoO ₃ is from about 1.9 mol% to about 12.1 mol%, WO ₃ is from about 1.7 mol% to about 4.5 mol%, or MoO ₃ is from about 0 mol%, WO ₃ is from about 1.0 mol% to about 7.0 mol%. With respect to MoO ₃ , the glass composition is from about 0.35 mol% to about 30 mol% MoO ₃ , or from about 1 mol% to about 30 mol% MoO ₃ , or from about 0.9 mol% to about 30 mol%. MoO ₃ , or about 0.9 mol% to about 20 mol% MoO ₃ , or about 0 mol% to about 1.0 mol% MoO ₃ , or about 0 mol% to about 0.2 mol% MoO _May have ₃ . With respect to WO ₃ , the glass composition is about 0.35 mol% to about 30 mol% WO ₃ , or about 1 mol% to about 30 mol% WO ₃ , or about 1 mol% to about 17 mol% WO. ₃ , or about 1.9 mol% to about 10 mol% WO ₃ , or about 0.35 mol% to about 1 mol% WO ₃ , or about 1.9 mol% to about 3.9 mol% WO _It may have ₃ or about 2 mol% to about 15 mol% WO ₃ , or about 4 mol% to about 10 mol% WO ₃ , or about 5 mol% to about 7 mol% WO ₃ . It will be appreciated that any and all values and ranges between the above-mentioned ranges of WO ₃ and / or MoO ₃ are possible.

The article is about 2 mol% to about 40 mol% B ₂ O ₃ , or about 4 mol% to about 40 mol% B ₂ O ₃ , or about 4.0 mol% to about 35 mol% B ₂ O. ₃ , or about 4.0 mol% to about 27 mol% B ₂ O ₃ , or about 5.0 mol% to about 25 mol% B ₂ O ₃ , or about 9.4 mol% to about 10.6 From mol% B ₂ O ₃ , or from about 5 mol% to about 20 mol% B ₂ O ₃ , or from about 4.6 mol% to about 20 mol% B ₂ O ₃ , or from about 9.3 mol% It may contain about 15.5 mol% B ₂ O ₃ , or about 10 mol% to about 20 mol% B ₂ O ₃ , or about 10 mol% to about 25 mol% B ₂ O ₃ . It will be appreciated that any and all values and ranges between the above ranges of B ₂ O ₃ are possible. B ₂ O ₃ may be a glass-forming oxide used to reduce CTE, density, and viscosity and facilitate the melting and formation of articles at low temperatures.

The article may contain at least one alkali metal oxide. The alkali metal oxide may be represented by the chemical formula R ₂ O, where R ₂ O is Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O and / or its. One or more of the combinations. The article is about 0.1 mol% to about 50 mol% R ₂ O, or about 0 mol% to about 14 mol% R ₂ O, or about 3 mol% to about 14 mol% R ₂ O, or About 5 mol% to about 14 mol% R ₂ O, or about 6.4 mol% to about 9.6 mol% R ₂ O, or about 2.9 mol% to about 12.2 mol% R ₂ O, or about 9.7 mol% to about 12.8 mol% R ₂ O, or about 0.6 mol% to about 10 mol% R ₂ O, or about 0 mol% to about 15 mol% R _It may have an alkali metal oxide composition of ₂ O, or about 3 mol% to about 12 mol% R ₂ O, or about 7 mol% to about 10 mol% R ₂ O. That any and all values and ranges between the above-described range of R 2 _O are conceivable it will be appreciated. Alkali metal oxides (eg, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O) (i) reduce the melting temperature, (ii) increase moldability, (i) It may be included in an article for a number of reasons, including iii) allowing chemical fortification by ion exchange and / or (iv) primarily for involvement in a particular crystallite.

According to various examples, the value obtained by subtracting Al ₂ O ₃ from R ₂ O is about -35 mol% to about 7 mol%, or about -12 mol% to about 2.5 mol%, or about -6. It ranges from mol% to about 0.25 mol%, or from about -3.0 mol% to about 0 mol%. It will be appreciated that any and all values and ranges between the above ranges of values obtained by subtracting Al ₂ O ₃ from R ₂ O are possible.

The article may contain at least one alkaline earth metal oxide. The alkaline earth metal oxide may be represented by the chemical formula RO, where RO is one or more of MgO, CaO, SrO, BaO, and ZnO. The article is about 0.02 mol% to about 50 mol% RO, or about 0.01 mol% to about 5 mol% RO, or about 0.02 mol% to about 5 mol% RO, or about. From 0.05 mol% to about 10 mol% RO, or from about 0.10 mol% to about 5 mol% RO, or from about 0.15 mol% to about 5 mol% RO, or about 0.05 mol% From about 1 mol% RO, or about 0.5 mol% to about 4.5 mol% RO, or about 0 mol% to about 1 mol% RO, or about 0.96 mol% to about 3.9 RO of mol%, or RO of about 0.2 mol% to about 2 mol%, or RO of about 0.01 mol% to about 0.5 mol%, or RO of about 0.02 mol% to about 0.22 mol May contain% RO. It will be appreciated that any and all values and ranges between the aforementioned ranges of RO are possible. According to various examples, R ₂ O may be higher than RO. In addition, the article may not contain RO. Other divalent oxides such as alkaline earth metal oxides (eg MgO, CaO, SrO, and BaO) and ZnO may improve the melting behavior of the article, CTE, Young's modulus, and shear of the article. It can also work to increase the rate.

The article is about 0.01 mol% to about 5 mol% SnO ₂ , or about 0.01 mol% to about 0.5 mol% SnO ₂ , or about 0.05 mol% to about 0.5 mol%. SnO ₂ , or about 0.05 mol% to about 2 mol% SnO ₂ , or about 0.04 mol% to about 0.4 mol% SnO ₂ , or about 0.01 mol% to about 0.4. Mol% SnO ₂ , or about 0.04 mol% to about 0.16 mol% SnO ₂ , or about 0.01 mol% to about 0.21 mol% SnO ₂ , or about 0 mol% to about 0 It may contain 2 mol% SnO ₂ , or about 0 mol% to about 0.1 mol% SnO ₂ . It will be appreciated that any and all values and ranges between the above-mentioned ranges of SnO ₂ are possible. The article should be used in low concentrations of finings (eg, other finings such as CeO ₂ , As ₂ O ₃ , Sb ₂ O ₃ , Cl ⁻ , F to help remove gaseous inclusions during melting. ^- it may also include a SnO ₂ as such). Certain fining agents may also act as redox pairs, color centers, and / or seeds that penetrate and / or nucleate the crystals formed in the article.

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

The article may be substantially free of cadmium and substantially free of selenium. According to various examples, the article has Ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, in order to change the ultraviolet, visible, color and / or near infrared absorbance. It may further comprise at least one dopant selected from the group consisting of Se, Ta, Bi, Ag, Ce, Pr, Nd, and Er. The dopant may have a concentration of about 0.0001 mol% to about 1.0 mol% in the article. For example, the article is about 0.01 mol% to about 0.48 mol% Ag, about 0.01 mol% to about 0.13 mol% Au, about 0.01 mol% to about 0.03 mol. _May contain at least one of% V ₂ O ₅ , about 0 mol% to about 0.2 mol% Fe ₂ O ₃ , and about 0.01 mol% to about 0.48 mol% Cu O. is there. According to another example, the article is from about 0.01 mol% to about 0.75 mol% Ag, about 0.01 mol% to about 0.5 mol% Au, from about 0.01 mol%. It may contain at least one of about 0.03 mol% V ₂ O ₅ and about 0.01 mol% to about 0.75 mol% Cu O. The article may contain in the range of about 0 mol% to about 5 mol% fluorine to soften the glass. The article may contain about 0 mol% to about 5 mol% phosphorus in order to further improve the physical properties of the article and regulate crystal growth. The article, physical and optical of the article (e.g., refractive index) in order to further improve the _{properties, Ga 2 O 3, In 2} O 3, and may include GeO _2. The following trace impurities further improve the absorbance of ultraviolet, visible (eg, from 390 nm to about 700 nm), and near infrared (eg, from about 700 nm to about 2500 nm) and / or cause the article to fluoresce. May be present in the range of about 0.001 mol% to about 0.5 mol%: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Te, Ta, Re, Os, Ir, Pt, Au, Ti, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Furthermore, in order to further improve the physical properties and the viscosity of the article, there may be a P ₂ O ₅ in a particular composition are added in small amounts.

In any other composition and / or composition range of the other components of the article outlined herein, SiO ₂ , Al ₂ O ₃ , WO ₃ , MoO ₃ , WO ₃ and MoO ₃ , B ₂ O ₃ , R ₂ O, It will be appreciated that the compositions and composition ranges described above for RO, V ₂ O ₅ , Ag, Au, CuO, SnO ₂ , and dopants may be used.

As described above, the conventional formation of tungsten, molybdenum, or alkali glass containing a mixture of tungsten and molybdenum has been hampered by the separation of molten components during the melting process. Due to the separation of the glass components during this melting process, the dissolution limits of the alkali tungstate in the molten glass and therefore in the articles cast from such melts were recognized. Traditionally, molten borosilicate, even when the melt of tungsten, molybdenum, or a mixture of tungsten and molybdenum is slightly superalkaline (eg, R ₂ O-Al ₂ O ₃ = about 0.25 mol% or more). The acid glass formed both the glass and the second phase of the dense liquid. The concentration of the second phase of this alkali tungstate could be reduced by complete mixing, melting at elevated temperatures, and the use of small batch sizes (up to 1000 g), but the second phase should be completely eliminated. Could not, resulting in the formation of a harmful second crystal phase. The formation of this alkaline tungstate phase is believed to occur in the early stages of melting, when tungsten oxide and / or molybdenum react with "free" or "unbound" alkaline carbonates. Due to the high density of alkali tungstate and / or alkali molybdate with respect to the borosilicate glass formed, they rapidly segregate and / or stratify and accumulate at the bottom of the crucible, due to significant density differences. , Does not solubilize rapidly in glass. Since R 2 _O component will provide beneficial properties to the glass composition, it may not be desirable to reduce the presence of R _{2 O} component in the melt simply.

The inventors of the present disclosure have determined that the use of "bound" alkali may result in a uniform single-phase W or Mo-containing per-alkali melt. For the purposes of the present disclosure, a "bound" alkali is an alkali element bound to alumina, boria, and / or silica, whereas a "free" or "unbound" alkali is an alkali that is attached to silica, boria, or alumina. Unbound alkaline carbonates, alkaline nitrates and / or alkaline sulfates. Illustrated binding alkalis include feldspar, nepheline, porcelain, spodium, other albite or potash feldspar, alkali aluminosilicates, alkali silicates, and / or alkalis and one or more aluminums, boron and / or. Other naturally occurring and artificially produced minerals containing silicon atoms may be mentioned. By introducing the bound form of alkali, the alkali will not react with W or Mo present in the melt to form a dense alkali tungstate and / or alkali molybdate liquid. Furthermore, when the batch material is modified in this way, a strong per-alkali composition (eg, R ₂ O-Al ₂ O ₃ = about) without forming any alkali tungstate and / or alkali molybdate second phase. More than 2.0 mol%) could be melted. This also allows for varying melting temperatures and mixing methods, yet single-phase uniform glass can be produced. It will be appreciated that the alkaline tungstate and borosilicate glasses are not completely immiscible, so long-term agitation can also mix the two phases to cast a single-phase article.

Once the glass melt has been cast and solidified into a glassy article, the article can be slowly cooled, heat treated or otherwise heat treated to form a crystalline phase within the article. Therefore, the article may be converted from a glassy state to a glass-ceramic state. The crystal phase in the glass-ceramic state may take various forms. 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 generally have a crystalline structure.

As used herein, "crystal phase" refers to an inorganic material within an article of the present disclosure, which is a solid consisting of atoms, ions or molecules arranged in a three-dimensional, periodic pattern. In addition, "crystal phases" as referred to in this disclosure are determined to exist using the following methods, unless otherwise stated. First, powder X-ray diffraction (“XRD”) is used to detect the presence of crystalline precipitates. Second, if XRD fails (eg, due to the size, quantity and / or chemistry of the precipitate), Raman spectroscopy (“Raman”) is used to detect the presence of crystalline precipitates. Be done. If desired, transmission electron microscopy (“TEM”) is used to visually confirm or otherwise substantiate the determination of crystalline precipitates obtained by XRD and / or Raman techniques. In certain situations, the amount and / or size of the precipitate may be small enough to find it particularly difficult to visually confirm the precipitate. Thus, larger sample sizes of XRD and Raman may be convenient for sampling large amounts of material to determine the presence of precipitates.

The crystalline precipitate may have a substantially rod-like or needle-like morphology. The precipitates are from about 1 nm to about 500 nm, or from about 1 nm to about 400 nm, or from about 1 nm to about 300 nm, or from about 1 nm to about 250 nm, or from about 1 nm to about 200 nm, or from about 1 nm to about 100 nm, or from about 1 nm. It may have the longest dimensions of about 75 nm, or about 1 nm to about 50 nm, or about 1 nm to about 25 nm, or about 1 nm to about 20 nm, or about 1 nm to about 10 nm. The size of the precipitate may be measured using electron microscopy. For purposes of the present disclosure, the term "electron microscopy" refers to the longest of precipitates by first using a scanning electron microscope and then using a transmission electron microscope if the precipitate cannot be resolved. It means measuring the length visually. Since the crystalline precipitate will generally have a rod-like or needle-like morphology, the precipitate may have a width of about 2 nm to about 30 nm, or about 2 nm to about 10 nm, or about 2 nm to about 7 nm. is there. It will be appreciated that the size and / or morphology of the precipitate may be uniform, substantially uniform, or varied. In general, the peraluminous composition of the article may produce a needle-shaped precipitate having a length of about 100 nm to about 250 nm and a width of about 5 nm to about 30 nm. The per-alkali composition of the article may produce needle-like precipitates having a length of about 10 nm to about 30 nm and a width of about 2 nm to about 7 nm. Ag, Au and / or Cu-containing examples of the article may produce rod-like precipitates having a length of about 2 nm to about 20 nm and a width or diameter of about 2 nm to about 10 nm. The volume fraction of the crystalline phase in the article is about 0.001% to about 20%, or about 0.001% to about 15%, or about 0.001% to about 10%, or about 0.001%. From about 5, or from about 0.001% to about 1%.

