Near-infrared-shielding transparent glass-ceramics

Abstract

The present application relates to transparent glass-ceramics that shield near-infrared. An optically transparent glass-ceramic material includes a glass phase and a crystalline tungsten bronze phase comprising nanoparticles and having a chemical formula MxWO3, where M includes at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 < x < 1. Aluminosilicate and zinc-bismuth-borate glasses including at least one of Sm2O3, Pr2O3, and Er2O3 are also provided.

Description

[0001] This patent application is a continuation-in-part of International Application No. PCT / US2017 / 037809, International Filing Date, June 16, 2017, which entered the National Stage in the United States as U.S. Patent Application No. 15 / 870, 677, filed on January 22, 2018, entitled "NEAR INFRARED-SCREENING TRANSPARENT GLASS-CERAMIC," the entire disclosure of which is hereby incorporated by reference herein in its entirety.

[0002] This application claims priority under 35 U.S.C. § 119 to U.S. Provisional Application Serial No. 62 / 352,602, filed June 21, 2016, and U.S. Provisional Application Serial No. 62 / 351,616, filed June 17, 2016, which are hereby incorporated by reference herein in their entirety and relied upon for all purposes. BACKGROUND

[0003] The present disclosure relates to glass-ceramic materials. More specifically, the present disclosure relates to optically transparent glass-ceramic materials. Even more specifically, the present disclosure relates to optically transparent glass-ceramic materials having a crystalline tungsten bronze phase.

[0004] Near infrared (NIR)-screening glasses have been developed to block and / or eliminate the wavelength range of 700-2500 nm for applications such as optical filters, lenses, and glass windows for medical, defense, aerospace, and consumer applications.

[0005] Low emissivity (low-E) coatings have been developed to minimize the amount of ultraviolet and infrared light that can pass through the glass without compromising the amount of visible light transmitted. Low-E coatings are typically sputtered or pyrolyzed coatings. Alternatively, low-E plastic stacks can be retrofitted onto glass substrates.

[0006] Thin films, coatings, and composites using nanosized or microsized particles of non-stoichiometric low tungsten oxide or doped non-stoichiometric tungsten trioxide (referred to herein as tungsten bronze) have been used to provide near infrared screening with high transparency in the visible spectrum. However, tungsten bronze thin films typically require expensive vacuum deposition chambers, have limited mechanical robustness, and are susceptible to oxygen, moisture, and UV light, all of which result in reduced NIR screening performance and discoloration of these materials and degradation of transparency in the visible range. SUMMARY

[0007] The present disclosure provides optically transparent glass-ceramic materials, which in some embodiments, include: a glass phase containing at least about 80 wt% silica; and a crystalline tungsten bronze phase having a chemical formula M xWO3, where M includes, but is not limited to, at least one of: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 < x < 1. The crystalline tungsten bronze phase comprises nanoparticles. In some embodiments, the glass-ceramic has a low coefficient of thermal expansion (CTE) and is strongly attenuating or blocking to ultraviolet (UV) radiation for wavelengths less than about 360 nm and near infrared radiation (NIR) for wavelengths from about 700 nm to about 3000 nm. Also provided are aluminosilicate and zinc-bismuth-borate glasses comprising at least one of Sm2O3, Pr2O3, and Er2O3.

[0008] Accordingly, one aspect of the disclosure provides a glass-ceramic comprising: a silicate glass phase and from about 1 mol% to about 10 mol% of a crystalline M x WO3 phase, the crystalline M x The crystalline tungsten bronze phase comprises nanoparticles, where M is at least one of: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 < x < 1.

[0009] A second aspect of the disclosure provides a glass-ceramic comprising a silicate glass phase and from about 1 mol% to about 10 mol% of a crystalline M x WO3 phase, the crystalline M

[0010] In another aspect, an aluminosilicate glass is also provided comprising: SiO2, Al2O3, and at least one of: Sm2O3, Pr2O3, and Er2O3, where Sm2O3+ Pr2O3+ Er2O3≤ 12 mol%. In some embodiments, the aluminosilicate glass further comprises at least one alkaline earth oxide and B2O3. In some embodiments, the glass has a transmittance of less than about 30% at wavelengths from about 1400 nm to about 1600 nm.

[0011] In another aspect, the zinc-bismuth-borate glass comprises: ZnO, Bi2O3, B2O3, and at least one of Sm2O3, Pr2O3, and Er2O3, wherein Sm2O3+ Pr2O3+ Er2O3≤ 12 mol%. In some embodiments, the Zn-Bi-borate glass further comprises at least one of Na2O and TeO2. In some embodiments, these glasses have a transmittance of less than about 30% at wavelengths from about 1400 nm to about 1600 nm.

[0012] These and other aspects, advantages, and salient features have been BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is a plot of the absorbance versus wavelength for a glass-ceramic sample that was splat-quenched, an annealed glass-ceramic sample, and a heat-treated glass-ceramic sample;

[0014] Figure 2 is a spectrum of a splat-quenched glass-ceramic composition (A), an annealed glass-ceramic composition (B), and a heat-treated glass-ceramic composition (C);

[0015] Figure 3 is a plot of the differential scanning calorimetry cooling curve measured for a glass-ceramic sample;

[0016] Figure 4 is a spectrum of glass-ceramics containing different alkali tungsten bronzes;

[0017] Figure 5 is an X-ray powder diffraction profile of a splat-quenched glass-ceramic;

[0018] Figure 6 is an X-ray powder diffraction profile of a heat-treated glass-ceramic;

[0019] Figure 7 is a flow chart of a method of infiltrating a glass to form a glass-ceramic;

[0020] Figure 8 is a plot of the dispersion curve for glass E listed in Table E;

[0021] Figure 9 is a plot of the transmittance for glass E listed in Table E; and

[0022] Figure 10 is a plot of the transmittance for glasses J, K, and L listed in Table F. DETAILED DESCRIPTION

[0023] In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as "top," "bottom," "outward," "inward," and the like are words of convenience and are not to be construed as limiting terms. Furthermore, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group can comprise, in addition to a single individual element or combination thereof all the elements of the group. Similarly, whenever a group is described as consisting of at least one of a group of elements and combinations thereof, it is understood that the group can consist of any number of those elements that are individually listed or combinations thereof. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range, as well as any ranges therebetween. As used herein, the indefinite articles "a" or "an" and their corresponding definite articles "the" mean "at least one" or "one or more," unless otherwise specified. It also should be appreciated that the various features described herein can be used in any and all combinations.

[0024] As used herein, the terms "glass article" and "glassy article" are used in their broadest sense to include any object made wholly or partly of glass and / or glass-ceramic, and include laminates of the glasses and glass-ceramics described herein with conventional glass. Unless otherwise indicated, all compositions are expressed in terms of mole percent (mol %). The coefficient of thermal expansion (CTE) is in units of 10 -7 / °C, measured over a temperature range of about 20-300°C, unless otherwise specified.

[0025] As used herein, the terms "nanoparticle" and "nanoscopic particle" refer to a particle having a size of about 1 to about 1000 nanometers (nm). As used herein, the terms "platelet" and "platelets" refer to flat or planar crystals. As used herein, the terms "nanorod" and "nanorods" refer to elongated crystals having a length of up to about 1000 nm and an aspect ratio (length / width) of at least 3, and in some embodiments, from about 3 to about 5.

