Transparent glass ceramic capable of shielding near infrared rays

Abstract

The invention relates to a near-infrared shielding transparent glass ceramic. An optically transparent glass ceramic material comprises: a glass phase and a crystalline tungsten bronze phase comprising nanoparticles and having the formula MxWO3 wherein M comprises 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 wherein 0 lt; x < lt >; 1. Also provided are aluminosilicate and zinc-bismuth-borate glasses comprising at least one of Sm < 2 > O < 3 >, Pr < 2 > O < 3 >, and Er < 2 > O < 3 >.

Description

[0001] This application claims priority to U.S. Provisional Application Series 62 / 352,602, filed June 21, 2016, and U.S. Provisional Application Series 62 / 351,616, filed June 17, 2016, pursuant to 35 USC § 119, which are based on and whose full texts are incorporated herein by reference. Background Technology

[0002] This disclosure relates to glass-ceramic materials. More specifically, this disclosure relates to optically transparent glass-ceramic materials. Even more specifically, this disclosure relates to optically transparent glass-ceramic materials having a crystalline tungsten bronze phase.

[0003] Develop near-infrared (NIR) shielding glass to block and / or eliminate wavelengths in the 700–2500 nm range for applications such as filters, lenses, and glass windows for medical, defense, aerospace, and consumer applications.

[0004] Low emissivity (low E) coatings have been developed to minimize the amount of ultraviolet and infrared light that can penetrate glass without impairing the amount of visible light transmitted. Low E coatings are typically sputtered or pyrolytic coatings. Alternatively, low E plastic laminates can be adapted to glass substrates.

[0005] Thin films, coatings, and composites containing nanoscale or microscale particles of nonstoichiometric low-stoichiometric tungsten oxide or doped nonstoichiometric tungsten trioxide (referred to herein as tungsten bronze) have been used to provide near-infrared shielding with high transparency in the visible spectrum. However, tungsten bronze films typically require expensive vacuum deposition chambers, have limited mechanical robustness, and are susceptible to the effects of oxygen, moisture, and UV light, all of which lead to reduced NIR shielding performance and discoloration of these materials, and deterioration of transparency in the visible light range. Summary of the Invention

[0006] This disclosure provides an optically transparent glass-ceramic material, which in some embodiments includes: a glass phase containing at least about 80% by weight silicon dioxide; and a crystalline tungsten bronze phase having the chemical formula M xWO3, wherein M includes, but is not limited to, at least one of the following: 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 wherein 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 exhibits strong attenuation or blocking for ultraviolet (UV) radiation with wavelengths less than about 360 nm and near-infrared (NIR) radiation with wavelengths from about 700 nm to about 3000 nm. Aluminosilicate and zinc-bismuth-borate glasses comprising at least one of Sm2O3, Pr2O3, and Er2O3 are also provided.

[0007] Therefore, one aspect of this disclosure provides a glass-ceramic comprising: a silicate glass phase and about 1 mol% to about 10 mol% crystalline M x WO3 phase, the crystal M x The WO3 phase comprises nanoparticles, wherein M is at least one of the following: 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 wherein 0 < x < 1.

[0008] A second aspect of this disclosure provides a glass-ceramic comprising a silicate glass phase and about 1 mol% to about 10 mol% crystalline M x The WO3 phase contains nanoparticles, wherein M is at least one alkali metal, and 0 < x < 1.

[0009] In another aspect, an aluminosilicate glass is also provided, comprising: SiO2, Al2O3, and at least one of the following: Sm2O3, Pr2O3, and Er2O3, wherein 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.

[0010] 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.

[0011] These and other aspects, advantages and distinctive features will become apparent from the following detailed description, the accompanying drawings and the appended claims. Attached Figure Description

[0012] Figure 1 This is a graph showing the absorbance versus wavelength for splat-quenched, annealed, and heat-treated glass-ceramic samples. Figure 2 These are spectra of a splat-quenched glass-ceramic composition (A), an annealed glass-ceramic composition (B), and a heat-treated glass-ceramic composition (C); Figure 3 It is a differential scanning calorimetry cooling curve obtained from a glass-ceramic sample; Figure 4 These are spectra of glass ceramics containing different alkaline tungsten bronzes; Figure 5 It is the X-ray powder diffraction distribution of glass-ceramics that have undergone spray-cooling. Figure 6 It is the X-ray powder diffraction distribution of heat-treated glass ceramics; Figure 7 This is a flowchart of a method for infiltrating glass to form glass-ceramics; Figure 8 This is the dispersion curve diagram of glass E listed in Table E; Figure 9 It is the transmission diagram of glass E listed in Table E; and Figure 10 These are the transmission diagrams of glasses J, K, and L listed in Table F. Detailed Implementation

[0013] In the following description, the same reference numerals denote similar or corresponding portions in several views shown in the accompanying drawings. It should also be understood that, unless otherwise indicated, terms such as “top,” “bottom,” “outward,” and “inward” are convenience terms and do not constitute limitation on the terminology. Furthermore, whenever a group is described as comprising at least one element from a set of elements and combinations thereof, it should be understood that the group may contain any number of these listed elements in the form of individual elements or combinations thereof, or consist primarily of them, or consist of them. Similarly, whenever a group is described as consisting of at least one element from a set of elements or combinations thereof, it should be understood that the group may consist of any number of these listed elements in the form of individual elements or combinations thereof. Unless otherwise stated, the enumerated numerical ranges include both the upper and lower limits of the ranges, as well as any range between the ranges. Unless otherwise stated, the indefinite article “a” or “an” and its corresponding definite article “the” as used herein mean “at least one” or “one or more”. It should also be understood that the various features disclosed in the specification and drawings can be used in any and all combinations.

[0014] As used herein, the terms “glass articles” and “articles made of glass” are used in their broadest sense to include any object made wholly or partially of glass and / or glass ceramics, and to include laminates of glass and glass ceramics described herein with conventional glass. Unless otherwise stated, all composition is expressed as mole percentage (mol%). The unit for the coefficient of thermal expansion (CTE) is 10⁻⁶. -7 / °C indicates a value measured over a temperature range of approximately 20–300°C, unless otherwise specified.

[0015] As used herein, the terms "nanoparticle" and "nanoparticle" refer to particles with 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 with a length of up to about 1000 nm and an aspect ratio (length / width) of at least 3, and in some embodiments, about 3 to about 5.

[0016] As used in this article, “transmission” and “transmittance” refer to external transmission or transmittance, taking into account absorption, scattering, and reflection. Fresnel reflection has not been subtracted from the transmission and transmittance values ​​recorded in this article.