The relatively small size of the precipitate may be convenient in reducing the amount of light scattered by the precipitate and providing high optical clarity of the article when in the glass-ceramic state. As described in more detail below, the size and / or amount of precipitate may vary across articles such that different parts of the article have different optical properties. For example, a portion of an article in which a precipitate is present has absorbance, color, light reflectance and / or a portion of an article in which a different precipitate (size and / or amount) is present and / or is not present. Alternatively, it may cause changes in transmittance and refractive index.

The precipitate may consist of tungsten oxide and / or molybdenum oxide. The crystal phase is at least one of (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation: about 0.1 mol of the crystal phase. Contains% to about 100 mol% oxide. Although not intended to be constrained in theory, during thermal processing of articles (eg, heat treatment), tungsten and / or molybdenum cations aggregate to form crystalline precipitates, thereby transforming the glass state into a glass-ceramic state. It is thought that it will be converted to. The molybdenum and / or tungsten present in the precipitate will be reduced or partially reduced. For example, molybdenum and / or tungsten in the precipitate may have an oxidation state between 0 and about +6. According to various examples, molybdenum and / or tungsten may have a +6 oxidation state. For example, the precipitate may have a general chemical structure of WO ₃ and / or MoO ₃ . However, tungsten and / or molybdenum in the +5 oxidation state can also be a significant fraction, the precipitates of which are non-stoichiometric tungsten trioxide, non-stoichiometric trioxide molybdenum, "molybdenum bronze", And / or sometimes known as "tungsten bronze". One or more of the alkali metals and / or dopants mentioned above may be present in the precipitate to compensate for the +5 charge on W or Mo. Tungsten and / or molybdenum bronze is a group of non-chemical quantitative tungsten trioxide and / or molybdenum in the general chemical form of M _x WO ₃ or M _x MoO ₃ , in the formula M = H, Li, Na. , K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho , Er, Tm, Yb, Lu, and / or U, and 0 <x <1. In the structure M _x WO ₃ or M _x MoO ₃ , holes (ie, holes or channels in the crystal lattice) in the reduced WO ₃ or MoO ₃ network are randomly occupied by M atoms, which are M + positive. It is considered to be a solid defect structure that dissociates into ions and free electrons. Depending on the concentration of "M", material properties can range from metals to semiconductors, thereby adjusting a wide variety of light absorption and electronic properties. The more 5 + W or Mo, the more M + will be needed to supplement and the larger the value of x.

Tungsten bronze is generally a non-stoichiometric compound of formula M _x WO ₃ , where M is a cationic dopant for some other metal, most commonly alkali, and x is less than 1. It is a variable of. Although referred to as "bronze" for clarity, these compounds are not structurally or chemically related to metal bronze, which is an alloy of copper and tin. Tungsten bronze is a range of solid phases whose uniformity varies as a function of x. Depending on the dopant M and the corresponding concentration x, the material properties of tungsten bronze may range from metal to semiconductor and exhibit adjustable light absorption. The structure of these bronze is a solid defect structure in which M'cations are inserted into holes or channels of the binary oxide host and dissociated into M + cations and free electrons.

For clarity, M _x WO ₃ has a variety of crystal structures that can be hexagonal, square, cubic, or pyrochloroa, where M is one of the specific elements in the periodic table. Or it can be a combination, x fluctuates with 0 <x <1, and the oxidation state of the bronze-forming species (W in this case) is the highest oxidation state (W ⁶⁺ ) and the lowest oxidation state (for example). , W ⁵⁺ ), and the number 3 (“3”) in WO ₃ represents the number of oxygen anions that can be between 2 and 3, non-stoichiometric or "semi-stoichiometric" A nomenclature for complex systems of "stoichiometric" compounds. Thus, M _x WO ₃ may instead be expressed as the chemical form M _x WO _z, as 0 <x <1, 2 <z <3, or the chemical form M _x WO _{3-z in} the formula. It may be expressed, and in the formula, 0 <x <1, 0 <z <1. However, for simplicity, the non-stoichiometric crystals of this group, M _x WO ₃ is used. Similarly, "Bronze" generally, _"applies to ternary metal oxides y _{O z,} wherein, (i) M" wherein M _'x M is a transition metal, (ii) _{M "y} O _z is its highest binary oxide, (iii) M'is some other metal, and (iv) x is a variable in the range 0 <x <1.

Some, most, substantially all or all of the articles may be heat processed to form precipitates. Thermal processing techniques may include, but are not limited to, other techniques for local and / or bulk heating of furnaces (eg, heat treatment furnaces), microwaves, lasers and / or articles. The crystalline precipitate forms internal nuclei within the article in a uniform fashion while undergoing thermal processing, where the article is thermally processed to convert from a glass state to a glass-ceramic state. Thus, in some examples, the article may include both glass and glass ceramic states. In an example where the article is heat-processed in bulk (eg, the entire article is placed in a furnace), precipitates may form uniformly over the entire article. In other words, the precipitates may be present from the outer surface of the article over most of the article (ie, more than about 10 μm from the surface). In an example where an article is heat-processed locally (eg, by a laser), the precipitates are only present where the thermal process reaches a sufficient temperature (eg, the surface of the article and the interior close to the heat source). Sometimes. It will be appreciated that the article may undergo multiple thermal processes to produce precipitates. In addition to or instead, thermal processing may be used to remove and / or alter the precipitates that have already formed (eg, as a result of the previous thermal processing). For example, thermal processing may decompose the precipitate.

According to various examples, the article is visible in the visible region of the electromagnetic spectrum (ie, the portion in the glass or glass ceramic state) both in the presence of the precipitate and in the absence of the precipitate (ie, the portion in the glass or glass ceramic state). It may be optically transparent at about 400 nm to about 700 nm). As used herein, the term "optically transparent" refers to about 1% (eg, for example) a path length of 1 mm over at least one 50 nm wide wavelength range of light in the range of about 400 nm to about 700 nm. % / Mm unit) Refers to the transmittance exceeding. In some examples, the articles are all about 5% / mm or more, about 10% / mm or more, about 15% / mm over at least one 50 nm wide wavelength range of light in the visible region of the spectrum. Above, about 20% / mm or more, about 25% / mm or more, about 30% / mm or more, about 40% / mm or more, about 50% / mm or more, about 60% / mm or more, about 70% / mm or more Has a transmission of about 80% / mm or greater, and greater than all lower limits between these values.

According to various examples, the glass-ceramic state of an article is light in the ultraviolet (“UV”) region (ie, wavelengths less than about 400 nm, based on the presence of precipitates, without the use of additional coatings or films. ) Is absorbed. In some practices, the glass-ceramic state of the article is less than 10% / mm, 9% for light in at least one 50 nm wide wavelength range of light in the UV region of the spectrum (eg, from about 200 nm to about 400 nm). Less than / 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 1% Characterized by a transmittance of less than / mm. In some examples, the glass-ceramic state is at least 90% / mm, at least 91% / mm, at least 92% / mm, for light in at least one 50 nm wide wavelength region of light in the UV region of the spectrum. Absorbs 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, or absorbs its absorbance. Have. The glass-ceramic state may have a sharp UV cutoff wavelength of about 320 nm to about 420 nm. For example, the glass-ceramic state is about 320 nm, about 330 nm, about 340 nm, about 350 nm, about 360 nm, about 370 nm, about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm, or any between them. May have a sharp UV cutoff at the value of.

In some examples, the glass-ceramic state of the article all spans at least one 50 nm wide wavelength range of light in the near infrared (NIR) region of the spectrum (eg, from about 700 nm to about 2700 nm). More than 5% / mm, more than about 10% / mm, more than about 15% / mm, more than about 20% / mm, more than about 25% / mm, more than about 30% / mm, more than about 40% / mm, about 50 It has a transmission of greater than% / mm, greater than about 60% / mm, greater than about 70% / mm, greater than about 80% / mm, greater than about 90% / mm, and above all lower limits between these values. In yet another example, the glass-ceramic state of the article is all less than about 90% / mm, less than about 80% / mm, about 70 over a wavelength range of at least one 50 nm width of light in the NIR region of the spectrum. Less than% / 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, about 15% Less than / mm, less than about 10% / mm, less than about 5% / mm, less than about 4% / mm, less than about 3% / mm, less than about 2% / mm, less than about 1% / mm, and about 0. It has a transmission of less than 1% / mm, as well as less than all upper limits between these values. In another example, the glass-ceramic state of the article is at least 90% / mm, at least 91% / mm, at least 92% / mm, for light in at least one 50 nm wide wavelength region of light in the NIR region of the spectrum. At least 93% / mm, at least 94% / mm, at least 95% / mm, at least 96% / mm, at least 97% / mm, at least 98% / mm, or at least 99% / mm, or at least 99.9% / mm It absorbs even mm, or has its absorbance.

The various examples of the present disclosure will provide a wide variety of properties and advantages. It will be appreciated that certain properties and benefits may be disclosed in connection with a particular composition, but the various properties and benefits disclosed will apply equally to other compositions. ..

With respect to the compositions in 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 coefficient of thermal expansion of about 10 × ^10-7 / ° C to about 60 × ^10-7 / ° C over a temperature range of about 0 ° C to about 300 ° C. Such a low CTE would allow the article to withstand large and sudden fluctuations in temperature, making it suitable for operation in harsh environments. In terms of optical properties, the article has less than 1% transmittance at wavelengths below about 368 nm, light transmission in the visible region (eg from about 500 nm to about 700 nm), and NIR wavelengths (eg from about 700 nm to about 700 nm). It may exhibit strong attenuation (eg, blocking) up to 1700 nm. Such articles are more convenient than traditional NIR operating methods in that they do not use coatings or membranes (eg, they may be mechanically fragile and sensitive to UV and moisture). Let's go. Because the article is less susceptible to oxygen, moisture, and UV wavelengths (ie, due to the nature of glass or glass ceramics), NIR-absorbing precipitates are subject to harsh environmental conditions (eg, moisture, corrosive acids, bases and gases). ) And will be protected from sudden temperature changes. In addition, the UV cutoff wavelength and refractive index changes of the glass-ceramic state of the article could be adjusted by post-formation heat treatment. The glass-ceramic state of the article may exhibit a change in refractive index or UV cutoff as a result of crystalline precipitates. The glassy state of the article may have a refractive index between about 1.505 and about 1.508, while the glass-ceramic state of the article has a refractive index of about 1.520 to about 1.522. May have. The heat-adjustable UV cutoff and index of refraction will allow one glass bath to be adapted on the fly to a number of UV cutoff glass specifications by varying the thermal processing conditions after the formation of the article. The thermally regulated index of refraction can produce a large index of refraction difference ( ^10-2 ). UV absorbance heat treatment required to adjust the a high viscosity (e.g., between 10 ⁸ and 10 ¹² poise) so takes place in the finished article, without compromising the surface, or without causing deformation, thermal processing can do.

With respect to the compositions in Tables 1 and 2, articles made from these compositions are a novel group of non-toxic, cadmium- and selenium-free articles that exhibit photoattenuation at sharply adjustable cutoff wavelengths. Will present. Unlike Cd-free alternatives to CdSe filter glass, which contain Se, these articles do not contain metals or other harmful substances involved in the Resource Conservation and Restoration Act (“RCRA”). In addition, the article may consist of lower cost elements, unlike Cd-free alternatives, which contain indium and / or gallium. With respect to optical properties, articles made from these compositions may exhibit high transparency (eg, greater than about 90%) over 2.7 micrometers from NIR. In addition, the article exhibits a steep visible cutoff wavelength ranging from about 320 nm to 525 nm, which can be adjusted by thermal processing conditions (eg, time and temperature), and composition.

With respect to the compositions in Table 3, the articles of these exemplary compositions may use molybdenum instead of tungsten, which would be convenient in that molybdenum is generally less expensive than tungsten. In addition, articles made from these compositions may be heat-processed into a glass-ceramic state, which state will present a wide variety of optical properties. For example, the transmittance of articles of such composition ranges from about 4% to about 30% in the visible spectrum (eg, from about 400 nm to about 700 nm) at a thickness of about 0.5 mm and NIR (eg, about about 700 nm). It can exhibit UV transmittance of about 5% to about 15% at wavelengths (from 700 nm to about 1500 nm) and less than about 1% at wavelengths below about 370 nm, or about 5% or less at wavelengths from about 370 nm to about 390 nm. According to some examples, an example of a mixture of molybdenum and tungsten in the article can absorb 92.3% of the sun's spectrum. Such optical properties will be visually perceived as a shade to the article. As with other compositions, its optical properties result from the growth of precipitates, and therefore its shade may vary across articles based on thermal processing. This thermally variable shade can be used to create a shade gradient within the article, such as the formation of shaded edges or edges in an article windshield or moon roof application. Such features would be convenient to eliminate the frit burned on the surface of conventional windshields or moon roofs. This thermally adjustable shade can also be used to create gradient absorption over the article. In addition, articles made from this composition can be decolorized and patterned with a laser (eg, operating at wavelengths of 355 nm, 810 nm, and 10.6 μm). The exposed area of the article is colorless and transparent from blue or gray (eg, its color is due to the precipitate) due to thermal decomposition of UV and NIR absorbing precipitates when laser exposed to these wavelengths. Or it turns pale yellow. A pattern can be formed within the article by scanning the laser along the surface of the article to selectively decolorize the desired area. When the article is bleached, the resulting glassy state is no longer absorbable in NIR as the bleaching process is self-regulating (ie, because the NIR absorption precipitate has decomposed). In addition, selective laser exposure can result in variable UV and NIR absorbance across the article as well as the pattern. According to yet another example, the article is ground to a sufficiently small size and functionalized for use as a photothermal susceptor for cancer treatment (ie, due to its NIR-absorbing optical properties). May be done.