[0026] As used herein, "transmission" and "transmittance" refer to external transmission or transmittance, taking into account absorption, scattering, and reflection. In the transmission and transmittance values reported herein, no Fresnel reflection is subtracted.

[0027] It is noted that the terms "substantially" and "about" can be utilized herein to represent the inherent determination of an amount by any quantitative comparison, numerical, measurement or other representation of quantity that can be caused by experimental error, measurement of the quantity or other factors. These terms are also used herein to represent that an amount that is represented to a certain precision can have some variation from the stated reference without resulting in a change in the basic function of the subject matter at issue. Thus, a "MgO-free" glass is one in which MgO is not intentionally added or formulated into the glass, but can be present in very small amounts (e.g., less than 400 parts per million (ppm) or less than 300 ppm) as a contaminant.

[0028] Compressive stress and depth of layer are measured using methods known in the art. Such methods include, but are not limited to, measuring surface stress (FSM) using a commercial instrument such as the FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Tokyo, Japan). Surface stress measurements rely on the accurate measurement of the stress-optical coefficient (SOC), which is related to the birefringence of the glass. In turn, the SOC is measured according to a modified version of Procedure C described in ASTM Standard C770-98(2013), entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," which is incorporated herein by reference in its entirety, referred to herein as the modified version. The modifications to Procedure C include the use of a glass disc as the test specimen, having a thickness of 5-10 mm and a diameter of 12.7 mm. The disc is isotropic and homogeneous, and is core drilled, with both sides polished and parallel. The modifications also include calculating the maximum force F 最大值 to be applied to the disc 最大值 :

[0029] F 最大值 = 7.854 · D · h

[0030] where F 最大值 is the maximum force (in Newtons), D is the diameter of the disc (in millimeters (mm)), and h is the thickness of the light path (also in mm). For each application of force, the stress is calculated using the following equation:

[0031] σ (MPa) = 8F / (π · D · h)

[0032] where F is the force (in Newtons), D is the diameter of the disc (in millimeters (mm)), and h is the thickness of the light path (also in mm).

[0033] Unless otherwise indicated, the terms "depth of layer," "DOL," and "FSM DOL" refer to the depth of compression determined by surface measurement (FSM) using commercially available instruments, such as, but not limited to, the FSM-6000 stress meter. The depth of compression DOC refers to the depth within the glass where the stress is effectively zero, which can be determined from the stress profile obtained by refracted near field (RNF) and polar methods known in the art. For a single ion exchange process, this DOC is typically less than the FSM DOL measured by the FSM instrument.

[0034] For strengthened glass articles in which the compressive stress layer extends to a relatively deep depth within the glass, the FSM technique can have contrast problems that affect the observed DOL value. At relatively deep depths of the compressive layer, there can be insufficient contrast between the TE and TM spectra, making it more difficult to calculate the difference between the spectra of the boundary optical modes for TE and TM polarizations and to accurately determine the DOL. In addition, the FSM software analysis cannot determine the compressive stress profile (i.e., the change in compressive stress as a function of depth within the glass). In addition, the FSM technique cannot determine the depth of layer in the glass resulting from ion exchange of certain elements (e.g., sodium for lithium).

[0035] When the DOL is a small fraction r of the thickness t and the depth profile of the refractive index curve approximates a simple linear truncation profile fairly well, the DOL determined by FSM is a reasonably good approximation of the depth of compression (DOC) of the compressive layer. When the DOL is a significant fraction of the thickness, for example, when DOL > 0.1-t, then the DOC is very commonly significantly lower than the DOL. For example, in the idealized case of a linear truncation profile, the relationship DOC = DOL-(1-r) is maintained, where r = DOL / t.

[0036] Alternatively, the scattering linearly polarized light (SCALP) technique known in the art can be employed to determine the compressive stress, stress profile, and depth of layer. The SCALP technique enables non-destructive measurement of surface stress and depth of layer.

[0037] Referring generally to the drawings, and more particularly to Figure 1 , it will be understood that the illustrations are for descriptive purposes only and do not limit the description or the appended claims in any way. For purposes of clarity and brevity, some features and some views of the drawings can be shown exaggerated in scale or in schematic in nature, and description of a feature in one or more of the figures is not intended to be limiting.

[0038] In some embodiments, the optically transparent glass-ceramic materials described herein include: a glass phase containing at least about 90 wt% silica, and a crystalline tungsten bronze phase. These glass-ceramics include: a silicate glass phase, and about 0.1 mol% to about 10 mol%, or about 1 mol% to about 4 mol%, or about 0.5 mol% to about 5 mol% of a crystalline tungsten bronze phase comprising crystalline M x WO3nanoparticles. In one embodiment, the crystalline M x WO3nanoparticles are surrounded and dispersed in and, in some embodiments, throughout the residual glass phase. In another embodiment, the M x WO3crystalline nanoparticles are disposed at or near the surface of the glass-ceramic. In some embodiments, the M x WO3crystalline nanoparticles are platelet-shaped and have an average diameter (determined by those means known in the art, e.g., SEM and / or TEM microscopy, X-ray diffraction, light scattering, centrifugation, etc.) of about 10 nm to 1000 nm, or about 10 nm to about 5 μιη, and / or are M x WO3nanorods having a high aspect ratio and an average length (determined by those means known in the art to be 10 nm to 1000 nm) and an average width (determined by those means known in the art to be about 2 to about 75 nm). In some embodiments, the tungsten bronze glass-ceramics exhibiting high visible light transmittance and strong UV and NIR absorption contain M x WO3rods having an average length of about 10 nm to about 200 nm and an average width of about 2 nm to about 30 nm. The crystalline tungsten bronze phase has the chemical formula MxWO3, where M is at least one of: H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 < x < 1. These glass-ceramics have a low coefficient of thermal expansion (CTE) and strong attenuation or blocking of ultraviolet (UV) radiation for wavelengths less than about 250 nm and near infrared radiation (NIR) for wavelengths of about 700 nm to about 2500 nm.

[0039] In some embodiments, the glass-ceramics described herein are optically transparent in the visible region of the optical spectrum (i.e., wavelengths from about 400 nm to about 700 nm). That is, the glass-ceramics have a transmittance greater than about 1% per mm path length over at least one 50 nm wide band of wavelengths of light in the range from about 400 nm to about 700 nm (expressed herein as "% / mm"). In some embodiments, the transmittance of the glass-ceramics is at least greater than about 10% / mm, in some embodiments, greater than about 30% / mm, in other embodiments, greater than about 50% / mm (e.g., > 75% / mm, > 80% / mm, > 90% / mm) over at least one 50 nm wide band of wavelengths of light in the visible region of the optical spectrum. Further, these glass-ceramics absorb light in the ultraviolet (UV) region (wavelengths less than about 370 nm) and near infrared (NIR) region (greater than about 700 nm to about 1700 nm) of the optical spectrum without the use of a coating or film that is mechanically fragile and sensitive to UV light and moisture. In some embodiments, the transmittance of the glass-ceramics is less than 10% / mm, or even less than 5% / mm, and in other embodiments, less than 2% / mm or even less than 1% / mm for light having a wavelength less than or equal to about 370 nm (e.g., a 370 nm wavelength). In some embodiments, the glass-ceramics absorb at least 90% / mm, or have an absorption of at least 90% / mm, in other embodiments, at least 95% / mm, and in other embodiments, at least 98% or even at least 99% / mm for light having a wavelength less than or equal to about 370 nm. In some embodiments, the transmittance of the glass-ceramics is less than 10% / mm, and in other embodiments, less than 5% / mm over at least one 50 nm wide band of wavelengths of light in the NIR region of the optical spectrum (i.e., from about 700 nm to about 2500 nm). In some embodiments, the glass-ceramics absorb at least 90% / mm, and in other embodiments, absorb at least 95% / mm over at least one 50 nm wide band of wavelengths of light in the NIR region of the optical spectrum (i.e., from about 700 nm to about 2500 nm).