[0017] It is important to note that the terms "substantially" and "about" are used herein to indicate the degree of inherent uncertainty that may arise from any quantitative comparison, numerical value, measurement, or other method of representation. These terms are also used herein to indicate that expressed values ​​of quantities may deviate to a certain extent from the stated reference values, but without altering the essential function of the subject matter under consideration. Thus, "MgO-free" glass is a glass in which no MgO is actively added to or incorporated into the glass, but may be present as a contaminant in very small amounts (e.g., less than 400 parts per million (ppm) or less than 300 ppm).

[0018] Compressive stress and layer depth are measured using methods known in the art. Such methods include, but are not limited to, measuring surface stress (FSM) using commercial instruments such as the FSM-6000 manufactured by Orihara Ltd. (Tokyo, Japan). Surface stress measurement relies on the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. The SOC is then measured according to a modified version of Scheme C as described in ASTM Standard C770-98 (2013) (referred to herein as the modified version), entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the entire text of which is incorporated herein by reference. The modification of Scheme C involves using a glass dish as the specimen, with a thickness of 5–10 mm and a diameter of 12.7 mm. The dish is isotropic and homogeneous, cored, and both sides are polished and parallel. The modification also includes calculating the maximum force F to be applied to the dish. 最大值 The applied force should be sufficient to produce a compressive stress of at least 20 MPa. Calculate F using the following equation. 最大值 : F 最大值 = 7.854·D·h In the formula, F 最大值 Let be the maximum force (in Newtons), D be the diameter of the disk (in millimeters (mm)), and h be the thickness of the light path (also in mm). For each applied force, the stress is calculated using the following equation: σ (MPa) = 8F / (π·D·h) In the formula, F is the force (in Newtons), D is the diameter of the disk (in millimeters (mm)), and h is the thickness of the light path (also in mm).

[0019] Unless otherwise stated, the terms “layer depth,” “DOL,” and “FSM_DOL” refer to the compressible layer depth determined by surface measurement (FSM) using commercially available instruments (e.g., but not limited to, the FSM-6000 stress meter). The compressible depth DOC refers to the depth at which the stress within the glass is effectively zero, and can be determined by stress distribution obtained using refractive near-field (RNF) and polarization methods known in the art. For single-ion exchange processes, this DOC is typically smaller than the FSM_DOL measured by an FSM instrument.

[0020] For reinforced glass articles where the compressive stress layer extends to a considerable depth within the glass, FSM technology may suffer from contrast issues, affecting the observed DOL value. At deeper compressive layer depths, insufficient contrast may exist between the TE and TM spectra, making it more difficult to calculate the difference between the spectral boundaries of the TE and TM polarization boundary optical modes and to accurately determine the DOL. Furthermore, FSM software analysis cannot determine the compressive stress curve (i.e., the variation of compressive stress with depth within the glass). In addition, FSM technology cannot determine the layer depth within the glass resulting from ion exchange of certain elements (e.g., sodium ions exchanging for lithium).

[0021] When the Depth of Compression (DOL) is a small fraction of the thickness *t* and the depth distribution of the refractive index profile approximates the simple linear cutoff curve quite well, the DOL determined by the FSM is a relatively good approximation of the depth of compression (DOC) of the compressed layer. This is especially true when the DOL is a significant fraction of the thickness, for example, when DOL ≥ 0.1. If t, then DOC is very often significantly lower than DOL. For example, in the idealized case of a linearly truncated curve, the relationship DOC = DOL·(1-r) is maintained, where r = DOL / t.

[0022] Alternatively, the Scattering Linear Polarizing Mirror (SCALP) technique, known in the art, can be used to determine compressive stress, stress distribution, and layer depth. SCALP technology enables non-destructive measurement of surface stress and layer depth.

[0023] See the attached diagram for an overall view, and refer to the diagram for details. Figure 1 It should be understood that the examples are for the purpose of describing specific embodiments of this disclosure and are not intended to limit the specification or appended claims. For clarity and brevity, the drawings are not necessarily drawn to scale, and some features and views may be shown enlarged to scale or schematically.

[0024] 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 comprise: 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 containing crystalline M x WO3 nanoparticles. In one embodiment, crystal M x WO3 nanoparticles are surrounded and dispersed within the residual glass phase, and in some embodiments, surrounded and dispersed throughout the entire residual glass phase. In another embodiment, M x WO3 crystalline nanoparticles are arranged at or near the surface of the glass-ceramic. In some embodiments, M x WO3 crystalline nanoparticles are in a sheet-like shape and have (as determined by those methods known in the art, such as SEM and / or TEM microscopy, X-ray diffraction, light scattering, centrifugation, etc.) an average diameter of about 10 nm to 1000 nm, or about 10 nm to about 5 μm, and / or M x WO3 nanorods possess a high aspect ratio and an average length (determined by those methods known in the art) of 10 nm to 1000 nm and an average width (determined by those methods known in the art) of about 2 to about 75 nm. In some embodiments, tungsten bronze glass-ceramics exhibiting high visible light transmittance and strong UV and NIR absorption contain M... x WO3 rods have 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 the following: 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 exhibit strong attenuation or blocking for ultraviolet (UV) radiation with wavelengths less than about 250 nm and near-infrared (NIR) radiation with wavelengths from about 700 nm to about 2500 nm.

[0025] In some embodiments, the glass-ceramics described herein are optically transparent in the visible light region of the spectrum (i.e., wavelengths from about 400 nm to about 700 nm). That is, the glass-ceramics have a transmittance greater than about 1% (referred to herein as "% / mm") over a 1 mm path length in at least a 50 nm wide wavelength band of light in the range of about 400 nm to about 700 nm. In some embodiments, the transmittance of the glass-ceramics is at least greater than about 10% / mm in at least a 50 nm wide wavelength band of light in the visible light region of the spectrum; in some embodiments, it is greater than about 30% / mm; and in other embodiments, it is greater than about 50% / mm (e.g., ≥75% / mm, ≥80% / mm, ≥90% / mm). Furthermore, without the use of mechanically fragile coatings or films that are sensitive to UV light and moisture, these glass-ceramics absorb light in the ultraviolet (UV) region of the spectrum (wavelengths less than about 370 nm) and the near-infrared (NIR) region (greater than about 700 nm to about 1700 nm). In some embodiments, for light with wavelengths less than or equal to about 370 nm (e.g., 370 nm wavelength), the transmittance of the glass-ceramic 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. In some embodiments, for light with wavelengths less than or equal to about 370 nm, the glass-ceramic absorbs at least 90% / mm or has an absorption of at least 90% / mm; in other embodiments, at least 95% / mm at this wavelength (e.g., 370 nm wavelength); and in other embodiments, at least 98% or even at least 99% / mm. In some embodiments, for light in the NIR region of the spectrum (i.e., about 700 nm to about 2500 nm), the transmittance of the glass-ceramic is less than 10% / mm over at least a 50 nm wide wavelength band, and in other embodiments, less than 5% / mm. In some embodiments, the glass-ceramic absorbs at least 90% / mm over at least one 50 nm wide optical wavelength band in the NIR region of the spectrum (i.e., from about 700 nm to about 2500 nm), and in other embodiments, it absorbs at least 95% / mm.