With respect to the compositions in Table 4, articles made from these compositions are heat treated after molding to modulate optical absorption and produce a wide range of colors from one composition (eg, glass ceramics). There are things that can be done (to form a state). In addition, such examples may be capable of fusion molding and / or ion exchange. Conventional colored glass compositions that utilize Ag, Au and / or Cu generally rely on the formation of nanoscale metal precipitates to produce color. As discovered by the inventors of the present disclosure, Ag ¹⁺ cations can penetrate between the oxides of tungsten and molybdenum to form silver tungsten bronze and / or silver molybdenum bronze, which can be applied to the article. May give multicolor. Surprisingly, the addition of Ag ₂ O or AgNO ₃ in small concentrations in _M x WO ₃ or _M x MoO ₃ into compositions in the article by hot working the article at different temperatures and times, various Colors (eg, red, orange, yellow, green, blue, various browns and / or combinations thereof) may occur. It will be appreciated that Au and / or Cu may be used in a similar fashion. Analysis demonstrates that color adjustability is not due to the formation of a collection of moldable metal nanoparticles on a crystalline phase (eg, M _x WO ₃ or M _x MoO ₃ ). Instead, the origin of color-adjustability in these multicolored articles penetrates into the precipitates, pure alkalis, pure metals and / or mixed alkali metals of various chemical theories, tungsten and / or molybdenum. It is believed that this is due to the change in bandgap energy of the doped tungsten oxide and / or molybdenum precipitates caused by the concentration of alkaline cations and Ag ¹⁺ , Au and / or Cu cations forming bronze. The change in bandgap energy of the precipitate is due to its stoichiometry and, in turn, is generally independent of the size and / or shape of the precipitate. Thus, the doped M _x WO ₃ or M _x MoO ₃ precipitates can remain of the same size and / or shape, yet many, depending on the uniqueness and concentration "x" of the dopant "M". Different colors could be produced. Heat treatment of such articles can result in a near-perfect iridescent color within one article. In addition, the temperature gradient applied to the article can widen or compress the color gradation over a physical distance. In yet another example, the article can be laser patterned to locally change the color of the article. Such articles may be convenient for the manufacture of colored sunglasses lens blanks, telephone and / or tablet covers and / or other products that may consist of glass ceramics and may be aesthetically colored. Since the precipitates are positioned within the glass-ceramic, they are more scratch resistant and environmentally durable than conventional metal and polymer colored layers applied to give color. Since the color of the article will be changed based on heat treatment, one tank of glass melt will be used to continuously produce blanks that can be heat treated to a particular color as determined by the customer's request. In addition, articles made from these glass compositions will absorb ultraviolet and / or infrared as well as the other compositions disclosed herein.

According to the various examples of the present disclosure, the article will be suitable for various fusion molding processes. For example, the various compositions of the present disclosure use single or two clear tungsten, molybdenum, mixed tungsten molybdenum, and / or titanium glass as the clad material around the substrate to form a laminated article. Sometimes used for heavy fusion laminates. The glass state clad may be converted to a glass ceramic state after being applied as a clad. The glass-ceramic state cladding of fusion laminated articles can have a thickness of about 50 μm to about 200 μm and has a high average visible transmittance (eg, for automotive front glass and / or architectural flat glass, from about 75% to about. Strong UV and IR attenuation in conditions (up to 85%), strong UV and IR in low visible transmission (eg, from about 5% to about 30% for automotive side windows, automotive sunroofs, and privacy glazing). IR attenuation and / or visible and infrared absorbance may have laminates that can be modulated by treatment in a gradient furnace, local heating and / or local decolorization. In addition, the use of the composition as a cladding for forming articles provides a new process for producing a toughened monolith glass layer while taking full advantage of its adjustable optical properties.

According to various examples, articles made from the compositions of the present disclosure may be powdered or granulated and added to various materials. For example, the powdered article may be added to paints, binders, polymeric materials (eg, polyvinyl butyral), sol-gel, and / or combinations thereof. Such features would be convenient in imparting one or more of the features of this article to the materials described above.

According to various examples, the article may contain TiO ₂ . The article is 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. 0.0 mol%, or about 17.0 mol%, or about 18.0 mol%, or about 19.0 mol%, or about 20.0 mol%, or about 21.0 mol%, or about 22.0 Mol%, or about 23.0 mol%, or about 24.0 mol%, or about 25.0 mol%, or about 26.0 mol%, or about 27.0 mol%, or about 28.0 mol% , Or about 29.0 mol%, or about 30.0 mol%, or any and all values and ranges of concentrations between them may contain TiO ₂ . For example, the article may be about 0.25 mol% to about 30 mol% TiO ₂ , or about 1 mol% to about 30 mol% TiO ₂ , or about 1.0 mol% to about 15 mol% TiO _2. or may contain TiO ₂ to about 2.0 mole% to about 15 mole% of TiO _2, or about 2.0 mol%, a concentration of TiO ₂ of about 15.0 mole%. It will be appreciated that any and all values and ranges between the aforementioned ranges of TiO ₂ are possible.

According to various examples, the article may contain one or more metal sulfides. For example, a metal sulfide, MgS, would include _Na 2 S, and / or ZnS. According to various examples, the article may contain one or more metal sulfides. For example, a metal sulfide, MgS, would include _Na 2 S, and / or ZnS. The article is 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. 0.0 mol%, or about 17.0 mol%, or about 18.0 mol%, or about 19.0 mol%, or about 20.0 mol%, or about 21.0 mol%, or about 22.0 Mol%, or about 23.0 mol%, or about 24.0 mol%, or about 25.0 mol%, or about 26.0 mol%, or about 27.0 mol%, or about 28.0 mol% , Or about 29.0 mol%, or about 30.0 mol%, or any and all values and ranges of concentrations between them may contain metal sulfide. For example, the article contains metal sulfides at concentrations of about 0.25 mol% to about 30 mol%, or about 1.0 mol% to about 15 mol%, or about 1.5 mol% to about 5 mol%. May include.

Similar to the previously highlighted tungsten oxide and molybdenum, examples of articles containing titanium may also give rise to a crystalline phase consisting of titanium oxide precipitates. The crystalline phase contains about 0.1 mol% to about 100 mol% of oxides of Ti and alkali metal cations of the crystalline phase. Although not constrained by theory, during thermal processing of articles (eg, heat treatment), titanium cations aggregate to form crystalline precipitates near and / or on metal sulfides, thereby creating a glassy state. It is thought that it will be converted to a glass-ceramic state. The metal sulfide is a nucleating agent (ie, the metal sulfide has a higher melting temperature than the melt, which may act as a seed crystal on which titanium will aggregate) and reduction. It may play a dual role as both agents (ie, metal sulfides are highly reducing agents and therefore aggregated titanium will be reduced to the 3+ state). Thus, the titanium present in the precipitate may be reduced or partially reduced due to the metal sulfide. For example, titanium in a precipitate may have an oxidation state between 0 and about +4. For example, the precipitate may have a general chemical structure of TiO ₂ . However, a significant proportion of titanium can also be in a +3 oxidation state, and in some cases these Ti ³⁺ cations are charge-stabilized by the species inserted into the channels within the titania crystal lattice and are non-chemical. Quantitative titanium oxide may form compounds known as "titanium bronze" or "bronze type" titanium crystals. One or more of the alkali metals and / or dopants mentioned above may be present in the precipitate to compensate for the +3 charge on Ti. Titanium bronze is a group of non-chemical quantitative sub-titanium oxides in the general chemical form of M _x TiO ₂ , and in the formula, M = H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, V, One or more dopant cations of Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce, where 0 <x <1. The structure M _x TiO ₂ is considered to be a solid defect structure in which holes (that is, holes or channels in the crystal lattice) in the reduced TiO ₂ network structure are randomly occupied by M atoms. The M atom is dissociated into M + cations and free electrons. Depending on the concentration of "M", material properties can range from metals to semiconductors, thereby adjusting a wide variety of light absorption and electronic properties. The more 3 + Ti, the more M + will be needed to make up, and the larger the value of x.

Consistent with the above disclosure, titanium bronze is generally a non-stoichiometric compound of formula M _x TiO ₂ , where M is a cation dopant such as some other metal, most commonly alkali. And x is a variable less than 1. Although referred to as "bronze" for clarity, these compounds are not structurally or chemically related to metal bronze, which is an alloy of copper and tin. Titanium bronze is a range of solid phases whose uniformity varies as a function of x. Depending on the dopant M and the corresponding concentration x, the material properties of titanium bronze may range from metal to semiconductor and exhibit adjustable light absorption. These bronze structures are solid defect structures in which M'dopant cations are inserted (ie, occupy) the holes or channels of the binary oxide host and dissociated into M + cations and free electrons.

For clarity, M _x TiO ₂ has a variety of crystal structures that can be monoclinic, hexagonal, square, cubic, or pyrochloroa, in which M is the specific element of the periodic table. Can be one or a combination of, x fluctuates with 0 <x <1, and the oxidation state of the bronze-forming species (Ti in this case) becomes the lowest oxidation state with the species in the highest oxidation state (Ti ⁴⁺ ). A non-stoichiometric or non-stoichiometric or non-stoichiometric mixture of certain (eg, Ti ³⁺ ), where the number 2 (“2”) in TiO ₂ represents the number of oxygen anions that can be between 1 and 2. A nomenclature for complex systems of "stoichiometric" compounds. Therefore, M _x TiO ₂ may instead be expressed as the chemical form M _x TiO _z, as 0 <x <1, 1 <z <2, or the chemical form M _x TiO _{2-z in} the formula. It may be expressed, and in the formula, 0 <x <1, 0 <z <1. However, for brevity, M _x TiO ₂ is utilized for this group of non-stoichiometric crystals. Similarly, "Bronze" generally, _"applies to ternary metal oxides y _{O z,} wherein, (i) M" wherein M _'x M is a transition metal, (ii) _{M "y} O _z is its highest binary oxide, (iii) M'is some other metal, and (iv) x is a variable in the range 0 <x <1.

According to various examples, titanium-containing glass-ceramic articles may be substantially free of W, Mo, and rare earth elements. As emphasized earlier, the ability of titanium to form its own suboxide may eliminate the need for tungsten and molybdenum, and titanium oxide may not require rare earth elements.

According to various examples, the glass-ceramic article may have a low concentration of iron or may not contain iron. For example, the article is 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 between them. It may contain Fe of any and all values and ranges.

According to various examples, the glass-ceramic articles may have low concentrations of lithium or may not contain lithium. For example, the article is about 1 mol% or less Li, or about 0.5 mol% or less Li, or about 0.1 mol% or less Li, or 0.0 mol% Li, or between them. It may contain Li of any and all values and ranges.

According to various examples, the glass-ceramic article may have a low concentration of zirconium or may not contain zirconium. For example, the article is 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 between them. It may contain Zr of any and all values and ranges.

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

The formation of titanium dioxide in the titanium-containing example of the article may cause differences in the absorption and transmittance of light in different wavelength ranges. In the ultraviolet (UV) band of light (eg, from about 200 nm to about 400 nm), articles in the glassy state may have an average UV transmission of about 18% to about 30% before precipitation of titanium hydroxide. .. For example, the average UV transmittance of an article in a glassy state is about 18%, or about 19%, or about 20%, or about 21%, or about 22%, or about 23%, or about 24%, or about. It may be in any and all values and ranges of 25%, or about 26%, or about 27%, or about 28%, or about 29%, or about 30%, or between them. Articles in the glass-ceramic state after the formation or precipitation of titanium oxide may have an average UV transmission of about 0.4% to about 18%. For example, the average UV transmittance of an article in a glass-ceramic state is 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 It may be in any and all values and ranges between 15%, or about 16%, or about 17%, or about 18%, or between them. It will be appreciated that the above-mentioned transmittance values may be present in articles having a thickness of about 0.4 mm to about 1.25 mm or a path length of light.

In the visible band of light (eg, from about 400 nm to about 750 nm), articles in the glassy state may have an average visible transmission of about 60% to about 85% before precipitation of titanium hydroxide. For example, the average visible transmittance of an article in a glassy state is 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%, 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%, about 80%, or about 81%, or about 82%, or about 83%, or about 84%, or about 85%, or any and all between them. May be in value and range. Articles in the glass-ceramic state after the formation or precipitation of titanium oxide may have an average visible transmission of about 4% to about 85%. For example, the average visible transmittance of an article in a glass-ceramic state is about 4%, or about 5%, or about 10%, or about 20%, or about 30%, or about 40%, or about 50%, or It may be in any and all values and ranges of about 60%, or about 70%, or about 80%, or about 85%, or between them. It will be appreciated that the above-mentioned transmittance values may be present in articles having a thickness of about 0.4 mm to about 1.25 mm or a path length of light.

In the infrared (NIR) band of light (eg, from about 750 nm to about 1500 nm), an article in a glassy state should have an average NIR transmission of about 80% to about 90% before precipitation of titanium hydroxide. There is. For example, the average NIR transmittance of an article in a glassy state is about 80%, or about 81%, or about 82%, or about 83%, or about 84%, or about 85%, or about 86%, or about. It may be in any and all values and ranges of 87%, or about 88%, or about 89%, or about 90%, or between them. Articles in the glass-ceramic state after the formation or precipitation of titanium oxide may have an average NIR transmission of about 0.1% to about 10%. For example, the average NIR transmittance of an article in a glass-ceramic state is about 1%, or about 2%, or about 3%, or about 4%, or about 5%, or about 6%, or about 7%, or It may be in any and all values and ranges of about 8%, or about 9%, or about 10%, or between them. It will be appreciated that the above-mentioned transmittance values may be present in articles having a thickness of about 0.4 mm to about 1.25 mm or a path length of light.

In the NIR band of light, articles in glass that do not contain titanium oxide are 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 between them, the average optical density per mm (ie, first. May have near-infrared absorbance). After the precipitation of titanium hydroxide, the article in the glass ceramic state containing titanium oxide is 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 It may have an average optical density per mm (ie, a second near-infrared absorbance) of .5 or less, or any and all values and ranges between them. Thus, in some cases, the ratio of the second average near-infrared absorbance to the first average near-infrared absorbance is about 1.5 or greater, or about 2.0 or greater, or about 2.5 or greater. Or it may be about 3.0 or more, or about 5.0 or more, or about 10.0 or more. In such an example, the average optical density per mm at a visible wavelength of an article in a glass-ceramic state, including titanium dioxide, may be 1.69 or less.

According to various examples, the article may exhibit low haze. For example, the article is about 20% or less, or about 15% or less, or about 12% or less, or about 11% or less, or about 10.5% or less, or about 10% or less, or about 9.5% or less. , Or about 9% or less, or about 8.5% or less, or about 8% or less, or about 7.5% or less, or about 7% or less, or about 6.5% or less, or about 6% or less, or About 5.5% or less, or about 5% or less, or about 4.5% or less, or about 4% or less, or about 3.5% or less, or about 3% or less, or about 2.5% or less, or About 2% or less, or about 1.5% or less, or about 1% or less, or about 0.5% or less, or about 0.4% or less, or about 0.3% or less, or about 0.2% or less , Or about 0.1% or less, or any and all values and ranges of haze between them. The haze of the article is measured for a 1 mm thick sample according to the techniques outlined above for haze measurement. According to various examples, the haze of the article is usually present in certain glass ceramics, but due to the absence of beta quartz (ie, Virgilite), which tends to increase haze, conventional glass. May be lower than ceramic. In other words, the glass-ceramic article may not contain a beta quartz crystal phase. Moreover, the haze of the article may be due to the small amount or absence of large crystals that tend to scatter light (eg, less than about 100 nm, or less than about 60 nm, or less than about 40 nm).