[0040] In some embodiments, the glass-ceramics described herein can withstand temperatures of at least about 300°C, or in other embodiments, at least about 200°C, without impairing their optical or mechanical properties. In some embodiments, when the glass-ceramics are heated in a temperature range of about 200°C to about 300°C for at least one hour, the transmittance of the glass-ceramics changes by less than 10% / mm in the range of about 500 nm to about 2500 nm. In some embodiments, these glass-ceramics are non-reactive and, in any other way, unaffected by oxygen, hydrogen, and moisture. The unaffected properties of the glass-ceramics were confirmed by exposing selected samples (e.g., samples 13, 14, 15, and 16 in Table 1) to light at 312 nm and 365 nm for periods up to 7 days. No change in the optical absorptivity of these samples was observed after such exposure, indicating that oxygen, moisture, and / or hydrogen did not react with M. x The WO3 crystalline phase undergoes reactions and changes.

[0041] In some embodiments, the coefficient of thermal expansion (CTE) of the glass-ceramic described herein over a temperature range of about 0°C to about 300°C is about 75 x 10⁻⁶. -7 ℃ -1 In some embodiments, the coefficient of thermal expansion (cTE) of the glass-ceramic over a temperature range of about 0°C to about 300°C is about 33.5 x 10⁻⁶. -7 ℃ -1 To approximately 66.3x10 -7 ℃ -1 (For example, samples 2, 11, 12, 13, and 54 in Table 1).

[0042] In some embodiments, the glass-ceramics described herein are bleachable, meaning that the crystals M can be "wiped away" by subjecting the glass / glass-ceramic to a short-term heat treatment above their respective softening points. x WO3. Such heat treatment can be performed using energy sources known in the art, such as, but not limited to, resistance furnaces, lasers, or microwaves. For example, composition 37 (Table 1) can be bleached by maintaining the material at a temperature of about 685°C to about 740°C for about 5 minutes. Then, by exposure to a UV pulsed laser, M x The WO3 bronze phase can be reformed or recrystallized on the surface of the material; that is, in areas exposed to laser light, the tungsten bronze phase will reform.

[0043] The glass-ceramics described herein can be used in low emissivity glazing in architectural, vehicular, medical, aerospace, or other applications, including heat face shields, medical eye shields, and optical filters, among others. In some embodiments, the glass-ceramics form a portion of a consumer electronic product, such as a cell phone or smart phone, a laptop or tablet, among others. Such consumer electronic products typically include a housing having a front surface, a back surface, and side surfaces, and include electronic components at least partially within the housing. The electronic components include at least a power source, a controller, a memory, and a display. In some embodiments, the glass-ceramics described herein comprise at least a portion of a protective element, such as, but not limited to, the housing and / or the display.

[0044] In some embodiments, the glass phase is a borosilicate glass, and the glass-ceramic comprises Si02, AI2O3, B2O3, WO3, and at least one alkali oxide R2O, where R2O is at least one of Na20, K2O, Cs2O, and / or Rb20, and the crystalline tungsten bronze phase is a tungsten bronze solid solution containing, comprising, or consisting essentially of MWO3, where M is at least one of Na20, K2O, Cs2O, and Rb20. In some embodiments, the crystalline alkali tungsten bronze phase is a crystalline alkali tungsten bronze phase that is an alkali tungsten bronze solid solution M1 x M2 y WO3, where M1 = Li, Na, K, Cs, Rb and M2 = Li, Na, K, Cs, Rb, where M1≠ M2 and 0 < (x + y) < 1.

[0045] In some embodiments, the glass-ceramic comprises: about 56 mol% to about 78 mol% Si02(56 mol% < Si02< 78 mol%) or about 60 mol% to about 78 mol% Si02(60 mol% < Si02< 78 mol%); about 8 mol% to about 27 mol% B203(8 mol% < B203< 27 mol%); about 0.5 mol% to about 14 mol% Al203(0.5 mol% < Al203< 14 mol%); greater than 0 mol% to about 10 mol% of at least one of Na20, K20, Cs20, and Rb20 (0 mol% < Na20 + K20 + Cs20 + Rb20 < 9 mol%); about 1 mol% to about 10 mol% W03(1 mol% < W03< 10 mol%) or in some embodiments about 1 mol% to about 5 mol% W03(1 mol% < W03< 5 mol%); and 0 mol% to about 0.5 Sn02(0 mol% < Sn02< 0.5). In some embodiments, the glass-ceramic can comprise: 0 mol% to about 9 mol% Li20; in some embodiments, 0 mol% to about 9 mol% Na20 (0 mol% < Na20 < 9 mol%); in some embodiments, 0 mol% to about 9 mol% K20 (0 mol% < K20 < 9 mol%) or 0 mol% to about 3 mol% K20 (0 mol% < K20 < 3 mol%); in some embodiments, 0 mol% to about 10 mol% Cs20 (0 mol% < Cs20 < 10 mol%) or greater than 0 mol% to about 7 mol% Cs20 (0 mol% < Cs20 < 7 mol%); and / or in some embodiments, 0 mol% to about 9 mol% Rb20 (0 mol% < Rb20 < 9 mol%). In some embodiments, the glass-ceramic comprises about 9.8 mol% to about 11.4 mol% B203(9.8 mol% < B203< 11.4 mol%).

[0046] In certain embodiments, the glass-ceramics described herein comprise: from about 80 mol% to about 97 mol% Si02(80 mol% < Si02< 97 mol%); from 0 mol% to about 5 mol% Al203(0 mol% < Al203< 5 mol%); from 0 mol% to about 2 mol% R20 (0 mol% < R20 < 2 mol%), where R20 = Li20, Na20, K20, and / or Cs20, or from greater than 0 mol% to about 2 mol% Cs20 (0 mol% < Cs20 < 2 mol%), or from greater than 0 mol% to about 0.5 mol% Cs20 (0 mol% < Cs20 < 0.5 mol%); and from about 0.2 mol% to about 2 mol% W03 (0.2 mol% < W03 < 2 mol%). In particular embodiments, the glass-ceramics comprise: from about 87 mol% to about 93 mol% Si02(87 mol% < Si02< 93 mol%); from 0 mol% to about 0.5 mol% Al203(0 mol% < Al203< 0.5 mol%); from 3 mol% to about 6 mol% B203(3 mol% < B203< 6 mol%); from 0.75 mol% W03 to about 1.25 mol% W03 (0.75 mol% < W03 < 1.25 mol%); and from 0.2 mol% to about 2 mol% R20, where R = Li, Na, K, and / or Cs (0.2 mol% < R20 < 2 mol%).