[0026] 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 at a 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.

[0027] In some embodiments, the coefficient of thermal expansion (CTE) of the glass-ceramic described herein is about 75 x 10⁻⁶ in the temperature range of about 0°C to about 300°C. -7 °C -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 °C -1 To approximately 66.3 x 10 -7 °C -1 (For example, samples 2, 11, 12, 13, and 54 in Table 1).

[0028] 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.

[0029] The glass-ceramics described herein can be used in low-emissivity glass windows for building, vehicle, medical, aerospace, or other applications (including thermal shielding, medical goggles, and filters). In some embodiments, the glass-ceramics form part of consumer electronic products (e.g., mobile phones or smartphones, laptops, or tablets). Such consumer electronic products typically include a housing having a front surface, a rear surface, and side surfaces, and include electronic components at least partially located within the housing. The electronic components include at least a power supply, a controller, memory, and a display. In some embodiments, the glass-ceramics described herein include at least a portion of protective elements, such as, but not limited to, the housing and / or the display.

[0030] In some embodiments, the glass phase is borosilicate glass, and the glass ceramic comprises SiO2, Al2O3, B2O3, WO3, and at least one alkali metal oxide R2O, wherein R2O is at least one of Na2O, K2O, Cs2O, and / or Rb2O, and the crystalline tungsten bronze phase is a tungsten bronze solid solution containing MWO3, comprising MWO3, or essentially composed of MWO3, wherein M is at least one of Na2O, K2O, Cs2O, and Rb2O. In some embodiments, the crystalline basic tungsten bronze phase is a crystalline basic tungsten bronze phase that is an basic tungsten bronze solid solution M1. x M2 y A mixture of WO3, wherein M1 = Li, Na, K, Cs, Rb and M2 = Li, Na, K, Cs, Rb, wherein M1 ≠ M2 and 0 < (x + y) < 1.

[0031] In some embodiments, the glass-ceramic comprises: about 56 mol% to about 78 mol% SiO2 (56 mol% ≤ SiO2 ≤ 78 mol%) or about 60 mol% to about 78 mol% SiO2 (60 mol% ≤ SiO2 ≤ 78 mol%); about 8 mol% to about 27 mol% B2O3 (8 mol% ≤ B2O3 ≤ 27 mol%); about 0.5 mol% to about 14 mol% Al2O3 (0.5 mol% ≤ Al2O3 ≤ 14 mol%); greater than 0 mol% to about 10 mol% of at least one of the following: Na2O, K2O, Cs2O, and Rb2O (0 mol% < Na2O + K2O + Cs2O + Rb2O ≤ 9 mol%); about 1 mol% to about 10 mol% WO3 (1 mol% ≤ WO3 ≤ 10 mol%) or in some embodiments about 1 mol% to about 5 mol% WO3 (1 mol% ≤ WO3 ≤ 9 mol%). 5 mol%); and 0 mol% to about 0.5 SnO2 (0 mol% ≤ SnO2 ≤ 0.5). In some embodiments, the glass ceramic may contain: 0 mol% to about 9 mol% Li2O; in some embodiments, 0 mol% to about 9 mol% Na2O (0 mol% < Na2O ≤ 9 mol%); in some embodiments, 0 mol% to about 9 mol% K2O (0 mol% < K2O ≤ 9 mol%) or 0 mol% to about 3 mol% K2O (0 mol% < K2O ≤ 3 mol%); in some embodiments, 0 mol% to about 10 mol% Cs2O (0 mol% < Cs2O ≤ 10 mol%) or greater than 0 mol% to about 7 mol% Cs2O (0 mol% < Cs2O ≤ 7 mol%); and / or in some embodiments, 0 mol% to about 9 mol% Rb2O (0 mol% < Rb2O ≤ 9 mol%). In some embodiments, the glass-ceramic contains about 9.8 mol% to about 11.4 mol% B2O3 (9.8 mol% ≤ B2O3 ≤ 11.4 mol%).

[0032] In some embodiments, the glass-ceramic described herein comprises: about 80 mol% to about 97 mol% SiO2 (80 mol% ≤ SiO2 ≤ 97 mol%); 0 mol% to about 5 mol% Al2O3 (0 mol% ≤ Al2O3 ≤ 5 mol%); 0 mol% to about 2 mol% R2O (0 mol% ≤ R2O ≤ 2 mol%), wherein R2O = Li2O, Na2O, K2O and / or Cs2O, or greater than 0 mol% to about 2 mol% Cs2O (0 mol% < Cs2O ≤ 2 mol%), or greater than 0 mol% to about 0.5 mol% Cs2O (0 mol% < Cs2O ≤ 0.5 mol%); and about 0.2 mol% to about 2 mol% WO3 (0.2 mol% ≤ WO3 ≤ 2 mol%). In a specific embodiment, the glass-ceramic comprises: about 87 mol% to about 93 mol% SiO2 (87 mol% ≤ SiO2 ≤ 93 mol%); 0 mol% to about 0.5 mol% Al2O3 (0 mol% ≤ Al2O3 ≤ 0.5 mol%); 3 mol% to about 6 mol% B2O3 (3 mol% ≤ B2O3 ≤ 6 mol%); 0.75 mol% WO3 to about 1.25 mol% WO3 (0.75 mol% ≤ WO3 ≤ 1.25 mol%); and 0.2 mol% to about 2 mol% R2O, wherein R = Li, Na, K and / or Cs (0.2 mol% ≤ R2O ≤ 2 mol%).

[0033] In some embodiments, the glass-ceramic may further comprise at least one of the following: up to about 0.5 mol% MgO (0 mol% ≤ MgO ≤ 0.5 mol%); up to about 2 mol% P2O5 (0 mol% ≤ P2O5 ≤ 2 mol%); and up to about 1 mol% (0 mol% ≤ ZnO ≤ 1 mol%). M can be increased by adding MgO (e.g., samples 55, 56, and 57 in Table 1), P2O5 (e.g., sample 58 in Table 1), and Zn (e.g., sample 59 in Table 1). x The formation rate of WO3 after cooling or heat treatment.