Using an article containing titanium dioxide, a crystal or non-stoichiometric titanium bronze with the general formula M _x TiO ₂ will offer a number of advantages.

First, the thermal processing time to produce titanium oxide may be shorter than in the production of other glass ceramics. In addition, the thermal working temperature may be lower than the softening point of the article. Such features would be beneficial in reducing manufacturing complexity and manufacturing costs.

Second, color packages (eg, TiO ₂ + ZnS) can be introduced into a wide range of melt compositions, including those with ion exchange capacity. In addition, the addition of such color packages will not significantly affect the chemical durability and other related properties of the article, as relatively low concentrations of color packages are required.

Third, using glass ceramics containing titanium hydroxide, fusion-moldable and chemically-strengthening materials for UV and / or infrared blocking materials that would not have the drawback of melting due to radiation trapping. Will be provided. For example, an article containing titanium hydroxide, when in a molten or cast state (ie, unprocessed before heat treatment), strongly absorbs in the near infrared even when melted, Fe ^2+. Unlike doped glass, it is extremely transparent at visible and NIR wavelengths.

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

Referring here to Table 1, the articles are about 58.8 mol% to about 77.58 mol% SiO ₂ , about 0.66 mol% to about 13.69 mol% Al ₂ O ₃ , about 4. .42 mol% to about 27 mol% B ₂ O ₃ , about 0 mol% to about 13.84 mol% R ₂ O, about 0 mol% to about 0.98 mol% RO, about 1.0 mol May have from% to about 13.24 mol% WO ₃ and from about 0 mol% to about 0.4 mol% SnO ₂ . All of the illustrated compositions in Table 1 have about 0 mol% to about 0.2 mol% MnO ₂ , about 0 mol% to about 0.1 mol% Fe ₂ O ₃ , and about 0 mol% to about 0. _May contain 0.01 mol% TiO ₂ , about 0 mol% to about 0.17 mol% As ₂ O ₅ , and / or about 0 mol% to about 0.1 mol% Eu ₂ O _3. Will be understood. The compositions in Table 1 are given in a batch blended state in the crucible.

Referring here to Table 2, the articles are about 65.43 mol% to about 66.7 mol% SiO ₂ , about 9.6 mol% to about 9.98 mol% Al ₂ O ₃ , about 9. .41 mol% to about 10.56 mol% B ₂ O ₃ , about 6.47 mol% to about 9.51 mol% R ₂ O, about 0.96 mol% to about 3.85 mol% RO Has about 1.92 mol% to about 3.85 mol% WO ₃ , about 0 mol% to about 1.92 mol% MoO ₃ , and about 0 mol% to about 0.1 mol% SnO ₂ . Sometimes. The compositions in Table 2 are given in a batch-blended state in the crucible.

Referring here to Table 3, the articles are about 60.15 mol% to about 67.29 mol% SiO ₂ , about 9.0 mol% to about 13.96 mol% Al ₂ O ₃ , about 4. .69 mol% to about 20 mol% B ₂ O ₃ , about 2.99 mol% to about 12.15 mol% R ₂ O, about 0.00 mol% to about 0.14 mol% RO, about 0 mol% to about 7.03 mol% WO ₃ , about 0 mol% to about 8.18 mol% MoO ₃ , about 0.05 mol% to about 0.15 mol% SnO ₂ , and about 0 mol. _May have V ₂ O ₅ from% to about 0.34 mol%. It will be appreciated that any of the illustrated compositions in Table 3 may contain from about 0 mol% to about 0.0025 mol% Fe ₂ O ₃ . The compositions in Table 3 are given in a batch-blended state in the crucible.

Referring here to Table 4, the articles are about 54.01 mol% to about 67.66 mol% SiO ₂ , about 9.55 mol% to about 11.42 mol% Al ₂ O ₃ , about 9. .36 mol% to about 15.34 mol% B ₂ O ₃ , about 9.79 mol% to about 13.72 mol% R ₂ O, about 0.00 mol% to about 0.22 mol% RO , About 1.74 mol% to about 4.48 mol% WO ₃ , about 0 mol% to about 1.91 mol% MoO ₃ , about 0.0 mol% to about 0.21 mol% SnO ₂ , It may have about 0 mol% to about 0.03 mol% V ₂ O ₅ , about 0 mol% to about 0.48 mol% Ag, and about 0 mol% to about 0.01 mol% Au. .. All of the illustrated compositions in Table 4 have about 0 mol% to about 0.19 mol% CeO ₂ , about 0 mol% to about 0.48 mol% CuO, and about 0 mol% to about 0.52 mol. % Br ⁻ , about 0 mol% to about 0.2 mol% Cl ⁻ , about 0 mol% to about 0.96 mol% TiO ₂ , and / or about 0 mol% to about 0.29 mol% It will be understood that it may contain Sb ₂ O ₃ . The compositions in Table 4 are given in a batch-blended state in the crucible.

Referring here to Table 5, the articles are about 60.01 mol% to about 77.94 mol% SiO ₂ , about 0.3 mol% to about 10.00 mol% Al ₂ O ₃ , about 10. B ₂ O ₃ from mol% to about 20 mol%, R ₂ O from about 0.66 mol% to about 10 mol%, WO ₃ from about 1.0 mol% to about 6.6 mol%, and about 0. It may have from 0 mol% to about 0.1 mol% SnO ₂ . It will be appreciated that any of the illustrated compositions in Table 5 may contain from about 0 mol% to about 0.09 mol% Sb ₂ O ₃ . The compositions in Table 5 are given in a batch-blended state in the crucible.

Referring here to Table 6, liquid tungstic acid separated during the melting process when melted using an unbound alkaline batch material (eg, alkali carbonate) instead of bound alkali (eg, Kasumi). A list of exemplary glass compositions for comparison to form alkali is given. As described above, the alkali tungstate phase of the second liquid may solidify as another crystal, which may make the substrate produced from it milky white.

With respect to the background of the examples, the glass containing cadmium and selenium (“CdSe glass”) has a significant amount of cadmium and selenium and may be characterized by its toxicity. Some effort has been devoted to developing non-toxic or less toxic alternatives to CdSe glass. For example, conventional alternatives include Cd-free glass compositions. Nevertheless, these compositions still contain selenium and other expensive dopants such as indium and gallium. In addition, conventional Cd-free selenium-containing glasses have been characterized by inferior cutoff wavelength and / or viewing angle dependence compared to CdSe glasses. Therefore, applicants believe that a cadmium- and selenium-free material with comparable or improved optical properties to conventional CdSe glass is needed. These materials preferably have adjustable bandgap and steep cutoffs as non-toxic alternatives to CdSe glass. Non-toxic CdSe glass characterized by low coefficient of thermal expansion (CTE), durability, thermal stress resistance and / or relatively simple and low cost manufacturing and processing requirements in view of the intended use of these materials. Alternatives are also needed.

According to some aspects of the disclosure, aluminoborosilicate glass; about 0.7 to about 15 mol% WO ₃ ; about 0.2 to about 15 mol% at least one alkali metal oxide; and Glass ceramics containing at least one alkaline earth metal oxide of from about 0.1 to about 5 mol% are provided.

According to some aspects of the disclosure, aluminoborosilicate glass; about 0.7 to about 15 mol% WO ₃ ; about 0.2 to about 15 mol% at least one alkali metal oxide; and Glass ceramics containing at least one alkaline earth metal oxide of from about 0.1 to about 5 mol% are provided. In addition, the glass-ceramic has a light transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.

According to some aspects of the disclosure, aluminoborosilicate glass; about 0.7 to about 15 mol% WO ₃ ; about 0.2 to about 15 mol% at least one alkali metal oxide; and Glass ceramics containing at least one alkaline earth metal oxide of from about 0.1 to about 5 mol% are provided. In addition, the glass ceramic comprises at least one of the crystalline phases of alkaline earth, alkaline and mixed alkaline earth / alkaline tungstate, the crystalline phase being stoichiometric or non-stoichiometric form. It is in.

In some implementations of the previous aspects of glass ceramics, the aluminoborosilicate glass is about 55 to about 80 mol% SiO ₂ , about 2 to about 20 mol% Al ₂ O ₃ , and about 5 to about 5. It contains 40 mol% B ₂ O ₃ , or 68 to 72 mol% SiO ₂ , 8 to 12 mol% Al ₂ O ₃ , and 5 to 20 mol% B ₂ O ₃ . In addition, at least one alkaline earth metal oxide may contain from 0.1 to 5 mol% MgO. At least one alkali metal oxide may contain 5 to 15 mol% Na ₂ O. In addition, the difference in the amount of at least one alkali metal oxide and Al ₂ O ₃ in this aluminoborosilicate glass can range from -6 mol% to + 2 mol%.

In an additional implementation of the previous embodiment of the glass-ceramic, the glass-ceramic may be substantially free of cadmium and substantially free of selenium. Further, the glass ceramic is 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. It may further contain at least one type of dopant. In a further implementation of the previous embodiment of the glass ceramic, the glass ceramic may further contain 0% to about 50% MoO ₃ of WO ₃ present in the glass ceramic.

According to an additional aspect of the present disclosure, the main surface and aluminoborosilicate glass; about 0.7 to about 15 mol% WO ₃ ; about 0.2 to about 15 mol% of at least one alkali metal oxidation. Articles; and articles comprising a substrate having a glass-ceramic composition comprising at least one alkaline earth metal oxide of from about 0.1 to about 5 mol% are provided. Further, in some implementations of this embodiment, the substrate further comprises a compressive stress region, which extends from the main surface to the first selective depth of the substrate and is generated by an ion exchange process. .. Also, in some embodiments of this embodiment, the substrate has a light transmission of at least 90% from 700 nm to 3000 nm and a steep cutoff wavelength of about 320 nm to about 525 nm.

According to a further aspect of the present disclosure, it is a method of making glass ceramics, aluminhosilicate glass, about 0.7 to about 15 mol% WO ₃ , and about 0.2 to about 15 mol% at least 1. The step of mixing a batch containing a type of alkali metal oxide and at least one type of alkaline earth metal oxide of about 0.1 to about 5 mol%; melting the batch between about 1500 ° C and about 1700 ° C. The step of forming the melt; the step of slowly cooling the melt between about 500 ° C. and about 600 ° C. to define the slow-cooled melt; and the slow-cooling melt of about 5 minutes to about 48. Provided is a method comprising a step of forming a glass ceramic by heat treatment between about 500 ° C. and about 1000 ° C. over time.

In some implementations of the previous method of making glass ceramics, the heat treatment step is to heat treat the slowly cooled melt between about 600 ° C. and about 800 ° C. for about 5 minutes to about 24 hours to make the glass ceramic. Includes the step of forming. Further, the heat treatment step may include a step of heat-treating the slow-cooled melt between about 650 ° C. and about 725 ° C. for about 45 minutes to about 3 hours to form a glass ceramic. In some embodiments of the method, the glass ceramic has a light transmittance of at least 90% from 700 nm to 3000 nm and a steep cutoff wavelength of about 320 nm to about 525 nm.

As detailed in the present disclosure, cadmium- and selenium-free glass-ceramic materials are provided that have comparable or improved optical properties to conventional CdSe glass. In embodiments, these materials have adjustable bandgap and steep cutoffs as non-toxic alternatives to CdSe glass. Embodiments of these materials can also be characterized by low coefficient of thermal expansion (CTE), durability, thermal stress resistance and / or relatively simple and low cost manufacturing and processing requirements.

More generally, the glass-ceramic materials disclosed herein, and the articles containing them, are the remaining aluminoborosilicate glass, tungsten oxide, at least one alkali metal oxide, and at least one alkaline earth metal oxidation. Including things. These glass-ceramic materials can be characterized by a light transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm. In addition, these materials may contain at least one alkaline earth tungstate crystal phase that remains generated, for example, under certain heat treatment conditions after the formation of the glass ceramic. In addition, embodiments of these glass-ceramic materials are characterized by a cutoff that can be adjusted by the choice of specific heat treatment conditions. As such, these glass-ceramic materials offer a non-toxic, cadmium- and selenium-free glass-ceramic as an alternative to conventional CdSe glass.

Various embodiments of the glass-ceramic materials of the present disclosure include the following applications: security and surveillance filters designed to suppress visible light for infrared illumination; airport runway lamps; eye protection for lasers. Lenses; Optical Barriers for Motion Control in Electromechanicals; Barcode Readers; Interatomic Force Microscopes; Nano Indenters; Laser Interferometer Measurement Solutions; Laser-Used Dynamic Calibration Systems; Lithmetic Solutions for Integrated Circuit Manufacturing; Optical bit error rate test solution; Photonic digital communication analyzer; Photonic jitter generation and analysis system; Optical modulation analyzer; Optical intensity measuring instrument; Optical attenuator; Light source; Optical wave component analyzer; Gas chromatograph; Spectrometer; Fluorescent microscope; Traffic monitoring camera; Environmental waste, water and exhaust gas monitoring device; Photographic camera spectrum filter; Radiation thermometer; Imaging brightness colorimeter; Industrial image processing; Wavelength control light source used for counterfeit tag detection; Color It can be used in the form of substrates, elements, covers and other elements in any of scanners for digitizing images; astronomical filters; Humphrey perimeters in medical diagnostic equipment; and optical filters for ultrashort pulse lasers: .. Embodiments of these glass-ceramic materials are also suitable for various artistic endeavors and applications utilizing colored glass, glass-ceramics and ceramics, such as glassblowers, flameworkers, stained glass artists, etc. Is.