[0047] In some embodiments, the glass-ceramics can further comprise at least one of: up to about 0.5 mol% MgO (0 mol% < MgO < 0.5 mol%); up to about 2 mol% P205(0 mol% < P205< 2 mol%); and up to about 1 mol% (0 mol% < ZnO < 1 mol%). The MgO, P205, and Zn can be added to increase the x Rate of formation of W03 after cooling or heat treatment.

[0048] Non-limiting compositions of glass-ceramics that are transparent in the visible range and absorbing in the UV and NIR are listed in Table 1. Compositions that do not absorb UV or NIR radiation are listed in Table 2.

[0049] Table 1: Compositions of glass-ceramics that are optically transparent in the visible range and absorbing in the UV and NIR light ranges

[0050] Mol % 1 2 3 4 5 6 7 8 9 10 SiO2 76.9 75.9 72.9 69.9 65.9 77.6 76.9 61.7 61.7 65.9 B2O3 17 17 20 23 27 20 17 20 20 20 Al2O3 2 2 2 2 2 0.66 1.32 6.6 6.6 5 Li2O 0 0 0 0 0 0 0 0 0 0 Na2O 0 0 0 0 0 0 0 0 0 0 K2O 0 0 0 0 0 0 0 0 0 0 Cs2O 1 2 2 2 2 0.66 0.66 1.32 6.6 5 WO3 3 3 3 3 3 1 1 1 5 4 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0

[0051] Mol % 1 2 3 4 5 6 7 8 9 10 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0052] Mol % 11 12 13 14 15 16 17 18 19 20 SiO2 64.9 63.9 63.9 63.9 63.9 63.9 62.9 61.9 64.9 62.9 B2O3 20 20 20 20 20 20 20 20 20 20 Al2O3 5 7 9 9 9 9 10 11 9 9 Li2O 0 0 0 3 0 0 0 0 0 0 Na2O 0 0 0 0 3 0 0 0 0 0 [K2O] 0 0 0 0 0 3 0 0 0 0 Cs2O 5 5 3 0 0 0 3 3 2 4 WO3 5 4 4 4 4 4 4 4 4 4 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0053] Mol % 21 22 23 24 25 26 27 28 29 30 SiO2 63.9 61.9 63.9 63.9 63.9 64 64.4 64.9 65.4 64.9 B2O3 20 20 20 20 20 20 20 20 20 20 Al2O3 10 12 9 9 9 9 9 9 9 9 Li2O 0 0 0 1.5 1.5 3 3 3 3 2 Na2O 0 0 0 0 0 0 0 0 0 0

[0054] Mol % 21 22 23 24 25 26 27 28 29 30 K2O 0 0 0 1.5 0 0 0 0 0 0 Cs2O 2 2 2.9 0 1.5 0 0 0 0 0 WO3 4 4 4 4 4 4 3.5 3 2.5 4 SnO2 0.1 0.1 0.1 0.1 0.1 0 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0.1 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0055] Mol % 31 32 33 34 35 36 37 38 39 40 SiO2 65.9 66.9 65.9 66.4 60.9 65.9 69.9 66 65.9 65.8 B2O3 20 20 20 20 20 15 10 20 20 20 Al2O3 9 9 9 9 9 9 10 9 9 9 Li2O 1 0 3 3 6 6 6 3 3 3 Na2O 0 0 0 0 0 0 0 0 0 0 K2O 0 0 0 0 0 0 0 0 0 0 Cs2O 0 0 0 0 0 0 0 0 0 0 [WO3] 4 4 2 1.5 4 4 4 2 2 2 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 0.1 0.2 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0056] Mol % 41 42 43 44 45 46 47 48 49 50 SiO2 65.6 65.8 65.9 70.1 70.1 69.85 70.35 70.1 69.9 68.1 B2O3 20 20 20 10.35 9.8 9.8 9.8 12.35 10.35 11.35 Al2O3 9 9 9 10 10 10 10 9 10 10 Li2O 3 3 3 0 8.475 8.6 8.35 7.7 8.2 8.7 Na2O 0 0 0 8.2 1.525 1.65 1.4 0.75 1.25 1.75 [K2O] 0 0 0 1.25 0 0 0 0 0 0 Cs2O 0 0 0 0 0 0 0 0 0 0 ​ 2 2 2 4 4 4 4 4 4 4 SnO2 0.4 0 0 0.1 0.1 0.1 0.1 0.1 0.3 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0 MnO2 0 0.2 0 0 0 0 0 0 0 0 Fe2O3 0 0 0.1 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0057] Mol % 51 52 53 54 55 56 57 58 59 60 61 SiO2 69.85 69.85 69.85 69.85 70.25 69.85 69.35 68.85 69.1 69.75 68.75 B2O3 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 10.8 Al2O3 10 10 10 9.75 10 10 9.375 10 10 10 10 Li2O 0 4 8 0 0 0 0 0 0 0 3 Na2O 8.6 4.6 0.6 8.725 8.35 8.35 8.975 8.6 8.6 8.6 7.25 [K2O] 1.65 1.65 1.65 1.775 1.4 1.4 1.4 1.65 1.65 1.65 0 Cs2O 0 0 0 0 0 0 0 0 0 0 0 WO3 4 4 4 3.5 4 4 4 4 4 4 4 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 0

[0058] Mol % 51 52 53 54 55 56 57 58 59 60 61 Eu2O3 0 0 0 0 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0.1 0.5 1 0 0 0 0.1 P2O5 0 0 0 0 0 0 0 0 0 0 0 ZnO 0 0 0 0 0 0 0 1 0 0 0 As2O5 0 0 0 0 0 0 0 0 0.75 0 0

[0059] Table 2: Compositions of glass-ceramics that do not absorb radiation in the UV and NIR range

[0060] Mol % 62 63 64 65 66 67 68 69 70 71 SiO2 77.9 77.94 72.3 65.7 64.7 63.7 65.7 65.7 64.2 62.7 B2O3 20.7 20 20 20 20 20 20 20 20 20 Al2O3 0 0.3 3.3 6.6 6.6 0.66 5.6 4.6 8.1 9.6 Li2O 0 0 0 0 0 0 0 0 0 0 Na2O 0 0 0 0 0 0 0 0 0 0 K2O 0 0 0 0 0 0 0 0 0 0 Cs2O 0.3 0.66 3.3 6.6 6.6 6.6 7.6 8.6 6.6 6.6 WO3 1 1 1 1 2 3 1 1 1 1 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0061] Mol % 72 73 74 75 76 77 78 79 80 81 SiO2 62.2 60.7 62.7 60.1 63.9 63.9 63.9 66.9 67.9 65.9 B2O3 20 20 20 20 20 20 20 20 10 10 Al2O3 8.1 9.6 6.6 6.6 5 9 9 9 10 10 Li2O 0 0 0 0 0 0 0 3 8 10 Na2O 0 0 0 0 0 0 0 0 0 0 K2O 0 0 0 0 0 0 0 0 0 0 Cs2O 6.6 6.6 6.6 6.6 7 0 0 0 0 0 WO3 3 3 4 6.6 4 4 4 1 4 4 SnO2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 3 0 0 0 0 Eu2O3 0 0 0 0 0 0 3 0 0 0 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0 0 0 0 0 0 0 0 0 Sb2O3 0 0 0 0 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0

