EP3700871A2 - Vitrocéramiques et verres - Google Patents

Vitrocéramiques et verres

Info

Publication number
EP3700871A2
EP3700871A2 EP18871435.6A EP18871435A EP3700871A2 EP 3700871 A2 EP3700871 A2 EP 3700871A2 EP 18871435 A EP18871435 A EP 18871435A EP 3700871 A2 EP3700871 A2 EP 3700871A2
Authority
EP
European Patent Office
Prior art keywords
mol
glass
ceramic
article
crystalline phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18871435.6A
Other languages
German (de)
English (en)
Other versions
EP3700871A4 (fr
Inventor
Matthew John Dejneka
Jesse KOHL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US15/840,040 external-priority patent/US10246371B1/en
Application filed by Corning Inc filed Critical Corning Inc
Publication of EP3700871A2 publication Critical patent/EP3700871A2/fr
Publication of EP3700871A4 publication Critical patent/EP3700871A4/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Definitions

  • the present disclosure generally relates to articles including glasses and/or glass- ceramics, and more specifically, to compositions and methods of forming such articles.
  • UV and R metallic Ultraviolet containing silicate glass-ceramics are a class of glass-ceramics which exhibit optical properties dependent on the wavelength of light which is incident on the glass-ceramics.
  • Conventional UV/IR-blocking glasses are formed by introducing certain cationic species (e.g., Fe2+ to absorb NIR wavelengths and Fe23+ to absorb UV wavelengths, and other dopants such as Co, Ni, and Se to modify the visible transmittance) which are bonded with the glass network.
  • these glass-ceramics were produced by melting the constituents together to form a glass, followed by the in situ formation of submicron precipitates through a post-formation heat treatment to form the glass-ceramic.
  • These submicroscopic precipitates e.g., tungstate- and molybdate-containing crystals
  • Such conventional glass-ceramics could be produced in both transparent as well as opalized forms.
  • tungsten oxide can react with alkali metal oxides in the batch to form a dense alkali tungstate liquid at a low temperature during the initial stages of the melt immediately after being put into a melting furnace (e.g., the reaction occurs at about 500° C). Because of the high density of this phase, it rapidly segregates at the bottom of the crucible.
  • tungsten- and/or molybdenum-rich phase separate from the silicate rich phase, they perceived a solubility limit of tungsten and/or molybdenum (e.g., about 2.5 mol%) within the silicate rich phase.
  • the perceived solubility limit prevented the glass from ever becoming super-saturated with tungsten or molybdenum oxides, thereby preventing either constituent from being controllably precipitated through post-forming heat-treatment to produce a glass-ceramic with a crystalline phase including these elements.
  • the perceived solubility prevented the development of glass-ceramic compositions which achieved a sufficient quantity of solubilized tungsten and/or molybdenum to allow the formation of tungsten and/or molybdenum containing wavelength dependent submicroscopic crystals through subsequent heat treatment.
  • peralkaline melt may be obtained through the use of "bound" alkalis as described herein.
  • exemplary bound alkalis may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali-aluminum-silicates and/or other naturally occurring and artificially created minerals containing an alkali and one or more aluminum and/or silicon atoms.
  • the alkalis may not react with the W or Mo present in the melt to form the dense alkali tungstate and/or alkali molybdate liquid.
  • a glass-ceramic includes silicate- containing glass and crystalline phases, where the crystalline phase includes non- stoichiometric suboxides of tungsten and/or molybdenum, or alternatively titanium, forming 'bronze'-type solid state defect structures in which vacancies are occupied with dopant cations.
  • a glass-ceramic includes an amorphous phase and a crystalline phase comprising a plurality of precipitates of formula MxWCb and/or MxMoCb, where 0 ⁇ x ⁇ l and M is a dopant cation.
  • the precipitates have a length of from about 1 nm to about 200 nm as measured by Electron Microscopy. Precipitates of the crystalline phase may be substantially homogenously distributed within the glass-ceramic.
  • a glass-ceramic may include an amorphous phase and a crystalline phase comprising a plurality of precipitates of formula MxTiCh, where 0 ⁇ x ⁇ l and M is a dopant cation.
  • the precipitates have a length of from about 1 nm to about 200 nm, or 1 nm to about 300 nm or 1 nm to about 500 nm as measured by Electron Microscopy. Precipitates of the crystalline phase may be substantially homogenously distributed within the glass-ceramic.