The glass-ceramic material, and articles containing it, offer various advantages over conventional glass, glass-ceramic and ceramic materials in the same field, including CdSe glass. As mentioned earlier, the glass-ceramic materials of the present disclosure are cadmium- and selenium-free, while presenting a sharp visible attenuation similar to the orange conventional CdSe filter glass. The glass-ceramic materials of the present disclosure also present sharper visible attenuation as compared to semiconductor-doped glass, which is a conventional alternative to CdSe glass. In addition, the glass-ceramic materials of the present disclosure are formulated with lower cost materials as compared to conventional alternatives to CdSe glass, which use indium, gallium, and / or other high cost metals and components. Another advantage of these glass-ceramic materials is that they are characterized by a cut-off wavelength that can be adjusted by the choice of heat treatment temperature and time conditions. A further advantage of these glass-ceramic materials is that they show no reduction in transmittance at wavelengths from 900 to 1100 nm and are transparent in the near infrared (“NIR”) spectrum, in contrast to CdSe glass. In addition, these glass-ceramic materials, unlike other traditional CdSe glass alternatives, such as semiconductor-doped glass containing indium and gallium, which require additional semiconductor synthesis and milling steps, are traditionally fused. Can be manufactured in the process of quenching.

Here, with reference to FIG. 1, an article 100 containing a substrate 10 made from the glass-ceramic composition according to the present disclosure is shown. These articles can be used for any of the applications outlined above (eg, optical filters, airport runway ramps, barcode readers, etc.). Therefore, in some embodiments, the substrate 10 can be characterized by a light transmittance of at least 90% from 700 nm to 3000 nm and a steep cutoff wavelength from about 320 nm to about 525 nm. The substrate 10 has a pair of opposite main surfaces 12, 14. In some embodiments of article 100, the substrate 10 includes a compressive stress region 50. As shown in FIG. 1, the compressive stress region 50 of the article 100 is exemplary and extends from the main surface 12 to the first selective depth 52 in the substrate. Some embodiments of Article 100 (not shown) include an additional comparable compressive stress region 50 (not shown) extending from the main surface 14 to a second selective depth. In addition, some embodiments of article 100 (not shown) include a number of compressive stress regions 50 extending from the main surfaces 12, 14 of the substrate 10. Furthermore, some embodiments (not shown) of article 100 include a number of compressive stress regions 50 extending from their respective main surfaces 12, 14 and short edges of the substrate 10 (ie, main surfaces 12, It also includes a compressive stress region extending from the edge perpendicular to 14.). As will be appreciated by those skilled in the art of the present disclosure, the processing conditions used to generate these compressive stress regions 50 (eg, complete immersion of the substrate 10 in a molten salt ion exchange bath, molten salt ion exchange). Various combinations of compressive stress regions 50 can be incorporated within the article 100, depending on the partial immersion of the substrate 10 in the bath, masking of specific edges and / or surfaces, full immersion of the substrate 10, etc.). ..

As used herein, "selection depth" (eg, selection depth 52), "compression depth" and "DOC" are the stresses on the substrate 10 from compression, as described herein. Used interchangeably to define the depth that changes to tension. The DOC may be measured by a surface stress meter such as FSM-6000 or a scattered light polarizing device (SCALP) depending on the ion exchange treatment. If the stress on the substrate 10 having a glass or glass-ceramic composition is generated by exchanging potassium ions in the glass substrate, a surface stress gauge is used to measure the DOC. SCALP is used to measure the DOC when stress is generated by exchanging sodium ions in the glass article. If the stress on the substrate 10 having a glass or glass-ceramic composition is caused by exchanging both potassium and sodium ions in the glass substrate, the DOC is measured by SCALP. This is because the exchange depth of sodium ions is considered to represent DOC, and the exchange depth of potassium ions is considered to represent the change in the magnitude of compressive stress (but not the change in stress from compression to tension). The exchange depth of potassium ions in such a glass substrate is measured with a surface stress meter. Further, as used here, the "maximum compressive stress" is defined as the maximum compressive stress in the compressive stress region 50 in the substrate 10. In some embodiments, the maximum compressive stress is obtained at or in close proximity to one or more main surfaces 12, 14 defining the compressive stress region 50. In other embodiments, the maximum compressive stress is obtained between one or more main surfaces 12, 14 and the selective depth 52 of the compressive stress region 50.

With reference to FIG. 1 again, the substrate 10 of article 100 can be characterized by a glass-ceramic composition. In embodiments, the glass-ceramic composition of substrate 10 is 0.7 to 15 mol% WO ₃ , 0.2 to 15 mol% at least one alkali metal oxide, 0.1 to 5 mol% at least. It is provided by one type of alkaline earth metal oxide and the remaining silicate-containing glass. Examples of these silicate-containing glasses include aluminoborosilicate glass, borosilicate glass, aluminosilicate glass, soda lime glass, and chemically enhanced ones of these silicate-containing glasses.

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

In some embodiments of Article 100, as illustrated in FIG. 1, the substrate 10 is selected from chemically fortified aluminoborosilicate glass. For example, the substrate 10 can be selected from chemically strengthened aluminoborosilicate glass that extends to a first selective depth of more than 10 μm and has a compressive stress region 50 with a maximum compressive stress of more than 150 MPa. .. In a further embodiment, the substrate 10 is selected from chemically strengthened aluminoborosilicate glass that extends to a first selective depth of 52 over 25 μm and has a compressive stress region 50 with a maximum compressive stress of over 400 MPa. Will be done. The substrate 10 of the article 100 is over about 150 MPa, over about 200 MPa, over about 250 MPa, over about 300 MPa, over about 350 MPa, over about 400 MPa, over about 450 MPa, over about 500 MPa, over about 550 MPa, over about 600 MPa, over about 650 MPa. Has a maximum compressive stress of greater than about 700 MPa, greater than about 750 MPa, greater than about 800 MPa, greater than about 850 MPa, greater than about 900 MPa, greater than about 950 MPa, greater than about 1000 MPa, and all maximum compressive stress levels between these values. It may also include one or more compressive stress regions 50 extending from one or more of the surfaces 12 and 14 to the (plural) selective depths 52. In some embodiments, the maximum compressive stress is 2000 MPa or less. In addition, the compressive depth (DOC) or first selective depth 52 may be 10 μm or greater, 15 μm or greater, 20 μm or greater, depending on the thickness of the substrate 10 and the machining conditions associated with the formation of the compressive stress region 50. It can be set to 25 μm or more, 30 μm or more, 35 μm or more, and even larger depths. In some embodiments, the DOC is 0.3 times or less the thickness (t) of the substrate 10, eg, 0.3t, 0.28t, 0.26t, 0.25t, 0.24t, 0. It is 23t, 0.22t, 0.21t, 0.20t, 0.19t, 0.18t, 0.15t, or 0.1t.

As outlined above, the glass-ceramic materials of the present disclosure, including the substrate used in Article 100 (see FIG. 1), have the following glass-ceramic composition: 0.7 to 15 mol% from WO ₃ , 0.2. Characterized by at least one alkali metal oxide of 15 mol%, at least one alkaline earth metal oxide of 0.1 to 5 mol%, and the remaining silicate-containing glass, such as aluminoborosilicate glass. Can be attached. In embodiments, the glass-ceramic material can be characterized by a light transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm. In some practices, the glass-ceramic material can be further characterized by the presence of at least one alkaline earth tungstate crystal phase and / or at least one alkali metal tungstate crystal phase. For example, the alkaline earth tungsten salt crystal phase can be obtained by M _x WO ₃ , where M is at least one of Be, Mg, Ca, Sr, Ba, and Ra. , 0 <x <1. In certain embodiments of the glass ceramics of the present disclosure, at least one alkaline earth metal tungstate crystal phase is the MgWO ₄ crystal phase (see, eg, FIG. 5 and its corresponding description) and MgW ₂ O. One or both of the _seven crystalline phases (see, eg, FIGS. 6A-6C, 7A and 7B, and their corresponding descriptions). As another example, the alkali tungstate crystal phase is given by M _x WO ₃ , where M is at least one of Li, Na, K, Cs, Rb and 0 <x <1. is there. As a further example, the tungstate crystal phase can be provided by M _x WO ₃ , where M is an alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra. And an alkali metal selected from the group consisting of Li, Na, K, Cs, and Rb, and 0 <x <1.

In embodiments, the glass ceramics of the present disclosure are optically transparent in the visible region of the spectrum (ie, from about 400 nm to about 700 nm). As used herein, the term "optically transparent" refers to about 1% (eg, for example) a path length of 1 mm over at least one 50 nm wide wavelength range of light in the range of about 400 nm to about 700 nm. Refers to the super transmittance (in% / mm units). In some embodiments, the glass ceramic is all over a wavelength range of at least one 50 nm width of light in the visible region of the spectrum, over about 5% / mm, over about 10% / mm, about 15. Over% / mm, over 20% / mm, over 25% / mm, over 30% / mm, over 40% / mm, over 50% / mm, over 60% / mm, about 70% It has a transmission of greater than / mm and greater than all lower limits between these values.

Embodiments of the glass ceramics of the present disclosure include the ultraviolet (“UV”) region of the spectrum (ie, wavelengths less than about 370 nm) and / or near infrared (“NIR”) without the use of additional coatings or films. ”) Absorbs light in the region (ie, from about 700 nm to about 1700 nm). In some practices, the glass ceramic is less than 10% / mm, less than 9% / mm, less than 8% / mm, 7 for light in at least one 50 nm wide wavelength region of light in the UV region of its spectrum. It is characterized by a transmittance of less than% / 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 is at least 90% / mm, at least 91% / mm, and at least 92% / mm for light in at least one 50 nm wide wavelength region of light in the UV region of its spectrum. Absorbs 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, or its absorbance. Has. In other practices, the glass ceramic is less than 10% / mm, less than 9% / mm, less than 8% / mm, 7% for light over at least one 50 nm wide wavelength region of light in the NIR region of the spectrum. Characterized by a transmission of less than / mm, less than 6% / mm, less than 5% / mm, less than 4% / mm, less than 3% / mm, less than 2% / mm, and less than 1% / mm. In other embodiments, the glass ceramic is at least 90% / mm, at least 91% / mm, at least 92% / mm, at least for light in the wavelength range of at least one 50 nm width of light in the NIR region of the spectrum. Absorbs 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, or absorbs its absorbance. Have.

Embodiments of the glass-ceramic materials of the present disclosure include aluminoborosilicate glass (containing, for example, SiO ₂ , Al ₂ O ₃ , and B ₂ O ₃ ), WO ₃ , and at least one alkali metal oxide. And contains at least one alkaline earth metal oxide. In some embodiments, the aluminoborosilicate glass is about 55 mol% to about 80 mol% SiO ₂ , about 60 mol% to about 74 mol% SiO ₂ , or about 64 mol% to about 70 mol%. Contains mol% SiO ₂ . Further, the glass-ceramic aluminoborosilicate glass is about 2 mol% to about 40 mol% B ₂ O ₃ , about 5 mol% to about 16 mol% B ₂ O ₃ , or about 6 mol% to about. It may contain 12 mol% B ₂ O ₃ . In addition, the glass ceramic aluminium silicate glass is about 0.5 mol% to about 16 mol% Al ₂ O ₃ , about 2 mol% to about 20 mol% Al ₂ O ₃ , or about 6 mol. May contain from% to about 14 mol% Al ₂ O ₃ .

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

The glass-ceramic material of the present disclosure contains at least one alkali metal oxide. In embodiments, the glass-ceramic material comprises from about 0.2 mol% to about 15 mol% at least one alkali metal oxide. The at least one alkali metal oxide can be selected from the group containing Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O. In some practices, the difference in the amount of at least one alkali metal oxide and Al ₂ O ₃ in aluminium borosilicate glass ranges from -6 mol% to + 2 mol%.

The glass-ceramic materials of the present disclosure also include at least one alkaline earth metal oxide. In embodiments, the glass ceramic comprises from about 0.1 mol% to about 5 mol% at least one alkaline earth metal oxide. The at least one alkaline earth metal oxide can be selected from the group containing MgO, SrO and BaO. In additional embodiments, the glass-ceramic materials of the present disclosure are 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. Includes% SnO ₂ .

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

Non-limiting compositions of glass ceramics according to the principles of the present disclosure are listed below in Tables 1A (reported in mass percent) and 1B (reported in mol%).

According to embodiments, the glass-ceramic materials of the present disclosure can be produced by using a melt quench process. Appropriate proportions of ingredients may be mixed and blended by turbulent mixing and / or ball mill milling. Batch materials include, but are not limited to, sand, spojumen, foliage stones, nepheline, flash rocks, alumina, borax, boric acid, alkaline and alkaline earth carbonates and lead nitrate, tungsten oxide and ammonium tungstate. Can be mentioned. The batch-blended material is then melted over a predetermined time at a temperature ranging from about 1500 ° C to about 1700 ° C. In some practices, the predetermined time ranges from about 6 to about 12 hours, after which the resulting melt is cast or molded, as will be appreciated by those skilled in the art of the present disclosure, and then cast or molded. , Can be slowly cooled. In some embodiments, the melt can be slowly cooled between about 500 ° C. and about 600 ° C. to define a slow cooling melt.

At this stage of the method, the slow-cooled melt is heat treated at about 500 ° C. to about 1000 ° C. for about 5 minutes to about 48 hours to form a glass ceramic. In embodiments, the heat treatment step is performed at a temperature at or slightly above the slow cooling point of the glass ceramic and below its softening point to generate one or more tungstate crystal phases.

In some embodiments, the slow-cooled melt is heat treated at about 600 ° C. to about 800 ° C. for about 5 minutes to about 24 hours to form a glass ceramic. According to some embodiments, the slow-cooled melt is heat treated at about 650 ° C to about 725 ° C for about 45 minutes to about 3 hours to form a glass ceramic. In another practice, the slow-cooled melt has certain optical properties, such as a light transmission of at least 90% from 700 nm to 3000 nm, and a temperature and temperature to obtain a sharp cut-off wavelength of about 320 nm to about 525 nm. Heat treated over time. In addition, additional heat treatment temperatures and times may be utilized to obtain the glass-ceramic material, as outlined below in the examples.

Examples for Illustrative Uses The following examples show specific non-limiting examples of the glass-ceramic materials and articles of the present disclosure, including methods of making them.