[0062] Mol % 82 83 84 85 86 87 88 89 90 79 SiO2 63.9 65.8 65.9 65.75 67 67 70.1 69.35 70.1 70.1 B2O3 10 20 20 20 8.1 9.1 9.35 9.8 9.35 9.35 Al2O3 10 9 9 9 12.6 12.6 10 10 10 10 Li2O 12 3 3 3 5.1 5.1 8.242 8.35 8.7 8.7 Na2O 0 0 0 0 6.2 5.7 2.208 1.4 1.75 1.75 [K2O] 0 0 0 0 0.8 0.3 0 0 0 0 Cs2O 0 0 0 0 0 0 0 0 0 0 WO3 4 2 2 2 4 4 4 4 2.5 2.5 SnO2 0.1 0 0 0 0.1 0.1 0.1 0.1 0.1 0.1 La2O3 0 0 0 0 0 0 0 0 0 0 Eu2O3 0 0 0 0 0 0 0 0 0 0

[0063] Mol % 82 83 84 85 86 87 88 89 90 79 MnO2 0 0 0 0 0 0 0 0 0 0 Fe2O3 0 0 0 0 0 0 0 0 0 0 CeO2 0 0.2 0 0.2 0 0 0 0 0 0 Sb2O3 0 0 0.1 0.05 0 0 0 0 0 0 MgO 0 0 0 0 0 0 0 1 0 0

[0064] In some embodiments, -10 mol% < R2O (mol%) - Al203(mol%) < 0.1 mol%. Peraluminous melts can be divided into three subcategories as to how the combination and heat treatment affect the optical properties of the glass-ceramics. As used herein, the term "peraluminous melt" refers to a melt in which the molar proportion or content of aluminum oxide is greater than the molar proportion or content of R2O, where R2O is at least one of Li20, Na20, K20, and Cs20; i.e., Al203(mol%) > R2O(mol%). The first subcategory is one in which the peraluminous melt is transparent in the visible wavelength range and the NIR region when rapidly quenched from the molten state and after annealing (e.g., samples 12, 15-17, 20, 23, 25, 33, 35-42, 44, 46, 47, and 48 in Table 1). These materials require a subsequent heat treatment that is at or slightly above the annealing temperature, but below the softening point, to establish the NIR-absorbing nanocrystalline WO3 phase. The change in optical properties as a function of heat treatment is shown in Table 2. x WO3 phase. The change in optical properties as a function of heat treatment is shown in Table 2. Figure 1The absorption-wavelength relationship for the splat-quenched sample, the annealed sample, and the heat-treated sample of composition 13 is shown. As used herein, the term "splat-quenching" refers to a process in which a small amount of molten glass or "glob" is poured onto an iron plate at room temperature and immediately pressed with an iron piston (also at room temperature) to cause the glass to cool rapidly and press the glob into a glass disk (3-6 mm). While the splat-quenched sample (A) and the annealed sample (B) of composition / sample 13 show no absorption in the visible or NIR region, the heat-treated samples (C, D, E) exhibit absorption in the NIR region (which increases with increasing heat treatment time) and some visible attenuation in the 600-700 nm wavelength range, resulting in a blue tint to the material. Figure 1

[0065] The second class of peraluminous melts remain transparent in the visible and NIR region if quenched rapidly, but exhibit NIR absorption upon annealing (see samples 12, 14, 19, 21, 22, 24, and 26-32 in Table 1). As with the first class of peraluminous melts described above, and as with the third class of peraluminous melts described below, the NIR absorption of these materials can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point. Figure 2 As shown (which shows the spectra of the splat-quenched sample (A), the annealed sample (B), and the heat-treated sample (C) of sample of glass-ceramic composition 11), the NIR absorption of the splat-quenched or annealed glass-ceramic can be enhanced by further heat treatment.

[0066] The third class of peraluminous melts exhibit NIR absorption even after rapid quenching (see samples 1 and 7 of Table 1). The NIR absorption of these materials can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.

[0067] Melts near charge balance (i.e., R2O (mol%) - Al2O3 (mol%) = 0 ± 0.25 mol%) can be either transparent in the visible after rapid quenching and NIR absorbing upon annealing (see samples 8-11 and 45 of Table 1), or NIR absorbing after rapid quenching or annealing (see samples 2-7 of Table 1). As with the melts described above, the NIR absorption can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.

[0068] ​Two peralkaline (i.e., R2O (mol%) > Al2O3 (mol%)) UV-absorbing and NIR-absorbing melts (samples 46 and 50 in Table 1) are transparent to visible and NIR light when rapidly quenched, but are NIR-absorbing after annealing. As with the melts described above, the NIR absorption can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.

[0069] crystalline M x The rate of formation of the WO3 phase (which determines the optical absorption) can also be adjusted by adjusting at least one of the following: heat treatment time and temperature, (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) ratio, R2O (mol%) / WO3 (mol%) ratio, Al2O3 (mol%) / WO3 (mol%); and the choice of alkali (or alkali species) to be batched. In all cases, for longer heat treatment times, more crystalline M x WO3 phase precipitates, resulting in a material with stronger NIR absorption. However, over-heat treatment can cause crystalline M x WO3 phase to coarsen. In some cases, coarsening can be completed by the formation of a second or ternary crystalline phase (e.g., borastalite or aluminum borate). The formation of these second phases can produce a material that scatters visible wavelengths, appearing hazy or milky. In addition, in most cases, as the heat treatment temperature increases and approaches the softening point of the glass, M x WO3 forms at an increased rate.

[0070] In some embodiments, 1 < (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) < 6. As the ratio (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) increases, M x WO3 forms at a decreased rate. When (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) > 6, the precipitation of the NIR-absorbing crystalline M x WO3 phase is stopped.