[0034] Table 1 lists non-limiting glass-ceramic compositions that are transparent in the visible light range and absorb UV and NIR radiation. Table 2 lists compositions that do not absorb UV or NIR radiation.

[0035] Table 1: Glass-ceramic compositions that are optically transparent in the visible light range and absorbent in the UV and NIR light ranges.

[0036] Table 2: Glass-ceramic compositions that do not absorb radiation in the UV and NIR light range

[0037] In some embodiments, -10 mol% ≤ R2O (mol%) – Al2O3 (mol%) ≤ 0.1 mol%. Peraluminous melts can be categorized into three subclasses based on how composition and heat treatment affect the optical properties of glass-ceramics. As used herein, the term "peraluminous melt" refers to a melt in which the molar proportion or content of alumina is greater than the molar proportion or content of R2O, wherein R2O is at least one of Li2O, Na2O, K2O, and Cs2O; that is, Al2O3 (mol%) > R2O (mol%). The first subclass is one in which the peraluminous melt is transparent in the visible wavelength range and 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 subsequent heat treatment at or slightly above the annealing temperature, but below the softening point, to establish NIR-absorbing nanocrystals M. x WO3 phase. The relationship between changes in optical properties and heat treatment is as follows: Figure 1 As shown, this is an absorptivity-wavelength graph of splat-quenched, annealed, and heat-treated samples of composition 13. As used herein, the term "splat-quenched" refers to a process in which a small amount of molten glass, or a molten glass "glob," is poured onto an iron plate at room temperature, and the drop is immediately pressed against it with an iron piston (also at room temperature), thereby rapidly cooling the glass and pressing the drop into a thin glass dish (3-6 mm). Although the splat-quenched samples of composition / sample 13 ( Figure 1 Samples A) and annealed sample B show no absorption in the visible or NIR regions, but those heat-treated samples (C, D, E) exhibit absorption in the NIR region (which increases with heat treatment time) and some visible light attenuation in the 600-700 nm wavelength range, resulting in a blue hue in the material.

[0038] If rapidly quenched, the second type of overaluminate melt retains transparency in the visible and NIR regions, but exhibits NIR absorption after annealing (see samples 12, 14, 19, 21, 22, 24, and 26-32 in Table 1). Like the overaluminate melts described above, and as... Figure 2 As shown (which displays the spectra of a sample of glass-ceramic composition 11 after spray quenching (A), annealing (B), and heat treatment (C), the NIR absorption of the spray quenched or annealed glass-ceramic can be enhanced by further heat treatment).

[0039] The third type of overaluminous melts even exhibits NIR absorption after rapid quenching (see samples 1 and 7 in 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.

[0040] A melt close to charge equilibrium (i.e., R₂O (mol%) – Al₂O₃ (mol%) = 0) 0.25 mol%) can be: transparent in visible light after rapid quenching and NIR-absorbing after annealing (see samples 8-11 and 45 in Table 1), or NIR-absorbing after rapid quenching or annealing (see samples 2-7 in Table 1). As described above, the melt can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.

[0041] Two over-basic (i.e., R2O (mol%) > Al2O3 (mol%)) UV-absorbing and NIR-absorbing melts (samples 46 and 50 in Table 1) are transparent to visible light and NIR when rapidly quenched, but become NIR-absorbing after annealing. As described above, the NIR absorption of these melts can be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.

[0042] Crystal M x The formation rate of the WO3 phase (which determines the optical absorptivity) can also be adjusted by regulating at least one of the following: heat treatment time and temperature, the ratio of (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%), the ratio of R2O (mol%) / WO3 (mol%), the ratio of Al2O3 (mol%) / WO3 (mol%), and the choice of the alkaline (or basic) substance to be added. In all cases, for longer heat treatment times, more crystals M... x WO3 phase precipitation yields materials with stronger NIR absorption. However, excessive heat treatment may cause crystal M... xThe WO3 phase becomes coarser. In some cases, this coarsening may be due to the formation of a second or ternary phase (e.g., borostalite or aluminum borate). The formation of these second phases can produce materials that scatter visible light wavelengths, thus appearing hazy or milky. Furthermore, in most cases, as the heat treatment temperature increases and approaches the softening point of the glass, M... x The rate of WO3 formation increases.

[0043] In some implementations, 1 ≤ (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) ≤ 6. As the ratio (R2O (mol%) + Al2O3 (mol%) / WO3 (mol%) increases, M... x The rate of WO3 formation decreases. When (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) ≥ 6, the absorption of NIR by crystals from the melt precipitation ceases. x WO3 phase.

[0044] In crystal M x In 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 that absorb NIR are formed... x WO3 bronze is formed, but very slowly. 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 in 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 crystalline 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.

[0045] Different alkali metal oxides lead to crystal M x The WO3 phase precipitates at different rates. For melts with the same feed composition but different alkali metal oxides R2O (where R = Li, Na, K, or Cs), when M (or R) is Cs, M... x WO3 precipitation rate is the slowest, and the fastest when M (or R) is Li, i.e., Cs < K < Na < Li (e.g., samples 14, 15, 16, and 13 in Table 1). The formation of crystals of M in the glass-ceramic depends on the presence of the alkali metal. x The temperature of the WO3 phase also shifts. Figure 3 The differential scanning calorimetry (DSC) cooling profiles for samples 14, 15, 16, and 13 are shown, and their composition is listed in Table 1. From Figure 3 As shown in Table A below, cesium-containing melts crystallize at the highest temperature, followed by potassium-containing melts, sodium-containing melts, and lithium-containing melts.

[0046] Table A: Crystal M x Crystallization temperature of WO3 phase

[0047] The peak or maximum transmission wavelength of the NIR absorption edge and visible light range of glass ceramics can be adjusted by the composition, heat treatment time and temperature, and the selection of alkali metal oxides. Figure 4 The spectra of glass-ceramics containing different basic tungsten bronzes and otherwise identical compositions (samples 14, 15, 16, and 13 in Table 1) are shown. Potassium and cesium analogs (samples 16 and 13, respectively) have shorter peak visible light transmission wavelengths (440–450 nm) than sodium and lithium analogs (samples 15 and 14, respectively) (which have peak visible light transmission wavelengths of 460 nm and 510 nm, respectively).