  • a glass-ceramic includes silicate-containing glass and crystals of non-stoichiometric tungsten and/or molybdenum suboxides intercalated with dopant cations homogenously distributed within the silicate-containing glass.
  • the glass-ceramic may have transmittance of about 5% per mm or greater over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
  • the dopant cations may be H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and/or Ce.
  • at least some of the crystals are at a depth of greater than about 10 ⁇ from an exterior surface of the glass-ceramic.
  • the crystals may have rod-like morphology.
  • a glass-ceramic includes a silicate-containing glass phase and a crystalline phase comprising suboxides of tungsten and/or molybdenum forming solid state defect structures in which holes are occupied with dopant cations.
  • the volume fraction of the crystalline phase in the glass-ceramic may be from about 0.001% to about 20%.
  • a glass-ceramic a silicate-containing glass and crystals of non- stoichiometric titanium suboxides intercalated with dopant cations homogenously distributed within the silicate-containing glass; and/or a silicate-containing glass phase and a crystalline phase comprising suboxides of titanium forming solid state defect structures in which holes are occupied with dopant cations.
  • an article includes at least one amorphous phase and one
  • the crystalline phase comprises an oxide, from about 0.1 mol% to about 100 mol% of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.
  • the article may be substantially Cd and Se free.
  • a glass such as a glass precursor to glass-ceramic
  • the glass if WO3 is from about 1 mol% to about 30 mol%, then the glass further comprises Fe203 of about 0.9 mol% or less, or then S1O2 is from about 60 mol% to about 99 mol%. If WO3 is from about 0.35 mol% to about 1 mol%, then the glass may comprise Sn02 from about 0.01 mol% to about 5.0 mol%.
  • M0O3 is from about 1 mol% to about 30 mol%, then S1O2 may range from about 61 mol% to about 99 mol%, or then Fe203 may be about 0.4 mol% or less and R2O is greater than RO. If M0O3 is from about 0.9 mol% to about 30% and S1O2 is from about 30 mol% to about 99 mol%, then the glass may further comprise Sn02 from about 0.01 mol% to about 5 mol%.
  • a method of forming a glass-ceramic includes steps of melting together, to form a glass melt, (1) a bound alkali, (2) silica, and (3) tungsten and/or molybdenum; solidifying the glass melt into a glass; and precipitating a crystalline phase within the glass to form the glass-ceramic article.
  • the glass may be a single homogenous, solid phase.
  • the crystalline phase may include the tungsten and/or molybdenum.
  • the bound alkali comprises: (A) feldspar, (B) nepheline, (C) sodium borate, (D) spodumene, (E) sodium feldspar, (F) potassium feldspar, (G) alkali-alumino- silicate, (H) alkali silicate, and/or (I) an alkali bonded to (I-i) alumina, (I-ii) bona and/or (I- iii) silica.
  • a method of forming a glass-ceramic includes steps of melting together silica and tungsten and/or molybdenum to form a glass melt, solidifying the glass melt to form a glass, and precipitating, within the glass, bronze-type crystals comprising the tungsten and/or molybdenum. Precipitating the crystalline phase may include thermally processing the glass. In at least some such embodiments, the method further includes a step of growing precipitates of the crystalline phase to a length of at least about 1 nm and no more than about 500 nm.
  • a glass-ceramic includes a silicate-containing glass phase; and a crystalline phase comprising suboxides of titanium, the suboxides of titanium comprising solid state defect structures in which holes are occupied with dopant cations.
  • a glass-ceramic includes an amorphous phase; and a crystalline phase comprising a plurality of precipitates of formula MxTiCh, where 0 ⁇ x ⁇ l and M is a dopant cation.
  • a glass-ceramic includes a silicate-containing glass; and a plurality of crystals homogenously distributed within the silicate-containing glass, wherein the crystals comprise non-stoichiometric titanium suboxides, and further wherein the crystals are intercalated with dopant cations.
  • a glass-ceramic article includes at least one amorphous phase and a crystalline phase; and SiCh from about 1 mol% to about 95 mol%; wherein the crystalline phase comprises a non-stoichiometric titanium suboxide from about 0.1 mol% to about 100 mol% of the crystalline phase, the oxide comprising at least one of: (i) Ti, (ii) V and an alkali metal cation.
  • a method of forming a glass-ceramic includes: melting
  • the glass- ceramic comprising: (a) a second average near-infrared absorbance, wherein a ratio of the second average near-infrared absorbance to the first average near-infrared absorbance is about 1.5 or greater, and (b) an average optical density per mm of about 1.69 or less.