With reference to FIGS. 2A and 2B, transmission vs. wavelength plots of comparative CdSe glass (“Comparative Example 1”) and heat-treated glass ceramic (“Example 1”) are given. Note that FIG. 2B is a plot of FIG. 2A scaled to show the cutoff wavelengths of comparative CdSe glass and heat treated glass ceramics. In this example, Comparative Example 1 of the comparative CdSe glass has a conventional CdSe glass composition according to: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2 ~ 2.0% CdO, 0.2-1% S, and 0-1% Se; the heat-treated glass ceramic has the same composition as shown in Tables 1A and 1B for the sample of Example 1. Has. Further, the glass-ceramics shown in FIGS. 2A and 2B include a heat treatment step comprising heating the slow-cooled melt at 700 ° C. for about 1 hour, as described above in the present disclosure. Was prepared according to the method of manufacturing. In addition, both samples shown in FIGS. 2A and 2B have a normalized pathway length of 4 mm. As is clear from these drawings, the glass ceramic sample (Example 1) heat-treated at 700 ° C. for 1 hour has a sharp cutoff in almost the same wavelength range and abruptness as the CdSe glass sample (Comparative Example 1). Is shown.

With reference to FIGS. 3A and 3B, transmission vs. wavelength plots of comparative CdSe glass (“Comparative Example 1”) and heat-treated glass ceramic (“Examples 1A-1K”) are given. Note that FIG. 3B is a plot of FIG. 3A scaled to show the cutoff wavelengths of comparative CdSe glass and heat treated glass ceramics. In this example, Comparative Example 1 of the comparative CdSe glass has a conventional CdSe glass composition according to: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2 ~ 2.0% CdO, 0.2-1% S, and 0-1% Se; each of the heat-treated glass-ceramic samples was shown in Tables 1A and 1B for the sample of Example 1. Has the same composition as. Further, each of the glass ceramics shown in FIGS. 3A and 3B was prepared according to the method for producing a glass ceramic material as described above in the present disclosure, which comprises the following heat treatment steps after slow cooling: 525 ° C. for 40 minutes (Example 1A), 525 ° C. for 10 hours and 39 minutes (Example 1B), 550 ° C. for 3 hours and 10 minutes (Example 1C), 600 ° C. for 6 hours and 24 minutes (Example 1C). Example 1D), 600 ° C. for 15 hours and 20 minutes (Example 1E), 650 ° C. for 2 hours (Example 1F), 650 ° C. for 3 hours (Example 1G), 650 for 5 hours and 35 minutes. ° C. (Example 1H), 650 ° C. for 23 hours and 10 minutes (Example 1I), 700 ° C. for 1 hour (Example 1J), and 700 ° C. for 2 hours (Example 1K). In addition, all of the samples shown in FIGS. 3A and 3B have a normalized pathway length of 4 mm. As is clear from these drawings, all of the glass ceramic samples (Examples 1A to 1K) heat-treated according to various conditions are steep in the same wavelength range and abruptness as the CdSe glass samples (Comparative Example 1). Indicates a cutoff. Furthermore, it is clear from these drawings that various heat treatment temperature and time conditions can be utilized to change and adjust the cutoff wavelength and its abruptness within the range of about 320 nm to about 525 nm.

According to another example, comparative CdSe glass samples and glass ceramic samples heat treated at 700 ° C. and 800 ° C. according to various conditions were prepared and evaluated for their optical properties. FIG. 4A is a plot of transmittance vs. wavelength of a comparative CdSe glass sample (“Comparative Example 1”) and a glass ceramic sample (Examples 1K and 2A) heat treated at 700 ° C. and 800 ° C. according to various conditions. is there. Note that FIG. 4B is a plot of FIG. 4A scaled to show the cutoff wavelengths of the comparative CdSe glass sample and the glass ceramic sample heat treated according to various conditions. In this example, Comparative Example 1 of the comparative CdSe glass has a conventional CdSe glass composition according to: 40-60% SiO ₂ , 5-20% B ₂ O ₃ , 0-8% P ₂ O ₅ , 1.5-6% Al ₂ O ₃ , 4-8% Na ₂ O, 6-14% K ₂ O, 4-12% ZnO, 0-6% BaO, 0.2 Examples 1K of heat-treated glass ceramics of ~ 2.0% CdO, 0.2-1% S, and 0-1% Se; are shown in Tables 1A and 1B for the sample of Example 1. Example 2A of the heat-treated glass ceramic has the same composition as shown in Tables 1A and 1B for the sample of Example 2. In addition, each of the glass ceramics shown in FIGS. 4A and 4B was prepared according to a method for producing a glass ceramic material, as previously described in the present disclosure, which comprises the following heat treatment steps after slow cooling: 2 700 ° C. over time (Example 1K) and 800 ° C. over 1 hour and 4 minutes (Example 2A). In addition, all of the samples shown in FIGS. 4A and 4B have a normalized pathway length of 4 mm. As is clear from these drawings, all of the glass-ceramic samples (Examples 1K and 2A) heat-treated according to various conditions are steep in the same wavelength range and abruptness as the CdSe glass samples (Comparative Example 1). Indicates a cutoff. In addition, from these drawings and the respective compositions of these glass-ceramics (see Tables 1A and 1B), certain heat treatments to change and adjust the cutoff wavelength and its abruptness within the range of about 320 nm to about 525 nm. It is clear that these magnesium-tungsten-glass-ceramic compositions can be used with the conditions. The high magnesium content of the glass ceramic of Example 2A (about 3.84 mol%) compared to the magnesium content of the glass ceramic of Example 1K (about 0.95 mol%) has a lower cutoff wavelength and probably It is also clear that it may contribute to high transmittance in the NIR range. Therefore, although not bound by theory, changing the magnesium content in these glass-ceramic compositions, along with various heat treatment conditions, can have the effect of changing the spectrum and cutoff wavelength of the glass-ceramic.

Referring here to FIG. 4C, the plot of FIG. 4A is given again, along with the transmission vs. wavelength plots of the comparative CuInSe and CuInS glass samples (“Comparative Example 2” and “Comparative Example 3”, respectively). The spectral plots of Comparative Example 2 and Comparative Example 3 were prepared on March 26, 2015 by Oko-Institut e. V. "Exemption Renewal Request 13 (b)" submitted to Spectaris e. V. Obtained from. Further, FIG. 4C shows Comparative Example 1 of comparative CdSe glass, glass ceramic samples heat-treated according to various conditions (Example 1K and Example 2A), and comparative CuInSe and CuInS samples (Comparative Example 2 and Comparative Example). It is enlarged to show the cutoff wavelength of 3). From FIG. 4C, it is clear that Examples 1K and 2A of the glass-ceramic materials according to the present disclosure outperform the comparative CuInSe and CuInS glasses in terms of approximating the cutoff wavelengths of the comparative CdSe glasses. .. That is, these glass ceramics have optical properties that better approximate those of CdSe glass as compared to other semiconductor-doped glass alternatives, CuInSe and CuInS.

With reference to FIG. 5, an X-ray diffraction (“XRD”) plot of Example 1L (see Tables 1A and 1B) of the heat treated glass ceramic is provided according to at least one example of the present disclosure. .. This sample was heat treated at 700 ° C. for 17 hours and 16 minutes. As evidenced by the peaks at the listed d intervals (eg, d = 3.6127, d = 3.2193, etc.), the glass ceramic of Example 1L may contain an MgWO ₄ crystalline tungsten oxide phase. .. Without being bound by theory, XRD plots of Figure 5, the glass ceramic _can be described as M x WO ₄ crystals, also suggest that includes non-stoichiometric MgWO ₄ phase or mixed alkali MgWO ₄ phase, wherein , M = Mg or M = Mg and one or more of the group of alkali metals consisting of Li, Na, K, Rb and Cd, 0 <x <1.

Referring here to FIGS. 6A-6C, splat-quenched glass-ceramic samples (ie, FIG. 6A, Example 1, no heat treatment after slow cooling) and 650 ° C. for 5 hours and 35 minutes according to the embodiments of the present disclosure. Raman spectroscopy plots of glass-ceramic samples heat-treated at 700 ° C. for 17 hours and 16 minutes (Examples 1H and 1L, respectively, as shown in FIGS. 6B and 6C) are provided. There is. As in the previous example, all of the glass-ceramic materials subjected to the Raman spectroscopy test had the glass-ceramic composition according to Example 1 in Tables 1A and 1B. Specific numbering associated with the data groups of FIGS. 6B and 6C (eg, "# 1", "# 2-orange", "2 # -gray", etc.) is specified on the sample subjected to the Raman spectroscopy test Corresponds to the evaluation positions of (including the color of the sample at those positions). FIG. 6A shows the splat-quenched sample without further heat treatment (Example 1) showing various increased strength levels showing non-crystalline phase (eg, bending Si—O, Al of reticulated structure at 470 cm ^-1). It has been demonstrated that it shows −O and BO). In contrast, FIGS. 6B and 6C show that the heat-treated samples (Examples 1H and 1L) are considerably higher at the same Raman shift position associated with the lower intensity levels observed in the splat-quenched sample (Example 1). It has an intensity level and its position demonstrates the presence of a crystalline phase (eg, WO-W associated with MgW ₂ O ₇ at 846 and 868 cm- ¹ ). Thus, depending on the heat treatment conditions, crystalline tungsten oxide, as can be seen from the presence of signal peaks at Raman shift positions including, but not limited to, 345, 376, 404, 464, 718, 846 and 868 cm ^-1 . It seems clear that a phase, eg, the generation of MgW ₂ O ₇ , is brought about. 6B and 6C show the crystalline tungsten oxide phase in combination with or instead of the crystalline tungsten oxide phase (ie, the MxWO ₄ crystal phase outlined above), depending on the heat treatment conditions (ie, non-chemical quantity theory). It also suggests that the occurrence of (target) will be brought about.

Referring here to FIGS. 7A and 7B, glass ceramic samples heat treated at 650 ° C. for 5 hours and 35 minutes and at 700 ° C. for 17 hours and 16 minutes, respectively, according to the examples of the present disclosure (Example 1H, respectively). And Example 1L), and Raman spectroscopy plots of a glass-ceramic sample that remains splat-quenched (ie, Example 1, no heat treatment after slow cooling) are provided. As in the previous example, all of the glass-ceramic materials subjected to the Raman spectroscopy test had the glass-ceramic composition according to Example 1 in Tables 1A and 1B. Specific numbering (eg, "# 1", "# 2-orange", etc.) associated with the data set in these drawings is a specific evaluation position (at those positions) on the sample subjected to the Raman spectroscopy test. (Including the color of the sample). First, FIGS. 7A and 7B show the same Raman shift in which the splat-quenched sample (Example 1) is associated with the high intensity levels observed in the samples (Examples 1H and 1L) subjected to specific heat treatment conditions. It shows that it has a substantially lower intensity level at the position. Thus, the heat treatment conditions, the crystal tungsten oxide phase (for example, mgw 2 _O 7 as shown in both FIGS. 7A and _7B) and / or crystalline tungsten suboxide phase (i.e., non-stoichiometric It is clear that it can result in the occurrence of (phase).

Referring here to FIG. 8, residual stress (MPa) vs. substrate for two glass-ceramic samples (Example 10-IOXA and Example 10-IOXB) having compressive stress regions derived from each of the two ion exchange process conditions. Depth (mm) plot of is given. In FIG. 8, the y-axis is the residual stress in the substrate, a positive value refers to tensile residual stress, and a negative value refers to compressive residual stress. Further, in FIG. 8, the x-axis is the depth at each of the substrates, and the values at 0 mm and 1.1 mm represent the main surface of the substrate (for example, the main surface of the substrate 10 as shown in FIG. 1). 12 and 14). Each of the glass-ceramic samples in this example, Example 10-IOXA and Example 10-IOXB, has the same composition as shown in Tables 1A and 1B for the sample of Example 10. In addition, each of those samples was melted and poured onto a steel table to form an optical putty, consistent with the method outlined earlier in this disclosure. Next, each sample was slowly cooled at 570 ° C. for 1 hour and then cooled to ambient temperature at the cooling rate of the furnace. Next, a sample having a size of 25 mm × 25 mm × about 1.1 mm was ground and polished to form a slowly cooled optical putty. Finally, a sample of Example 10-IOXA was immersed in a 100% NaNO ₃ molten salt bath at 390 ° C. for 8 hours to form a compressive stress region. Similarly, a sample of Example 10-IOXB was immersed in a 100% NaNO ₃ molten salt bath at 390 ° C. for 16 hours to form a compressive stress region. Note that the actual thicknesses of the samples of Example 10-IOXA and Example 10-IOXB were measured to be 1,10 mm and 1.06 mm, respectively.

As is apparent from FIG. 8, longer ion exchange periods increase the magnitude of the glass-ceramic DOC, storage strain energy and peak tension (ie, maximum tensile stress in the central tension region) while reducing maximum compressive stress. It tends to make you. Specifically, Example 10-IOXA, which is a glass-ceramic sample having a shorter ion exchange period, is given by a compressive stress region of 136.7 μm compressive depth (DOC), a maximum compressive stress of about −320 MPa, and a peak tension of 57 MPa. The central tension (CT) region and the stored strain energy of 16.6 J / m ² are shown. In contrast, Example 10-IOXB, which is a glass-ceramic sample with a longer ion exchange period, has a DOC of 168.0 μm, a maximum compressive stress of about -270 MPa, a CT region given by a peak tension of 72 MPa, and 25 J /. The storage strain energy of m ² is shown. Therefore, due to the longer ion exchange period of Example 10-IOXB, it was given by a larger DOC, lower maximum compressive stress, higher peak tension compared to Example 10-IOXA with a shorter ion exchange period. The CT region and greater storage strain energy are provided.

It is clear that the glass-ceramic sample shown in FIG. 8 showed a compressive stress region resulting from immersion in a molten salt bath of 100% NaNO ₃ , but other methods are also considered within the present disclosure. Be done. For example, the glass-ceramic can be ion-exchanged in a bath of molten KNO ₃ or a mixture of NaNO ₃ and KNO ₃ to increase the level of compressive stress on or near the surface of the substrate, or first. Ion exchange may be continuous in the NaNO ₃ bath and then in the KNO ₃ bath. Therefore, sulfates, chlorides, and other salts of metal ions that undergo ion exchange (eg, Na ⁺ , K ^+, etc.) can also be used in these baths. Further, the ion exchange temperature can vary from about 350 ° C to about 550 ° C, but is preferably from about 370 ° C to about 450 ° C to avoid salt decomposition and stress relaxation.

Broadly referring to FIGS. 9-11B, clear size regions of crystals were found in the tungsten bronze and multicolored tungsten bronze glass ceramics described above. The crystal size depended on the basic glass composition, but could be adjusted slightly by the heat treatment time and temperature. In addition, the crystallization rate is significantly increased by the addition of small amounts of calcium oxide (CaO), which may react with tungsten oxide to function as scheelite nanocrystals, or nucleation sites. It is thought to form a stoichiometric scheelite-like structure.