[0048] In some embodiments (e.g., Examples 37, 44, 46, and 50 in Table 1), the glass-ceramics described herein have a low boron concentration, approximately 9.8 mol% to approximately 11.4 mol% B₂O₃ (9.8 mol% ≤ B₂O₃ ≤ 11.4 mol%). In these samples, NIR absorption crystals M₂O₃ exhibit NIR absorption over a narrow and low temperature range. x The precipitation of the WO3 phase is shown in Table B. These compositions can be heated above their respective softening points, and droop, collapse, or form without crystallization. x Growth of the WO3 phase. This is achieved by first forming and / or shaping a glass article, followed by subsequent heat treatment of the material at a low temperature to precipitate NIR absorbing crystals M. x The WO3 second phase enables the control and adjustment of the optical properties of these glass-ceramics. Furthermore, by heating the glass for a short time above its corresponding softening point, crystals M in the glass-ceramics with the above composition are formed. x The second phase of WO3 can be "wiped off" (and the glass ceramic can be "bleached"). For example, composition 44 (Table 1) can be bleached by maintaining the material at a temperature of about 685°C to about 740°C for about 5 minutes.

[0049] Table B: Crystal M in samples with low B2O3 content x Crystallization temperature range of WO3 phase

[0050] In some embodiments, these glasses and glass-ceramics can be patterned using a UV laser. For example, M can be deposited in rapidly quenched compositions (e.g., sample 14 in Table 1) by exposing the material to a 10-watt 355 nm pulsed laser. x WO3 phase.

[0051] Table C lists the measured physical properties of the selected sample compositions listed in Table 1, including: strain point, annealing point, 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). Furthermore, X-ray powder diffraction (XRD) profiles of the spray-quenched glass-ceramic compositions and the heat-treated glass-ceramic compositions listed in Table 1 were obtained. Figure 5 and 6 These are representative XRD curves of the spray-quenched material and the heat-treated material, respectively, both of which have the composition shown in Table 1. These XRD curves confirm that the freshly quenched material (… Figure 5 It is amorphous and does not contain crystalline M prior to heat treatment. x WO3 phase, and heat-treated glass materials containing crystalline M xWO3, second phase.

[0052] Table C: Physical properties measured for glass ceramics with compositions selected from Table 1

[0053] In embodiments where the glass-ceramic comprises alumina (Al₂O₃) and at least one alkali metal, the glass-ceramic can be ion-exchangeable. Ion exchange is commonly used for the chemical strengthening of glass. In one specific example, basic cations in such a cation source (e.g., a molten salt or "ion exchange" bath) exchange with smaller basic cations within the glass, thereby achieving a layer at compressive stress (CS) extending from the surface into the glass phase at a depth of layer (DOL) or depth of compression (DOC), where CS is the maximum value of the glass. For example, potassium ions from the cation source typically exchange with sodium ions within the glass phase.

[0054] In some embodiments, the glass-ceramic is ion-exchanged and has a compression layer extending from at least one surface into the glass-ceramic to a depth of at least about 10 μm (denoted as DOC and / or DOL). The compressive stress CS of the compression layer at the surface is at least about 100 MPa and less than about 1500 MPa.

[0055] In a non-limiting example, compositions 51 and 54 underwent ion exchange. The samples were first heat-treated at 550°C for 15 hours, then cooled to 475°C at a rate of 1°C / min, and further cooled to room temperature at a furnace cooling rate (furnace rate) when the power was turned off. The ceramized samples were 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 micrometers, respectively, for glass-ceramic compositions 51 and 54.

[0056] In one embodiment, the glass-ceramic described herein can be manufactured using a melt quenching process. Appropriate proportions of the components can be mixed and blended by turbulent mixing or ball milling. The batching material is then melted at a temperature range of approximately 1550°C to approximately 1650°C for approximately 6 to approximately 12 hours, after which it can be cast or shaped and then annealed. Depending on the composition of the material, additional heat treatment at or slightly above the annealing point but below the softening point establishes the crystal structure M. xWO3 is a second phase that provides UV and NIR absorption properties. Optimal UV and NIR absorption properties were obtained using the compositions of samples 12-16, 37, 46, 50-53, and 61 in Table 1. Table D lists the exemplary compositions used to establish crystal M. x Heat treatment time and temperature range for the second phase of WO3.

[0057] Table D: Table of Materials Used for Producing UV Absorbers and NIR Absorbers via Melt Quenching Process x Heat treatment temperature and time range for WO3 glass ceramics

[0058] In other embodiments, glass-ceramics are formed by infiltrating nanoporous glasses (such as, but not limited to, VYCOR®, high-silica glasses manufactured by Corning Incorporated). Such 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] exist( Figure 7In 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 to about 550°C in ambient air to remove moisture and organic contaminants, and then kept stored at about 150°C until use.

[0063] First, the glass is impregnated with a tungsten-containing first solution at room temperature (approximately 25°C) to permeate the nanoporous glass (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.

[0064] In the next step of method 100, the permeated nanoporous glass sample is heated in flowing oxygen to decompose ammonium tungstate and form WO3 (step 130). The glass is first heated to about 225°C at a rate of about 1°C / min, then heated from about 225°C to about 450°C at a rate of 2.5°C / min, 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 may include preheating the glass at about 80°C for up to about 24 hours after the heat treatment described above.

[0065] Following step 130, the glass is immersed in the second solution at room temperature (approximately 25°C) (step 140), thereby allowing the M-cation solution to permeate the glass. In some embodiments, step 140 may be performed as follows: the glass is preheated at approximately 80°C for up to approximately 24 hours prior to immersion. In a non-limiting example, the nanoporous glass is immersed in the second solution for approximately 1 hour. The glass sample is then removed from the second solution, immersed in deionized water for approximately 1 minute, and dried in ambient air for approximately 24 hours to approximately 72 hours.

[0066] After step 140, the nanoporous glass sample is heated to form crystal M. x WO3 tungsten bronze phase (step 150). Heating step 150 includes: first heating the glass from about 5°C to about 200°C at a rate of about 1°C / min in a nitrogen atmosphere, then heating it 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 it at 575°C for 1 hour, and then rapidly cooling the glass to about 300°C by opening the furnace used for the heating step. In some embodiments, the sample is then placed in ambient air for an unspecified time.

[0067] Following 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 its boiling point and gently stirred. In some embodiments, the glass sample is immersed in the boiling solution for approximately 30 minutes. After being removed from the third solution, in some embodiments, the sample is washed with deionized water and left to stand in ambient air for approximately 24 hours. The glass is then heated in a nitrogen atmosphere to form and solidify the glass-ceramic (step 170). In step 170, the glass is first heated from room temperature to approximately 225°C at a heating rate of approximately 1°C / min, and then heated from approximately 225°C to approximately 800°C at a rate of approximately 5°C / min. The glass is held at 800°C for approximately 1 hour and then cooled from approximately 800°C to room temperature at a rate of approximately 10°C / min.

[0068] In another aspect, glasses doped with rare earth oxides (REOs) are provided, which exhibit high absorption in the NIR region of the spectrum. In some embodiments, these glasses contribute to the high refractive index of the glass in the IR region. Rare earth oxide dopants, including Sm₂O₃, Pr₂O₃, and Er₂O₃, account for up to about 12 mol% of the glass.