[0071] In crystalline M xIn glasses where the WO3 NIR absorbing phase precipitates, the R2O (mol%) / WO3 (mol%) ratio is greater than or equal to 0 and less than or equal to about 4 (0 ≤ R2O (mol%) / WO3 (mol%) ≤ 4), and the Al2O3 (mol%) / WO3 (mol%) ratio is about 0.66 to about 6 (0.66 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 6). When R2O (mol%) / WO3 (mol%) is greater than 4 (R2O (mol%) / WO3 (mol%) > 4), the glass may precipitate a dense, immiscible second phase and separate, resulting in a heterogeneous melt. When the Al2O3 (mol%) / WO3 (mol%) ratio exceeds 6 (Al2O3 (mol%) / WO3 (mol%) > 6), the glass stops precipitating crystals M. x WO3 NIR absorbing phase. When the Al2O3 (mol%) / WO3 (mol%) ratio is equal to 6 (Al2O3 (mol%) / WO3 (mol%) = 6) (e.g., sample 34 in Table 1), although nanocrystals M absorbing NIR are formed. x WO3 bronze, but its formation is very slow. Preferably, the R2O (mol%) / WO3 (mol%) ratio is about 0 to about 3.5 (0 ≤ R2O / WO3 ≤ 3.5) (e.g., sample 26 in Table 1). Most preferably, the R2O / WO3 ratio is about 1.25 to about 3.5 (1.25 ≤ R2O (mol%) / WO3 (mol%) ≤ 3.5) (e.g., sample 53 in Table 1), because samples with this composition range rapidly precipitate to obtain MnO that absorbs UV and NIR. x The WO3 crystal phase exhibits high visible light transparency and strong NIR absorption, and is bleachable (i.e., can be "erased" from M). x WO3 crystal phase). In some embodiments, the Al2O3 (mol%) / WO3 (mol%) ratio is about 0.66 to about 4.5 (0.66 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 4.5) (e.g., sample 40 in Table 1), and most preferably, the Al2O3 (mol%) / WO3 (mol%) ratio is about 2 to about 3 (1 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 3) (e.g., sample 61 in Table 1). Above this range, absorbing NIR nanocrystals M are formed. x WO3 Bronze is slow.

[0072] Different alkali metal oxides lead to crystal M x The WO3 phase precipitates at different rates. For melts with the same composition but different alkali metal oxides R2O (where R = Li, Na, K, or Cs), when M (or R) is Cs, M... xWO3precipitation rates are slowest for WO3and fastest when M (or R) is Li, i.e., Cs < K < Na < Li (e.g., samples 14, 15, 16, and 13 of Table 1). Depending on the alkali metal present, crystals M x The temperature of the WO3phase also shifts. Figure 3 Differential scanning calorimetry (DSC) cooling curves are shown for samples 14, 15, 16, and 13, whose compositions are listed in Table 1. From Figure 3 As seen from Table A below, the cesium-containing melts crystallize at the highest temperatures, followed by the potassium-containing melts, the sodium- containing melts, and the lithium-containing melts.

[0073] Table A: Crystals M x Crystallization temperature of the WO3phase

[0074] Sample Alkali metal M Crystallization temperature (°C) 14 Li 593.8 15 Na 682.2 16 K 706.3

[0075] 13 Cs 714.1

[0076] The NIR absorption edge and the peak or maximum transmission wavelength in the visible range of the glass-ceramics can be adjusted by the composition, the heat treatment time and temperature, and the choice of alkali metal oxide. Figure 4 Spectrograms of glass-ceramics with different alkali tungsten bronzes and otherwise identical compositions (samples 14, 15, 16, and 13 of Table 1) are shown. The potassium and cesium analogs (samples 16 and 13, respectively) have a shorter peak visible transmission wavelength (440-450 nm) than the sodium and lithium analogs (samples 15 and 14, respectively) which have peak visible transmission wavelengths of 460 nm and 510 nm, respectively.

[0077] In some embodiments (e.g., examples 37, 44, 46, and 50 of Table 1), the glass-ceramics described herein have a lower boron concentration, i.e., from about 9.8 mol% to about 11.4 mol% B2O3(9.8 mol% < B2O3< 11.4 mol%). In these samples, the NIR-absorbing crystals M x WO3phase. These compositions can be heated above their respective softening points and sag, slump, or shape without the precipitation of the NIR-absorbing crystals M x WO3phase. This is achieved by first forming and / or shaping a glass article, and then subsequently heat treating the material at a low temperature to precipitate the NIR-absorbing crystals M x WO3second phase, enabling control and adjustment of the optical properties of these glass-ceramics. Furthermore, by heating the glasses above their respective softening points for a short time, the crystals M xThe WO3 second phase can be "erased" (and the glass-ceramic "bleached"). For example, composition 44 (Table 1) can be bleached by holding the material at a temperature of about 685 °C to about 740 °C for about 5 minutes.

[0078] Table B: Crystalline M in samples with low B2O3 content x Crystallization temperature range of WO3 phase

[0079] Sample B2O3 (mole %) Crystallization temperature range (°C) 37 10 575-625 44 10.4 500-550 46 9.8 500-575 50 11.4 500-650

[0080] In some embodiments, these glasses and glass-ceramics can be patterned with a UV laser. For example, M x WO3 phase can be precipitated in a rapidly-quenched composition (e.g., sample 14 in Table 1) by exposing the material to a 10 watt 355 nm pulsed laser.

[0081] Table C lists measured physical properties for selected sample compositions listed in Table 1, including: strain point, annealing point, and softening point, coefficient of thermal expansion (CTE), density, refractive index, Poisson's ratio, shear modulus, Young's modulus, liquidus (maximum crystallization) temperature, and stress optical coefficient (SOC). In addition, X-ray powder diffraction (XRD) curves were obtained for the as-sprayed glass-ceramic compositions and the heat-treated glass-ceramic compositions for selected samples listed in Table 1. Figure 5 and 6 are representative XRD curves for the as-sprayed material and the heat-treated material, respectively, both of which have composition 14 of Table 1. These XRD curves confirm that the as-quenched material Figure 5 ) is amorphous and does not contain crystalline M x WO3 phase prior to heat treatment, and the heat-treated glass material contains crystalline M x WO3 second phase.

[0082] Table C: Measured physical properties for glass-ceramics having compositions selected from Table 1

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089] In those embodiments where the glass-ceramic comprises alumina (AI2O3) and at least one alkali metal, the glass-ceramic can be ion exchangeable. Ion exchange is commonly used to chemically strengthen a glass. In one particular example, alkali cations in such a cation source (e.g., a molten salt or "ion exchange" bath) exchange with smaller alkali cations within the glass, resulting in a layer under compressive stress (CS) extending from the surface to a depth of layer (DOL) or depth of compression (DOC) in the glass phase, where CS is a maximum in the glass. For example, potassium ions from the cation source typically exchange with sodium ions within the glass phase.

[0090] In some embodiments, the glass-ceramic is ion exchanged and has a compressive layer extending from at least one surface to a depth of at least about 10 um (expressed as DOC and / or DOL) within the glass-ceramic. The compressive stress CS of the compressive layer is at least about 100 MPa and less than about 1500 MPa at the surface.

[0091] In non-limiting examples, compositions 51 and 54 are ion exchanged. The samples are first heat treated at 550°C for 15 hours, then cooled at 1°C / minute to 475°C, and further cooled to room temperature at the furnace cooling rate (furnace rate) when the power is turned off. The cerammed samples are then ion exchanged in a KNO3 molten salt bath at 390°C for 3 hours, resulting in surface compressive stresses of 360 MPa and 380 MPa and layer depths of 31 and 34 microns for glass-ceramic compositions 51 and 54, respectively.

[0092] In one embodiment, the glass-ceramics described herein can be made using a melt quenching process. The components can be mixed by turbulent mixing or ball milling and compounding in the appropriate proportions. The batch materials can then be melted at a temperature in the range of about 1550°C to about 1650°C for a time in the range of about 6 to about 12 hours, after which they can be cast or shaped and then annealed. Depending on the composition of the material, an additional heat treatment at the annealing point or slightly above the annealing point but below the softening point establishes the crystalline M x WO3 second phase and provides UV absorption and NIR absorption properties. The best UV absorption and NIR absorption properties are obtained with the compositions of samples 12-16, 37, 46, 50-53, and 61 in Table 1. The heat treatment time and temperature ranges for establishing the crystalline M x WO3 second phase are listed in Table D for exemplary compositions.