Referring here to FIG. 9, relatively large crystals were found in the highly peraluminum tungsten bronze melt (eg, M _x WO ₃ glass ceramic) described above and shown in FIG. These crystals had a needle-like shape, a length of 100 to 250 nm, and a width of 5 to 30 nm. In the as-quenched state, these glass-ceramic materials are X-ray amorphous after being quenched (ie, splat-quenched) between two iron plates and scanned electron microscope (SEM) analysis. It was found that there were no precipitates (crystals, crystals). After heat treatment of the quenching glass at 700 ° C. for more than 30 minutes and cooling to room temperature at 10 ° C. per minute, tungsten bronze precipitates were formed along the alumina-rich needles. Increasing the heat treatment time and temperature, such as after heat treatment at 700 ° C. for 1 hour and 40 minutes and cooling to room temperature at 10 ° C. per minute, increased the concentration of precipitates. X-ray energy dispersive X-ray spectroscopic analysis (EDS) maps of crystals formed after heat treatment show that they consist of tungsten, oxygen, and potassium.

With reference to FIGS. 10A and 10B, for at least some peralkali tungsten bronze melts (R ₂ O-Al ₂ O ₃ > 0), the crystallite size is smaller than that in the peraluminum melt (FIG. 9). No alumina-rich needles were formed. Like the peraluminum melt, this peralkali material was X-ray amorphous when quenched (ie, splat quenched) between two iron plates. Micrographs show that there are no crystals in the material prior to heat treatment. Heat treatment of splat quenching at 550 ° C. for a period between 15 and 30 hours, then cooling to 475 ° C. at 1 ° C./min, then cooling to room temperature at the cooling rate of the furnace, followed by TEM analysis. As a result, the formation of needle-shaped tungsten bronze crystals having a high aspect ratio as shown in FIGS. 10A to 10B was found. Most of the resulting needles were between 2 nm and 7 nm in diameter and between 10 nm and 30 nm in length. X-ray EDS of the heat-treated splat quenching sample showed that the crystals contained tungsten.

With reference to FIGS. 11A and 11B, the silver tungsten bronze glass ceramic has a substantially rod-like shape with an aspect ratio between 2 and 4, usually about 2 to 20 nm in length and usually about 2 to 10 nm in diameter. Approximately 11 to 14.8 percent by volume of the glass-ceramic material was contained. The samples shown in FIGS. 11A and 11B were heat treated at 550 ° C. for 4 hours, cooled to 475 ° C. at 1 ° C./min, and then cooled to room temperature at a furnace cooling rate. The cane was then placed in a gradient furnace for 5 minutes so that one end of the cane remained at room temperature and the other end of the cane was at 650 ° C. The region between each end was exposed to a nearly uniform gradient of temperature between 25 ° C and 650 ° C. In the region where the temperature was above about 575 ° C., the color began to shift from blue to green, yellow, orange and finally red. The transparency of all colors was high.

As previously disclosed, glass ceramics according to some exemplary embodiments have a transmittance of about 5% / mm or more over at least one 50 nm wide wavelength range of light in the range of about 400 nm to about 700 nm. Has. However, in other embodiments, glass-ceramics, such as those that are opaque, have lower transmittances. According to at least some of such embodiments, these glass-ceramics are unique in that they absorb light intensely but do not scatter and have a very low haze. According to various such embodiments, the glass ceramic has an optical density of at least 0.07 per millimeter (OD / OD /) for at least some (eg, most,> 90%) of light having a wavelength of 200-400 nm. M), with a haze of at most 25 OD / mm and / or less than 10% of the same wavelength, where the optical density is calculated from the measurement of optical absorption made with a spectrophotometer, the haze is Measured by the haze meter wide-angle scattering test. According to various such embodiments, the glass ceramic has an optical density of at least 0.022 millimeters per millimeter (OD / OD /) for at least some (eg, most,> 90%) of light having a wavelength of 400-750 nm. mm), with haze of at most 10 OD / mm and / or less than 10% of the same wavelength. According to various such embodiments, the glass ceramic has an optical density of at least 0.04 millimeters per millimeter (OD / OD /) for at least some (eg, most,> 90%) of light having a wavelength of 750 to 2000 nm. mm), with a haze of at most 15 OD / mm and / or less than 10% of the same wavelength.

Examples Containing Titanium With reference to FIGS. 8A and 8B here, a list of exemplary glass-ceramic compositions of articles containing titanium is given.

Here, with reference to Tables 8C and FIGS. 12A-17B, optical data for samples of compositions from Tables 8A and 8B are given.

For the various compositions in Table 8C and FIGS. 12A-17B, the batch components were weighed, the batch components were mixed in a shaker mixer or ball mill and 4 to 1300 ° C. to 1650 ° C. in a molten silica crucible. Prepared by melting for 32 hours. Glass was poured onto a metal table to produce a 0.5 mm thick glass putty. Some melt was poured onto a steel table and then rolled into sheets using steel rollers. Samples were heat treated in an electric oven with ambient air at temperatures ranging from 425 to 850 ° C. for a period of 5 to 500 minutes to create and control the transmission and absorption of light. The sample putty was then ground to a thickness of 0.5 mm and tested.

As is clear from the data in Table 8C and FIGS. 12A-17B, the as-made state of the titanium-containing glass is highly transparent in the NIR region and generally transparent at visible wavelengths. During heat treatment at temperatures ranging from about 500 ° C to about 700 ° C, crystalline phases (ie, titanium phosphite) precipitate, reducing the light transmittance of these samples, some of which are strongly absorbed by NIR. Become a sex.

Powder X-ray diffraction was performed on each of the compositions in Table 8C, and all compositions were X-ray amorphous as they were produced and in the uncooled state. The heat-treated sample showed evidence of several titanium-supported crystalline phases, including anatase (889FLY) and rutile (889FMC and 889FMD). The sample showed low haze (ie, about 10% or less, or about 5% or less, or about 1% or less, or about 0.1% or less). Although not constrained by theory, the low haze exhibited by these compositions in their as-manufactured and heat-treated conditions is that the crystals are extremely small (ie, about 100 nm or less) and small amounts (ie, TiO). Due to the fact that ₂ is (due to the fact that only about 2 mol% has been introduced). Therefore, the seeds formed in these materials are considered to be below the detection limits (size and abundance) of conventional powder XRD. This hypothesis was confirmed by TEM microscopy.

Here, referring to FIGS. 18A-D, four different magnification TEM micrographs of titania-containing crystals in a sample of glass cord 889FMC heat treated at 700 ° C. for 1 hour are given. These crystals are rod-shaped in appearance and have an average width of about 5 nm and an average length of about 25 nm.

Referring here to FIGS. 19A and 19B, a TEM micrograph (FIG. 19A) of a heat treated sample of glass code 889FMC and a corresponding EDS element map (FIG. 19B) are given. As can be seen from FIG. 19A, the sample contains a plurality of crystals. The EDS map was set to detect titanium. The results of EDS mapping of titanium are in close agreement with the crystals, indicating that the crystals are rich in titanium. In this map, bright or "white" areas indicate the presence of Ti.

Here, referring to Table 9A, an exemplary glass composition containing no titanium is given.

Table 9B gives the solar performance evaluation indexes of various glasses. In Table 9B, the composition 196 KGA is incorporated as the clad layer of the double fusion laminate (ie, the total thickness of the clad and glass ceramic = 0.2 mm), and the core composition of the laminate is Corning Traded (ie). It was a chemically strengthened Gorilla® glass from (Registered Trademark). The composition 196 KGA was 1 mm thick, was heat treated at 550 ° C for 30 minutes and cooled to 475 ° C at 1 ° C / min. The 889 FMD sample was 5 mm thick and was heat processed at 600 ° C. for 1 hour. The 889 FMG sample was 0.5 mm thick and was heat processed at 700 ° C. for 2 hours. The VG10 sample refers to glass sold under the trade name SGG VENUS (VG10) under the Saint-Gobain®, with different thicknesses.

In Table 9B, T_L is the total visible light transmittance (weighted average transmittance of light passing through the plate glass in the wavelength range of 380 nm to 780 nm, which is tested according to ISO9050 Section 3.3). T_TS is also referred to as total transmitted sunlight (solar factor (“SF”) or total solar heat transmission (“TSHT”), which is absorbed by plate glass as measured by ISO 13837-2008 Annex B and ISO 9050-2003 section 3.5. And then the sum of T_DS (total direct sunlight), plus the fraction of the solar energy re-radiated into the cabin). In this case, T_TS is calculated under the condition of a stopped vehicle at a wind speed of 4 m / s (14 km / hr)%, and T_TS is equal to (% T_DS) + 0.276 ^* (% solar absorption). T_DS, also referred to as total direct solar transmittance (“solar transmittance” (“Ts”) or “energy transfer”, passes through plate glass in the wavelength range of 300 nm to 2500 nm, as measured by ISO13837 section 6.3.2. It is the weighted average transmittance of light). R_DS is a reflected sunlight component (ie, including a nominal 4% Fresnel reflection). T_E is the direct sunlight transmittance. T_UV is the UV transmission measured at ISO 9050 and ISO 13837A. T_IR is the infrared transmittance measured according to the Volkswagen standard TL957.

As is obvious from the data in Table 9B, glass code 196KGA has the best optical performance and can produce the lowest UV, VIS, and NIR transmittance with a very short path length (0.2 mm). .. The titanium-containing compositions 889FMD and 889FMG at a thickness of 0.5 mm produce better optical performance than VG10 glass with a path length of 3.85 mm or shorter. In other words, the titanium-containing compositions 889FMD and 889FMG had better performance than VG10, despite having shorter pathway lengths.

Further referring to at least some glass ceramics disclosed or conceivable herein, the glass ceramic comprises an amorphous phase and a crystalline phase, the crystalline phase being of the formula M _x TiO as disclosed herein. _2. Includes (e.g., contains, most) bronze structures as disclosed herein, such as precipitates such as M _x WO ₃ . The volume fraction of the crystalline phase is from about 0.001% to about 20%, or from about 1% to about 20%, or from about 5% to about 20%, or from about 10% to about 20%, or from about 10%. It can range from about 30%, or about 0.001% to about% 50. In other embodiments, the volume fraction of the crystalline phase is from about 0.001% to about 20%, or from about 0.001% to about 15%, or from about 0.001% to about 10%, or about 0. It can range from .001% to about 5%, or from about 0.001% to about 1%. In another possible embodiment, the volume fraction of the crystalline phase in the glass ceramic may be greater than 50%.

Further referring to at least some glass ceramics disclosed or conceivable herein, the glass ceramic comprises an amorphous phase and a crystalline phase, the crystalline phase as disclosed herein, of the formula M _x thio. _2. Containing bronze structures as disclosed herein (eg, containing, and most), such as precipitates such as M _x WO ₃ , M is a dopant positive as disclosed herein. Representing an ion, the precipitate (eg, crystal) is a suboxide, and in the formula, 0 <x <1, 0 <x <0.9, 0 <x <0.75, 0 <x <0. 0 <x <1, such as 5, 0 <x <0.2, and / or 0.01 <x <1, 0.1 <x <1, 0.2 <x <1, 0.5 <x < 0.01 <x <1, such as 1, and / or 0.01 <x <0.99, 0.1 <x <0.9, 0.2 <x <0.9, 0.1 <x < 0.001 <x <0.999 such as 0.8.

The structure and arrangement of methods and products, as shown in various exemplary embodiments, are merely examples. Although only a few embodiments have been described in detail in this disclosure, many modifications (eg, size, dimensions, structure, etc.) have been made without substantially departing from the novel teachings and advantages of the subject matter described herein. , Shape, and ratio of various elements, parameter values, mounting methods, material use, color, orientation changes) are possible. Some elements shown to be integrally molded may be composed of a large number of parts or elements, and the position of the elements may be reversed or otherwise changed, the nature of the individual elements or positions or The numbers may be varied or varied. The sequence or sequence of steps of any process, logical algorithm, or method may be altered or rearranged according to alternative embodiments. Other substitutions, improvements, modifications and omissions may be made to the design, operating conditions and arrangement of various exemplary embodiments without departing from the scope of the art of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in terms of terms.

Embodiment 1
In glass-ceramic
A crystalline phase containing an amorphous phase and a plurality of precipitates having the formula M _x WO ₃ and / or M _x MoO ₃ , where 0 <x <1 and M is a dopant cation. Crystal phase,
Including glass ceramic.

Embodiment 2
The glass ceramic according to embodiment 1, wherein the precipitate has a length of about 1 nm to about 200 nm as measured by electron microscopy.

Embodiment 3
The glass ceramic according to the first or second embodiment, wherein the precipitates of the crystal phase are substantially uniformly distributed in the glass ceramic.

Embodiment 4
In glass-ceramic
Silicate glass, and crystals uniformly distributed within the silicate glass, containing non-stoichiometric tungsten and / or molybdenum suboxide, with dopant cations inserted.
Including glass ceramic.

Embodiment 5
The glass ceramic according to the fourth embodiment, wherein the glass ceramic has a transmittance of about 5% / mm or more over at least one wavelength region of 50 nm width of light in the range of about 400 nm to about 700 nm.

Embodiment 6
The dopant cations are H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, At least one of Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce. The glass ceramic according to the fourth embodiment.

Embodiment 7
The glass ceramic according to the fourth embodiment, wherein the crystal has a rod-like shape.

8th Embodiment
The glass ceramic according to the fourth embodiment, wherein a part of the crystal is at a depth of more than about 10 μm from the outer surface of the glass ceramic.

Embodiment 9
In glass-ceramic
A crystal that contains a glass phase and a suboxide of tungsten and / or molybdenum, wherein the suboxide of tungsten and / or molybdenum has a solid defect structure in which holes are occupied by dopant cations. phase,
Including glass ceramic.

Embodiment 10
The glass ceramic according to embodiment 9, wherein the crystal phase has a volume fraction in the glass ceramic of about 0.001% to about 20%.

Embodiment 11
In the article
With at least one amorphous phase and one crystalline phase,
With about 1 mol% to about 95 mol% SiO ₂
Including
The crystal phase contains about 0.1 mol% to about 100 mol% of oxides of the crystal phase, and the oxides are (i) W, (ii) Mo, (iii) V and alkali metal cations. , And (iv) Ti and an alkali metal cation: an article comprising at least one of.