[0069] In some embodiments, the REO-doped glass is an aluminosilicate glass comprising Al₂O₃ and SiO₂, and at least one of Sm₂O₃, Pr₂O₃, and Er₂O₃, wherein Sm₂O₃ + Pr₂O₃ + Er₂O₃ ≤ 12 mol%. In some embodiments, the glass also 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. Non-limiting examples of aluminosilicate glass compositions are listed in Table E. The measured refractive indices (RI) of these glasses are also listed in Table E. Even at 1650°C, glasses A, B, and C without alkaline earth modifiers are too viscous to pour. Glasses E and F containing considerable amounts (> 21 mol%) of alkaline earth modifiers (and B₂O₃) can be easily poured at 1650°C. Figure 8 and 9 The percentage transmittance and dispersion of glass E in the visible and NIR regions of the spectrum are plotted separately. Glass E also exhibits a high refractive index in the infrared (IR) region and a high absorption rate at 1550 nm. Figure 10 The UV-VIS-IR spectra of these compositions containing 3-5 mol% Pr2O3 were plotted, and the high absorption rate of these glasses at 1550 nm was shown.

[0070] Table E: Composition of Rare Earth Doped Aluminosilicate Glass

[0071] 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 wavelengths from 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 indices (RI) of these glasses are also listed in Table F.

[0072] Table F: Composition of rare earth-doped Zn-Bi-borate glasses

[0073] While typical embodiments have been given for illustrative purposes, the foregoing description should not be considered as limiting the scope of this specification or the appended claims. Therefore, various modifications, alterations, and substitutions will arise to those skilled in the art without departing from the spirit and scope of this specification or the appended claims.

Claims

1. A type of glass comprising: 56 mol% ≤ SiO2 ≤ 78 mol% 8 mol% ≤ B2O3 ≤ 27 mol% 0.5 mol% ≤ Al2O3 ≤ 14 mol% 1 mol% ≤ WO3 ≤ 10 mol%; and R2O, in mole% such that -10 mole% ≤ (R2O – Al2O3) ≤ 0.1 mole%, wherein R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O and / or Rb2O.

2. The glass as claimed in claim 1, wherein, The glass contains 60 mol% ≤ SiO2 ≤ 78 mol%.

3. The glass as claimed in claim 1, wherein, The glass contains 1 mol% ≤ WO3 ≤ 5 mol%.

4. The glass as claimed in claim 1, further comprising 0 mol% ≤ SnO2 ≤ 0.5 mol%.

5. The glass of claim 1, further comprising 0 mol% < Li₂O ≤ 9 mol%.

6. The glass of claim 1, further comprising 0 mol% < Na2O ≤ 9 mol%.

7. The glass of claim 1, further comprising 0 mol% < K2O ≤ 9 mol%.

8. The glass of claim 1, further comprising 0 mol% < Cs₂O ≤ 10 mol%.

9. The glass of claim 1, further comprising 0 mol% < Rb₂O ≤ 9 mol%.

10. The glass as claimed in claim 1, wherein, The glass contains 9.8 mol% ≤ B2O3 ≤ 11.4 mol%.

11. The glass of claim 1, further comprising at least one of the following: 0 mol% ≤ MgO ≤ 0.5 mol% 0 mol% ≤ P2O5 ≤ 2 mol%; and / or 0 mol% ≤ ZnO ≤ 1 mol%.

12. The glass as claimed in claim 1, wherein, In mole percent, 0 < (Na2O + K2O + Cs2O + Rb2O) ≤ 9.

13. The glass as claimed in claim 1, wherein, In mole percent, 0 ≤ (R2O / WO3) ≤ 4.

14. The glass as claimed in claim 1, wherein, In mole percent, 1 ≤ [(R2O + Al2O3) / WO3] ≤ 6.

15. A method for manufacturing glass-ceramic articles, comprising: The glass is heat-treated to grow crystals of M x WO3, where 0 < x < 1 and M comprises H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Ti, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu and / or U, Specifically, at least prior to heat treatment, the glass comprises SiO2, B2O3, Al2O3, WO3, and R2O, based on the constituent oxides, where R2O is the sum of the alkali metal oxides Li2O, Na2O, K2O, Cs2O, and / or Rb2O in the glass. In this context, based on the molar percentage of glass, at least prior to heat treatment, Al2O3 and R2O satisfy -10≤(R2O-Al2O3)≤0.

1.

16. The method of claim 15, wherein, At least prior to heat treatment, the glass comprises 0 ≤ (R2O / WO3) ≤ 4 in mole percent.

17. The method of claim 15, wherein, At least prior to heat treatment, the glass comprises, in mole percent, 1 ≤ [(R2O + Al2O3) / WO3] ≤ 6.

18. The method of claim 15, wherein, At least prior to heat treatment, the glass comprises 0 ≤ (Na2O + K2O + Cs2O + Rb2O) ≤ 9 in mole percent.

19. The method of claim 15, wherein, The heat treatment lasts for at least 0.2 hours.

20. The method of claim 15, wherein, The heat treatment temperature is at least 5000°C.

21. The method of claim 15, wherein, In the range of 400 to 700 nm, over a 1 mm path, the glass-ceramic transmittance is greater than 1% for at least one 50 nm wide optical wavelength band.

22. The method of claim 15, wherein, For wavelengths of 370 nm or shorter, the transmittance of glass ceramics for light is less than 5% over a 1 mm path.

23. The method of claim 15, wherein, In the range of 700 to 2500 nm, over a 1 mm path, the glass-ceramic transmittance for at least one 50 nm wide optical wavelength band is less than 10%.

24. The method of claim 15, further comprising, in at least a portion of the article of manufacture, for at least some M x WO3 crystals are bleached or wiped off.

25. The method of claim 24, wherein, Bleaching involves further heating the portion.

26. The method of claim 25, wherein, The further heating includes using a laser for the further heating.

27. The method of claim 25, wherein, The further heating includes heating the portion to 685°C to 740°C for 5 minutes.

28. A method for manufacturing glass-ceramic articles, comprising: Bleaching the crystals of WO3 in at least a part of a glass-ceramic article, where 0 < x < 1 and M comprises 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 / or U, where the glass-ceramic of the article is made from a glass which, calculated as constituent oxides, contains SiO2, B2O3, Al2O3, WO3 and R2O, where R2O is the sum of the alkali metal oxides Li2O, Na2O, K2O, Cs2O and / or Rb2O in the glass, and where, in mol%, the Al2O3 and R2O of the glass are such that -10 ≤ (R2O - Al2O3) ≤ 0.