[0093] Table D: Heat treatment temperature and time ranges for producing UV absorbing and NIR absorbing M x WO3 glass-ceramics

[0094]

[0095] In other embodiments, by permeation into nanoporous glass (e.g., but not limited to) Corning Incorporated manufactures high-silica glasses that form glass-ceramics. These nanoporous glasses can be 20 to 30% porous, with an average pore diameter of 4.5–16.5 nm and a narrow pore size distribution (approximately 96% of the pores in the glass are within 0.6 nm of the average diameter). The average pore diameter can be increased to approximately 16.5 nm by adjusting the heat treatment scheme required for glass phase separation and by changing the etching conditions. Figure 7 A flowchart showing the process of infiltrating glass and forming glass-ceramics.

[0096] In step 110 of method 100, a first solution containing tungsten, a second solution containing the metal cation M, and a third solution containing boric acid are prepared or provided to deliver these components to a nanoporous glass substrate. In one embodiment, a tungsten solution is obtained by dissolving ammonium metatungstate (AMT) in deionized water to produce the desired tungsten ion concentration. In some embodiments, organic precursors (e.g., tungsten carbonyl or tungsten hexachloride) can be used to deliver tungsten into the pores of the nanoporous glass substrate. Various aqueous precursors (including nitrates, sulfates, carbonates, or chlorides) can also be used to provide M. x Metallic M cations in WO3 bronze.

[0097] In a non-limiting example, a first aqueous solution of 0.068 M AMT and a second aqueous solution of 0.272 M cesium nitrate are prepared or provided, such that the cesium cation concentration is 1 / 3 of the tungsten cation concentration.

[0098] The third solution is a supersaturated boric acid solution, which in some embodiments can be prepared by adding boric acid hydrate to deionized water and heating the mixture to boiling while stirring.

[0099] exist( Figure 7 In some embodiments (not shown), the nanoporous glass can be cleaned before forming the glass-ceramic. A sample of the glass (e.g., a 1 mm sheet) can first be slowly heated in ambient air to about 550°C to remove moisture and organic contaminants, and then stored at about 150°C until use.

[0100] First, the glass is immersed in a tungsten-containing first solution at room temperature (approximately 25°C) to permeate the nanoporous glass with the tungsten solution (step 120). In a non-limiting example, the nanoporous glass is immersed in the first solution for approximately 1 hour. Then, the glass sample is removed from the first solution, immersed in deionized water for approximately 1 minute, and dried in ambient air for approximately 24 to approximately 72 hours.

[0101] In the next step of the method 100, the infiltrated nanoporous glass sample is heated in flowing oxygen to decompose the ammonium paratungstate and form WO3 (step 130). The glass is first heated at a rate of about 1 °C / min to about 225 °C, then heated from about 225 °C to about 450 °C at a rate of 2.5 °C / min, after which it is held at 450 °C for 4 hours, and then cooled from about 450 °C to room temperature at a rate of about 5 °C to about 7 °C per minute. In some embodiments, step 130 can include pre-heating the glass at about 80 °C for up to about 24 hours after the heat treatment described above.

[0102] After step 130, the glass is immersed in a second solution at room temperature (about 25 °C) (step 140), thereby infiltrating the glass with a solution of M cations. In some embodiments, step 140 can be performed by pre-heating the glass at about 80 °C for up to about 24 hours prior to immersion. In one non-limiting example, the nanoporous glass is soaked in the second solution for about 1 hour. The glass sample is then removed from the second solution, soaked in deionized water for about 1 minute, and dried in ambient air for a period of about 24 hours to about 72 hours.

[0103] After step 140, the nanoporous glass sample is heated to form crystalline M x WO3tungsten bronze phase (step 150). The heating step 150 includes heating the glass in a nitrogen atmosphere at a rate of about 1 °C / min (ramp rate) from about 5 °C to about 200 °C, then heating from about 200 °C to about 575 °C at a rate of about 3 °C / min in a 3% hydrogen and 97% nitrogen atmosphere, holding at 575 °C for 1 hour, and then rapidly cooling the glass to about 300 °C by opening the furnace in which the heating step is performed. In some embodiments, the sample is then left to sit in ambient air for an unspecified period of time.

[0104] After step 150, the glass sample is immersed in a third solution, which is a supersaturated boric acid solution (step 160). During step 160, the third solution is maintained at boiling point and gently stirred. In some embodiments, the glass sample is soaked in the boiling solution for about 30 minutes. After removal from the third solution, in some embodiments, the sample is rinsed with deionized water and left to sit in ambient air for about 24 hours. The glass is then heated in a nitrogen atmosphere to form and consolidate the glass-ceramic (step 170). In step 170, the glass is first heated from room temperature to about 225 °C at a ramp rate of about 1 °C / min, then heated from about 225 °C to about 800 °C at a rate of about 5 °C / min. The glass is held at 800 °C for about 1 hour, and then cooled from about 800 °C to room temperature at a rate of about 10 °C / min.

[0105] In another aspect, glasses doped with rare earth oxides (REO) are provided that have high absorption in the NIR region of the optical spectrum. In some embodiments, these glasses contribute to the high refractive index of the glasses in the IR. Rare earth oxide dopants including Sm2O3, Pr2O3, and Er2O3 make up up to about 12 mole % of the glass.

[0106] In some embodiments, the REO-doped glasses are aluminosilicate glasses comprising: Al2O3 and SiO2, and at least one of Sm2O3, Pr2O3, and Er2O3, wherein Sm2O3 + Pr2O3 + Er2O3 < 12 mole %. In some embodiments, the glasses further comprise at least one alkaline earth oxide and B2O3. In some embodiments, the glasses have a transmittance of less than about 30% at a wavelength of about 1400 nm to about 1600 nm. Non-limiting examples of compositions of aluminosilicate glasses are listed in Table E. The measured refractive indices (RI) of these glasses are also listed in Table E. Glasses A, B, and C, which do not contain alkaline earth modifiers, are too viscous to be poured even at 1650 °C. Glasses E and F, which contain appreciable amounts (> 21 mole %) of alkaline earth modifiers (and B2O3), can be easily poured at 1650 °C. In some embodiments, the glasses have a refractive index of at least about 1.8 at a wavelength of about 1550 nm. Figure 8 The percent transmittance and dispersion of glass E for both the visible and NIR regions of the optical spectrum are plotted in FIGS. 1 and 2, respectively. Glass E exhibits both high refractive index in the infrared (IR) region and high absorption at 1550 nm. 9 The UV-VIS-IR spectra of these compositions containing 3-5 mole % Pr2O3 are plotted in FIG. 3, and show high absorption at 1550 nm for these glasses. Figure 10 The UV-VIS-IR spectra of these compositions containing 3-5 mole % Pr2O3 are plotted in FIG. 3, and show high absorption at 1550 nm for these glasses.