Embodiment 12
The article according to embodiment 11, wherein the crystal phase is substantially uniformly distributed in the article as a plurality of precipitates.

Embodiment 13
The article according to embodiment 12, wherein at least a part of the precipitate is located at a depth of more than about 10 μm from the outer surface of the article.

Embodiment 14
The article according to embodiment 11, wherein the crystal phase comprises a plurality of precipitates having a length of about 1 nm to about 500 nm as measured by electron microscopy.

Embodiment 15
The article according to embodiment 11, wherein the article is substantially free of Cd and Se.

Embodiment 16
Glass, in batch ingredients,
About 25 mol% to about 99 mol% SiO ₂ ,
About 0 mol% to about 50 mol% Al ₂ O ₃ ,
About 0.35 mol% to about 30 mol% WO ₃ + MoO ₃ ,
About 0.1 mol% to about 50 mol% R ₂ O, where R ₂ O is one or more of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O. R ₂ O-Al ₂ O ₃ is from about -35 mol% to about 7 mol%, and (i) about 0.02 mol% to about 50 mol% RO, and (ii) about 0.01 mol. % To about 5 mol% of SnO ₂ , where RO is one or more of MgO, CaO, SrO, BaO and ZnO.
Including
If WO ₃ is from about 1 mol% to about 30 mol%, and thus the glass contains less than about 0.9 mol% Fe ₂ O ₃ , or thus SiO ₂ is from about 60 mol% to about. 99 mol%
If WO ₃ is from about 0.35 mol% to about 1 mol%, then the glass contains from about 0.01 mol% to about 5.0 mol% SnO ₂ .
If MoO ₃ is from about 1 mol% to about 30 mol%, thus SiO ₂ is from about 61 mol% to about 99 mol%, or Fe ₂ O ₃ is from about 0.4 mol%. R ₂ O is more than RO,
If MoO ₃ is from about 0.9 mol% to about 30 mol% and SiO ₂ is from about 30 mol% to about 99 mol%, then the glass is from about 0.01 mol% to about 5 mol. A glass further comprising% SnO ₂ .

Embodiment 17
It further contains from about 2.0 mol% to about 40 mol% B ₂ O ₃ , SiO ₂ from about 45 mol% to about 80 mol%, and Al ₂ O ₃ from about 0.5 mol% to about 15 mol. %, R ₂ O is from about 0 mol% to about 14 mol%, RO is from about 0 mol% to about 1 mol%, and (1) MoO ₃ is about 0 mol% and WO ₃ is from about 1.0 mol% to about 17 mol%, (2) SnO ₂ is from about 0.01 mol% to about 0.4 mol%, and / or (3) Fe ₂ O ₃ is The glass according to embodiment 16, which is at least one of about 0 mol% to about 0.2 mol%.

Embodiment 18
It further comprises from about 5 mol% to about 20 mol% B ₂ O ₃ , SiO ₂ from about 55 mol% to about 75 mol%, Al ₂ O ₃ from about 8 mol% to about 12 mol%, and so on. R ₂ O is from about 3 mol% to about 14 mol%, RO is from about 0.5 mol% to about 4.5 mol%, and WO ₃ is from about 1.9 mol% to about 10 mol%. The glass according to embodiment 16, wherein MoO ₃ is from about 0 mol% to about 1.0 mol%.

Embodiment 19
It further comprises from about 4 mol% to about 35 mol% B ₂ O ₃ , SiO ₂ from about 55 mol% to about 75 mol%, Al ₂ O ₃ from about 9 mol% to about 14 mol%, and so on. R ₂ O is from about 2.9 mole% to about 12.2 mole%, RO is from about 0.01 mole% to about 0.5 mol%, MoO ₃ from about 0 mole% to about 8. 2 mol%, WO ₃ is from about 0 mol% to about 9 mol%, and (1) SnO ₂ is from about 0.04 mol% to about 0.4 mol%, (2) Fe ₂ O. ₃ is at least one of about 0 mol% to about 0.2 mol% and / or (3) V ₂ O ₅ is about 0 mol% to about 0.4 mol%, embodiment 16. The glass described in.

20th embodiment
It further comprises from about 5 mol% to about 25 mol% B ₂ O ₃ , SiO ₂ from about 50 mol% to about 75 mol%, Al ₂ O ₃ from about 7 mol% to about 14 mol%, and so on. R ₂ O is from about 5 mol% to about 14 mol%, RO is from about 0.02 mol% to about 0.5 mol%, and MoO ₃ is from about 1.9 mol% to about 12.1 mol. %, WO ₃ is from about 1.7 mol% to about 12 mol%, and (1) the glass is from about 0.01 mol% to about 0.75 mol% Ag, about 0.01 mol. At least one of% to about 0.5 mol% Au, about 0.01 mol% to about 0.03 mol% V ₂ O ₅ , and about 0.01 mol% to about 0.75 mol% Cu O. The glass according to embodiment 16, wherein the glass further comprises, and / or (2) SnO ₂ is at least one of about 0.01 mol% to about 0.5 mol%.

21st embodiment
It further contains from about 10 mol% to about 20 mol% B ₂ O ₃ , SiO ₂ from about 60 mol% to about 78 mol%, and Al ₂ O ₃ from about 0.3 mol% to about 10 mol%. Yes, R ₂ O is about 0.6 mol% to about 10 mol%, RO is about 0.02 mol%, Mo O ₃ is about 0 mol%, WO ₃ is about 1.0 mol. The glass according to embodiment 16, which is from% to about 7.0 mol%.

Embodiment 22
In the method of forming glass-ceramic articles
A step of forming a glass melt by melting together components containing (1) bound alkali, (2) SiO ₂ , and (3) tungsten and / or molybdenum.
A step of solidifying the glass melt into glass, and a step of precipitating a crystal phase in the glass to form the glass-ceramic article.
How to have.

23rd Embodiment
22. The method of embodiment 22, wherein the glass is a single homogeneous phase.

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

25.
The binding alkalis are (A) feldspar, (B) nepheline, (C) sodium borate, (D) spojumen, (E) albite, (F) potassium feldspar, (G) alkali aluminosilicate, (H). ) Alkaline silicate and / or any one of embodiments 22-24, comprising an alkali bonded to (I) (I) alumina, (I-ii) boria and / or (I-iii) silica. The method described in one.

Embodiment 26
In the method of forming glass ceramics
The process of melting silica and components containing tungsten and / or molybdenum together to form a glass melt,
A step of solidifying the glass melt to form a glass, and a step of precipitating a plurality of bronze-type crystals containing tungsten and / or molybdenum in the glass.
How to have.

Embodiment 27
The method according to embodiment 26, wherein the step of precipitating the plurality of bronze type crystals includes a step of heat-processing the glass.

28.
The method according to embodiment 26 or 27, further comprising the step of growing a plurality of bronze type crystals to a length of at least about 1 nm and about 500 nm or less.

Embodiment 29
In glass-ceramic
A crystalline phase containing an amorphous phase and a precipitate of the formula M _x TiO ₂ , in which 0 <x <1 and M is a dopant cation, the crystalline phase,
Including glass ceramic.

30th embodiment
The glass ceramic according to embodiment 29, wherein the glass ceramic exhibits a transmittance of about 1% / mm or more over at least one wavelength range of 50 nm width of light in the range of about 400 nm to about 700 nm.

Embodiment 31
The glass ceramic according to embodiment 29, wherein at least some of the precipitates are at least 1 nm long and 300 nm or less in length.

Embodiment 32
The glass ceramic according to embodiment 31, wherein the precipitates of the crystal phase are uniformly distributed in the glass ceramic.

Embodiment 33
The glass ceramic according to embodiment 31, wherein the precipitate of the formula M _x TiO ₂ is contained in the glass ceramic at a volume fraction of at least 0.001% and 20% or less.

Embodiment 34
The glass ceramic according to embodiment 33, wherein the precipitate of the formula M _x TiO ₂ is contained in the glass ceramic at a volume fraction of at least 5%.

Embodiment 35
The dopant cations are H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Including Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and / or Ce. The glass ceramic according to form 34.

Embodiment 36
In glass-ceramic
A silicate glass, and a crystal uniformly distributed in the silicate glass and containing a titanium hydroxide in which a dopant cation is inserted.
Including glass ceramic.

Embodiment 37
The glass ceramic according to embodiment 36, wherein the glass ceramic exhibits a transmittance of about 1% / mm or more over at least one wavelength range of 50 nm width of light in the range of about 400 nm to about 700 nm.

38.
The glass ceramic according to embodiment 36, wherein the crystals are at least 1 nm long and 300 nm or less in length.

Embodiment 39
The glass ceramic according to embodiment 38, wherein the crystals are uniformly distributed in the glass ceramic.

Embodiment 40
38. The glass ceramic according to embodiment 38, wherein the crystals are contained in the glass ceramic at a volume fraction of at least 0.001% and 20% or less.

Embodiment 41
The glass ceramic according to embodiment 40, wherein the crystals are contained in the glass ceramic at a volume fraction of at least 5%.

42.
The dopant cations are H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Including Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and / or Ce. The glass ceramic according to form 41.

Embodiment 43
In glass-ceramic
The glass phase, and the crystal phase containing titanium suboxide, which forms a solid defect structure in which holes are occupied by dopant cations.
Including glass ceramic.

Embodiment 44
The glass ceramic according to embodiment 43, wherein the glass ceramic exhibits a transmittance of about 1% / mm or more over at least one wavelength range of 50 nm width of light in the range of about 400 nm to about 700 nm.

Embodiment 45
In glass-ceramic articles
With at least one amorphous phase and one crystalline phase,
With about 1 mol% to about 95 mol% SiO ₂
Including
The crystal phase contains from about 0.1 mol% to about 100 mol% of non-stoichiometric titanium suboxide of the crystal phase, and the suboxides are (i) Ti, (ii) V and alkali metals. Cation: A glass-ceramic article containing at least one of.

Embodiment 46
The glass-ceramic article according to embodiment 45, wherein the crystal phase is substantially uniformly distributed in the glass-ceramic article as a plurality of precipitates.

Embodiment 47
The article of embodiment 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.

Embodiment 48
The article according to embodiment 45, wherein the crystalline phase comprises a plurality of precipitates having a length of about 1 nm to about 500 nm as measured by electron microscopy.

Embodiment 49
The glass-ceramic article according to embodiment 45, wherein the article is substantially free of Cd and Se.

Embodiment 50
In the method of forming glass ceramics
The process of melting components containing silica and titanium together to form a glass melt,
A step of solidifying the glass melt to form a glass, wherein the glass contains a first average near-infrared absorbance, and a crystal phase is precipitated in the glass to form the glass ceramic. The glass ceramic comprises (a) a second average infrared absorbance and (b) an average optical density of about 1.69 or less per mm, and the first average infrared absorbance. The ratio of the second average infrared absorbance to the glass is about 1.5 or more.
How to have.

Embodiment 51
The method according to embodiment 50, wherein the step of precipitating the crystal phase is carried out at a temperature of about 450 ° C to about 850 ° C.

52.
The method according to embodiment 50, wherein the step of precipitating the crystal phase is carried out at a temperature of about 500 ° C to about 700 ° C.

Embodiment 53
The method according to embodiment 50, wherein the step of precipitating the crystal phase is carried out for a period of about 15 minutes to about 240 minutes.

Embodiment 54
The method according to embodiment 50, wherein the step of precipitating the crystal phase is carried out for a period of about 60 minutes to about 90 minutes.

Embodiment 55
In glass, in batch components,
About 1 mol% to about 90 mol% SiO ₂ ,
About 0 mol% to about 30 mol% Al ₂ O ₃ ,
Approximately 0.25 mol% to approximately 30 mol% of TiO ₂ ,
About 0.25 mol% to about 30 mol% metal sulfide,
About 0 mol% to about 50 mol% R ₂ O, and about 0 mol% to about 50 mol% RO,
Here, R ₂ O is one or more of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O, and RO is BeO, MgO, CaO, SrO, BaO and A glass that is one or more of ZnO and the glass is substantially free of Cd.

Embodiment 56
The glass according to embodiment 55, wherein the TiO ₂ is from about 1.0 mol% to about 15 mol%.

Embodiment 57
The glass according to embodiment 55, wherein the TiO ₂ is from about 2.0 mol% to about 10 mol%.

Embodiment 58
The glass according to embodiment 55, wherein the metal sulfide is from about 1.0 mol% to about 15 mol%.

Embodiment 59
The glass according to embodiment 58, wherein the metal sulfide is from about 1.5 mol% to about 5 mol%.

Embodiment 60
The metal sulfide, MgS, including at least one of _Na 2 S, and ZnS, glass according to any one of embodiments 55 59.

Embodiment 61
The glass according to embodiment 55, wherein the glass is substantially free of Li.

Embodiment 62
The glass according to embodiment 55, wherein the glass is substantially free of Zr.

10 Substrate 12, 14 Main surface 50 Compressive stress region 52 First selection depth 100 Article

Claims (8)

In glass-ceramic
Silicate glass, and crystals uniformly distributed within the silicate glass, containing non-stoichiometric tungsten and / or molybdenum suboxide, with dopant cations inserted.
Including glass ceramic. The glass ceramic according to claim 1, wherein the glass ceramic has a transmittance of about 5% / mm or more over at least one wavelength region of 50 nm width of light in the range of about 400 nm to about 700 nm. The dopant cations are H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, At least one of Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and Ce. The glass ceramic according to claim 1. The glass ceramic according to claim 1, wherein the crystal has a rod-like shape. In the method of forming glass-ceramic articles
A step of forming a glass melt by melting together components containing (1) bound alkali, (2) SiO ₂ , and (3) tungsten and / or molybdenum.
A step of solidifying the glass melt into glass, and a step of precipitating a crystal phase in the glass to form the glass-ceramic article.
How to have. 5. The method of claim 5, wherein the glass is a single homogeneous phase. The method of claim 5 or 6, wherein the crystalline phase comprises tungsten and / or molybdenum. The binding alkalis are (A) feldspar, (B) nepheline, (C) sodium borate, (D) spojumen, (E) albite, (F) potassium feldspar, (G) alkali aluminosilicate, (H). ) Alkaline silicate and / or (I) (I-i) alumina, (I-ii) boria and / or (I-iii) silica-bound alkali, any one of claims 5-7. The method described.

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