1. x ​ 29. The method of claim 28, wherein, Bleaching involves heating the product.

30. The method of claim 29, wherein, Heating includes the use of lasers.

31. The method of claim 29, wherein, Heating involves heating the article at 685°C to 740°C for 5 minutes.

32. The method of claim 28, further comprising a glass ceramic from which the article is made.

33. A method for manufacturing glass-ceramic articles, comprising: The glass is heat-treated to grow crystals of M x WO3, where 0 < x < 1 and M comprises 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 / or U, Specifically, at least prior to heat treatment, the glass comprises SiO2, B2O3, Al2O3, WO3, and R2O, based on the constituent oxides, where R2O is the sum of the alkali metal oxides Li2O, Na2O, K2O, Cs2O, and / or Rb2O in the glass. After heat treatment, in the range of 400 to 700 nm, the glass ceramic has a transmittance of greater than 1% for at least one 50 nm wide optical wavelength band along a 1 mm path.

34. The method of claim 33, wherein, The duration of the heat treatment is at least 0.2 hours, and the temperature of the heat treatment is at least 5000°C.

35. A glass-ceramic comprising: Silicate glass phase; and 0.1 mol% to 10 mol% of crystals M x The WO3 phase contains nanoparticles, where M is at least one alkali metal, and 0 < x < 1.

36. The glass-ceramic of claim 35, wherein, Glass ceramics contain 0.1 mol% to 5 mol% crystalline M x WO3 phase.

37. The glass-ceramic of claim 35, wherein, The silicate glass phase is a borosilicate glass phase.

38. The glass-ceramic as described in claim 35, wherein, The glass-ceramic comprises: 56 mol% to 78 mol% SiO2, 9 mol% to 27 mol% B2O3, 0.5 mol% to 14 mol% Al2O3, at least one of the following from 0 mol% to 9 mol%: Li2O, Na2O, K2O, Cs2O and Rb2O, 1 mol% to 10 mol% WO3, and 0 mol% to 0.5 SnO2.

39. The glass-ceramic as described in claim 35, wherein, M is Cs, and the glass ceramic contains more than 0 mol% to 10 mol% Cs2O.

40. The glass-ceramic of claim 35, wherein, -10 mol% ≤ R2O (mol%) – Al2O3 (mol%) ≤ 0.1 mol%, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O and Rb2O.

41. The glass-ceramic as claimed in claim 35, wherein, 0 < R2O (mol%) / WO3 (mol%) ≤ 2.61, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O and Rb2O.

42. The glass-ceramic as described in claim 35, wherein, 0.66 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 6.

43. The glass-ceramic as described in claim 35, wherein, The glass ceramic also contains at least one of the following: up to 0.5 mol% MgO; up to 2 mol% P2O5; and up to 1 mol% ZnO.

44. The glass-ceramic as described in claim 35, wherein, For light with a wavelength range of 400 nm to 700 nm, the glass ceramic has a transmittance of at least 1% / mm over at least one 50 nm wide wavelength band of light.

45. The glass-ceramic of claim 35, wherein, For light with wavelengths of 370 nm or shorter, glass ceramics have a transmittance of less than 1% / mm.

46. ​​The glass-ceramic as described in claims 35-45, wherein, For light with a wavelength range of 700 nm to 2500 nm, the glass ceramic has a transmittance of less than 5% / mm over at least one 50 nm wide wavelength band of light.

47. The glass-ceramic of claim 46, wherein, When glass-ceramics are heated in the temperature range of 200°C to 300°C, the transmittance of the glass-ceramics changes by less than 10% / mm in the range of 500 nm to 2500 nm.

48. The glass-ceramic as claimed in claim 35, wherein, Glass ceramics are ion-exchangeable.

49. The glass-ceramic as claimed in claim 39, wherein, The glass-ceramic undergoes ion exchange and has a compression layer extending from the surface of the glass-ceramic to a depth of at least 10 μm within the glass-ceramic, the compression layer having a maximum compressive stress of at least 100 MPa and less than 1500 MPa at the surface.

50. The glass-ceramic as claimed in claim 35, wherein, Glass ceramics can be bleached through heat treatment.

51. The glass-ceramic as described in claim 35, wherein, Glass ceramics are unaffected by moisture and oxygen.

52. The glass-ceramic as described in claim 35, wherein, M includes Cs, and the glass ceramics contain: 80 mol% to 97 mol% SiO2; 0 mol% to 5 mol% Al2O3; greater than 0 mol% to 2 mol% Cs2O; and 0.2 mol% to 2 mol% WO3.

53. The glass-ceramic as described in claim 35, wherein, Crystal M x The WO3 phase includes at least one of the following: multiple lamellar shapes M x WO3 nanoparticles and multiple M x WO3 nanorods.

54. The glass-ceramic as described in claim 53, wherein, The multiple thin sheet shapes M x The average diameter of WO3 nanoparticles ranges from 10 nm to 5 μm.

55. The glass-ceramic as described in claim 53, wherein, The multiple M x The average length of WO3 nanorods ranges from 10 nm to 1000 nm, and the average width ranges from 2 nm to 75 nm.

56. The glass-ceramic as claimed in claim 53 or 55, wherein, The multiple M x The average length of WO3 nanorods ranges from 10 nm to 200 nm, and the average width ranges from 2 nm to 30 nm.

57. The glass-ceramic according to any one of claims 35-56, wherein, Glass-ceramics are at least a part of heat shields, filters, building components, automotive components, or protective elements for electronic displays.

58. A glass-ceramic comprising: The glass phase comprises at least 80% by weight silica; and Crystalline tungsten bronze phase, which contains nanoparticles and has the chemical formula M x WO3, wherein M includes, but is not limited to, at least one of the following: 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 wherein 0 < x < 1.

59. The glass-ceramic as claimed in claim 58, wherein, M is at least one alkali metal.

60. The glass-ceramic of claim 59, wherein, Glass ceramics include: The following are included: about 56 mol% to about 78 mol% SiO2, about 8 mol% to about 27 mol% B2O3, about 0.5 mol% to about 14 mol% Al2O3, greater than 0 mol% to about 10 mol% of at least one of the following: Li2O, Na2O, K2O, Cs2O and Rb2O, about 1 mol% to about 10 mol% WO3, and 0 mol% to about 0.5 mol% SnO2.

61. The glass-ceramic as claimed in claim 58, wherein, M is Cs, and the glass ceramic contains greater than 0 mol% to about 10 mol% Cs2O.