[0107] Table E: Compositions of Rare Earth Doped Aluminosilicate Glasses

[0108] (mol %) A B C D E F MgO 0 0 0 9.2 9.2 9.2 CaO 0 0 0 9.2 9.2 9.2 BaO 0 6 6 3.4 3.4 3.4 Al2O3 18 18 18 10.7 10.7 10.7 B2O3 0 0 0 4.6 4.6 4.6 SiO2 70 70 70 62.9 62.9 62.9

[0109] (mol %) A B C D E F Pr2O3 12 6 0 0 5 0 Sm2O3 0 0 6 0 0 5 RI at 1550 nm 1.604 1.565 1.562 1.528 1.58 1.576

[0110] In some embodiments, the REO-doped glass is a zinc-bismuth-borate glass comprising: ZnO, Bi2O3, B2O3, and at least one of Sm2O3, Pr2O3, and Er2O3, wherein Sm2O3+ Pr2O3+ Er2O3≤ 12 mol%. In some embodiments, the REO-doped Zn-Bi-borate glass further comprises at least one of Na2O and TeO2. In some embodiments, the glass has a transmittance of less than about 30% at a wavelength of about 1400 nm to about 1600 nm. Non-limiting examples of compositions of Zn-Bi-borate glasses are listed in Table F. The measured refractive index (RI) of these glasses is also listed in Table F.

[0111] Table F: Compositions of Rare Earth Doped Zn-Bi-Borate Glasses

[0112]

[0113] While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or of the appended claims. Accordingly, various modifications, adaptations, and alternatives to the embodiments described herein can be contemplated by those skilled in the art without departing from the spirit and scope of the disclosure or the appended claims.

Claims

1. A glass-ceramic comprising: a borosilicate glass phase; and Crystalline M x WO3 phase, which comprises nanoparticles, wherein, M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu, and 0 < x < 1 ; wherein the crystal M x The nanoparticles of the WO3 phase are surrounded and dispersed throughout the borosilicate glass phase, and also wherein the glass-ceramic comprises 0.1 to 5 mole percent crystals M x WO3 phase.

2. A glass-ceramic comprising: a borosilicate glass phase; and Crystalline M x WO3 phase, which comprises nanoparticles, wherein, M comprises at least one alkali metal, and 0 < x < 1 ; wherein the crystal M x The nanoparticles of the WO3 phase are surrounded and dispersed throughout the borosilicate glass phase.

3. A glass-ceramic comprising: a borosilicate glass phase; and Crystalline M x WO3 phase, which comprises nanoparticles, wherein, M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu, and 0 < x < 1 ; wherein the crystal M x The nanoparticles of the WO3 phase are surrounded and dispersed throughout the borosilicate glass phase, and also wherein the glass-ceramic comprises: 56-78 mol% Si02, 8-27 mol% B203, 0.5-14 mol% AI2O3, greater than 0-10 mol% of at least one of Na20, K20, CS2O, and Rb20, 1-10 mol% W03, and 0-0.5 Sn02.

4. The glass-ceramic according to any one of claims 1-3, wherein: (i) for light having a wavelength range of 400-700 nm, the glass-ceramic has a transmittance of at least 1% / mm over at least one 50 nm wide wavelength band of light; or (ii) for light having a wavelength of 370 nm or less, the glass-ceramic has a transmittance of less than 1% / mm.

5. The glass-ceramic according to any one of claims 1-3, wherein, for light having a wavelength range of 700-2500 nm, the glass-ceramic has a transmittance of less than 5% / mm over at least one 50 nm wide wavelength band of light.

6. The glass-ceramic according to claim 5, wherein, when heated at a temperature range of 200-300 °C, the glass-ceramic has a change in transmittance of less than 10% / mm at 500-2500 nm.

7. The glass-ceramic according to any one of claims 1-3, wherein, the glass-ceramic is: (i) ion-exchangeable; or (ii) ion-exchanged and has a compressive layer extending from a surface of the glass-ceramic to a depth of at least 10 pm into the glass-ceramic, the compressive layer having a compressive stress at the surface of at least 100 MPa and less than 1500 MPa.

8. The glass-ceramic according to any one of claims 1-3, wherein, The glass-ceramic is: (i) bleachable by heat treatment; and / or (ii) has a coefficient of thermal expansion in the temperature range of 0°C to 300°C of less than or equal to 75 x 10 -7 °C -1 .

9. The glass-ceramic according to any one of claims 1-3, wherein, M is at least one alkali species, and: (i) wherein, M is Cs, and wherein the glass-ceramic comprises greater than 0-10 mol% CS2O; or (ii) -10 mol% < R20 - AI2O3 < 0.1 mol%, where R20 is at least one of Na20, K20, CS2O, and Rb20; or (iii) 0 < R20 / W03 < 2.61, where R20 is at least one of Na20, K20, CS2O, and Rb20; or (iv) 0.66 < AI2O3 / W03 < 6; or (v) 1 < (R2O + Al2O3) / WO3 < 6, where R2O is at least one of Na2O, K2O, Cs2O, and Rb2O; or (vi) where the glass-ceramic further comprises at least one of: up to 0.5 mol% MgO; up to 2 mol% P2O5.

10. The glass-ceramic according to any one of claims 1-2, wherein, The glass-ceramic comprises: 80-97 mol% SiO2; 0-5 mol% Al2O3; greater than 0-2 mol% Cs2O; and 0.2-2 mol% WO3.

11. The glass-ceramic according to any one of claims 1-3, wherein, said crystalline M x WO3 phase comprises at least one of: a plurality of platelet-shaped M x WO3 nanoparticles and a plurality of M x WO3 nanorods.

12. The glass-ceramic according to claim 11, wherein: (i) the plurality of flake shapes M x The average diameter of the WO3 nanoparticles is 10 nm to 5 μm; and / or (ii) the plurality of M x The average length of the WO3 nanorods is 10 nm to 1000 nm, and the average width is 2 nm to 75 nm.

13. The glass-ceramic according to claim 11, wherein The plurality of M x The average length of the WO3nanorods is 10 nm to 200 nm, and the average width is 2 nm to 30 nm.

14. The glass-ceramic according to any one of claims 1-3, wherein, The glass-ceramic is at least a portion of a heat shield, optical filter, building element, automotive component, or electronic display housing.

15. A method of bleaching a glass-ceramic comprising crystalline M x WO3, wherein, M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu, and 0 < x < 1, the method comprising heat treating the glass-ceramic above the softening point of the glass-ceramic.

16. The method of claim 15, wherein, The heat treating is performed using a laser.

17. The method of claim 15, further comprising holding the glass-ceramic at a temperature of 685 °C to 740 °C for 5 minutes.

18. A glass-ceramic comprising: SiO2, Al2O3, B2O3, WO3, and at least one alkali oxide R2O, where R2O is at least one of Na2O, K2O, Cs2O, and / or Rb2O; where the glass phase of the glass-ceramic is a borosilicate glass; and where the glass-ceramic is a glass-ceramic according to any one of claims 1-17. wherein the crystalline phase of the glass-ceramic is an alkaline tungsten bronze solid solution M1 x M2 y a mixture of WO3, where M1 = Li, Na, K, Cs, Rb, and M2 = Li, Na, K, Cs, Rb, where M1≠ M2 and 0 < (x+y) < 1.

Images