62. The glass-ceramic as described in claim 59, in, -10 mol% ≤ R2O (mol%) – Al2O3 (mol%) ≤ 0.1 mol%, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O and Rb2O; Wherein, 0 < R2O (mol%) / WO3 (mol%) ≤ 2.61, and R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O, and Rb2O; or Wherein, 1 ≤ (R2O(mol%) + Al2O3(mol%)) / WO3(mol%) ≤ 6, and R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O and Rb2O.

63. The glass-ceramic as described in claim 59, wherein, 0.66 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 6.

64. The glass-ceramic as described in claim 59, wherein, The glass ceramic also includes at least one of the following: up to about 0.5 mol% MgO; up to about 2 mol% P2O5; and up to about 1 mol% ZnO.

65. The glass-ceramic as claimed in claim 58, wherein, M is at least one of the following: H, 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 0 < x < 1.

66. The glass-ceramic of claim 65, wherein, M is Ag.

67. The glass-ceramic as described in claim 58 or 59, wherein, The silicate glass phase is a borosilicate glass phase.

68. The glass-ceramic as claimed in claim 58 or 59, wherein, The glass-ceramic contains approximately 0.1 mol% to approximately 10 mol% of crystalline M. x WO3 phase, optionally wherein the glass ceramic contains about 0.1 mol% to about 5 mol% crystalline M x WO3 phase.

69. The glass-ceramic as claimed in claim 58 or 59, wherein, Crystal M x The WO3 phase includes at least one of the following: multiple lamellar shapes M x WO3 nanoparticles and multiple M x WO3 nanorods, optionally wherein the plurality of thin sheets are of shape M x The average diameter of WO3 nanoparticles is approximately 10 nm to 5 µm.

70. The glass-ceramic of claim 69, wherein, The multiple M x The WO3 nanorods have an average length of about 10 nm to about 1000 nm and an average width ranging from about 2 nm to about 75 nm, optionally wherein... Multiple M x The average length of the WO3 nanorods is about 10 nm to about 200 nm and the average width ranges from about 2 nm to about 30 nm.

71. The glass-ceramic as claimed in claim 58 or 59, wherein, The glass phase comprises at least 90% by weight silica.

72. The glass-ceramic as described in claim 58 or 59, wherein, The glass-ceramic is ion-exchangeable, optionally wherein the glass-ceramic is ion-exchangeable and has a compression layer extending from the surface of the glass-ceramic to a depth of at least about 10 μm within the glass-ceramic, the compression layer having a compressive stress at the surface of at least about 100 MPa and less than about 1500 MPa.

73. A glass-ceramic comprising: 56 mol% to 78 mol% SiO2; 8 mol% to 27 mol% B2O3; 0.5 mol% to 14 mol% Al2O3; At least one of the following: Li₂O, Na₂O, K₂O, and Cs₂O, in amounts greater than 0 mol% to 10 mol%; 1 mol% to 10 mol% WO3; 0 mol% to 0.5 mol% SnO2; and 0.1 mol% to 10 mol% of crystals M x The WO3 phase comprises nanoparticles, wherein M is at least one of Li, Na, K, and Cs, and 0 <x<1。 74. The glass-ceramic of claim 73, wherein: (i) For light with a wavelength range of 400 nm to 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 with a wavelength of 370 nm or less, the glass ceramic has a transmittance of less than 1% / mm.

75. The glass-ceramic as claimed in claim 73, wherein, For light with a wavelength range of 700 nm to 2500 nm, the glass ceramic has a transmittance of less than 5% / mm over at least one 50 nm wide wavelength band of light.

76. The glass-ceramic of claim 74, wherein, When glass-ceramics are heated in the temperature range of 200°C to 300°C, the transmittance of the glass-ceramics changes by less than 10% / mm in the range of 500 nm to 2500 nm.

77. The glass-ceramic of claim 73, wherein, The glass-ceramic is: (i) ion-exchangeable; or (ii) ion-exchangeable and having a compression layer extending from the surface of the glass-ceramic to a depth of at least 10 μm within the glass-ceramic, the compression layer having a compressive stress of at least 100 MPa and less than 1500 MPa at the surface.

78. The glass-ceramic of claim 73, wherein, Glass ceramics are those that: (i) can be bleached by heat treatment; and / or (ii) have a coefficient of thermal expansion of less than or equal to 75 x 10⁻⁶ over a temperature range of 0°C to 300°C. -7 °C -1 .

79. The glass-ceramic as claimed in claim 73, wherein, Glass ceramics contain 0.1 mol% to 5 mol% crystalline M x WO3 phase.

80. The glass-ceramic of claim 73, wherein: (i) M is Cs, and the glass ceramic contains greater than 0 mol% to 10 mol% CS2O; or (ii) -10 mol% ≤ R2O (mol%) – Al2O3 (mol%) ≤ 0.1 mol%, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O, and Rb2O; or (iii) 0 < R2O (mol%) / WO3 (mol%) ≤ 2.61, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O, and Rb2O; or (iv) 0.66 ≤ Al2O3 (mol%) / WO3 (mol%) ≤ 6; or (v) 1 ≤ (R2O (mol%) + Al2O3 (mol%)) / WO3 (mol%) ≤ 6, where R2O is at least one of the following: Li2O, Na2O, K2O, Cs2O, and Rb2O; or (vi) The glass ceramic also contains at least one of the following: up to 0.5 mol% MgO; up to 2 mol% P2O5.

81. The glass-ceramic as claimed in claim 73, wherein, Crystal M x The WO3 phase includes at least one of the following: multiple lamellar shapes M x WO3 nanoparticles and multiple M x WO3 nanorods.

82. The glass-ceramic as claimed in claim 81, wherein: (i) The shape M of the plurality of thin sheets 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 WO3 nanorods ranges from 10 nm to 1000 nm, and the average width ranges from 2 nm to 75 nm.

83. The glass-ceramic as described in claim 81, wherein, The multiple M x The average length of WO3 nanorods ranges from 10 nm to 200 nm, and the average width ranges from 2 nm to 30 nm.

84. The glass-ceramic as claimed in claim 81, wherein, Glass-ceramics are at least a part of heat shields, filters, building components, automotive components, or electronic display housings.

85. A zinc-bismuth-borate glass comprising: Approximately 20 mol% to approximately 30 mol% ZnO Approximately 4 mol% to approximately 20 mol% Bi₂O₃ Approximately 40 mol% to approximately 50 mol% of B₂O₃, and At least one of Sm2O3, Pr2O3 and Er2O3 in, Sm₂O₃ + Pr₂O₃ + Er₂O₃ ≤ 10 moles.

86. The zinc-bismuth-borate glass as described in claim 85, wherein, Zinc-bismuth-borate glass has a transmittance of less than 30% in the wavelength range of 1400 nm to 1600 nm.

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