  • a glass comprising in batch constituents: S1O2 from about 1 mol% to about 90 mol%; AI2O3 from about 0 mol% to about 30 mol%; T1O2 from about 0.25 mol% to about 30 mol%; a metal sulfide from about 0.25 mol% to about 30 mol%; R2O from about 0 mol% to about 50 mol%, wherein R2O is one or more of L12O, Na20, K2O, Rb20 and CS2O; and RO from about 0 mol% to about 50 mol%, wherein RO is one or more of BeO, MgO, CaO, SrO, BaO and ZnO, wherein the glass is substantially Cd free.
  • FIG. 1 is a cross-sectional view of an article including a substrate comprising a glass- ceramic composition, according to at least one example of the disclosure.
  • FIG. 2A is a plot of transmittance vs. wavelength of a comparative CdSe glass and a heat-treated glass-ceramic, according to at least one example of the disclosure.
  • FIG. 2B is the plot in FIG. 2A, as rescaled to show the cutoff wavelength of the
  • FIG. 3 A is a plot of transmittance vs. wavelength of a comparative CdSe glass and glass-ceramic samples heat treated from 525°C to 700°C according to various conditions, according to examples of the disclosure.
  • FIG. 3B is the plot in FIG. 3 A, as rescaled to show the cutoff wavelength of the
  • FIG. 4A is a plot of transmittance vs. wavelength of a comparative CdSe glass and glass-ceramic samples heat treated at 700°C and 800°C according to various conditions, according to examples of the disclosure.
  • FIG. 4B is the plot in FIG. 4A, as rescaled to show the cutoff wavelength of the comparative CdSe glass and the glass-ceramic samples heat treated according to various conditions.
  • FIG. 4C is the plot in FIG. 4A, along with the transmittance vs. wavelength for
  • FIG. 5 is an x-ray diffraction ("XRD") plot of a heat-treated glass-ceramic, according to at least one example of the disclosure.
  • FIGS. 6A-6C are respective Raman spectroscopy plots of splat-quenched glass- ceramic samples and glass-ceramic samples heat treated at 650°C and 700°C according to various conditions, according to examples of the disclosure.
  • FIGS. 7A & 7B are Raman spectroscopy plots of glass-ceramic samples heat treated at 650°C and 700°C according to various conditions and as splat-quenched, according to examples of the disclosure.
  • FIG. 8 is a plot of residual stress vs. substrate depth of two glass-ceramic samples with compressive stress regions derived from two respective ion-exchange process conditions, according to examples of the disclosure.
  • FIG. 9 is a scanning electron microscope (SEM) micrograph of a glass-ceramic
  • FIGS. 10A and 10B are SEM and transmission electron microscope (TEM)
  • FIGS. 11 A and 1 IB are SEM and TEM micrographs, respectively, of a glass-ceramic according to yet another exemplary embodiment.
  • FIGS. 12A and 12B are transmittance spectra and absorbance spectra in OD/mm
  • FIGS. 13 A and 13B are transmittance spectra and absorbance spectra in OD/mm
  • FIGS. 14A and 14B are transmittance spectra and absorbance spectra in OD/mm
  • FIGS. 15A and 15B are transmittance spectra and absorbance spectra in OD/mm collected of 0.5 mm polished flats of composition 889FMD in the as-made un-annealed state and heat treated condition (500° C lh and 600° C lh).
  • FIGS. 16A and 16B are transmittance spectra and absorbance spectra in OD/mm
  • composition 889FME collected of 0.5 mm polished flats of composition 889FME in the as-made un-annealed state and heat treated condition (600° C lh and 700° C lh).
  • FIGS. 17A and 17B are transmittance spectra and absorbance spectra in OD/mm
  • composition 889FMG collected of 0.5 mm polished flats of composition 889FMG in the as-made un-annealed state and heat treated condition (700° C lh and 700° C 2h).
  • FIGS. 18A-18D are TEM micrographs at four different magnifications of titanium- containing crystals within a heat treated sample of composition 889FMC that was heat treated at 700° C for one hour.
  • FIG. 19A is a TEM micrograph of titanium-containing crystals within a heat treated sample of composition 889FMC that was heat treated at 700° C for one hour.
  • FIG. 19B is an electron dispersive spectroscopy (EDS) elemental map of titanium of the TEM micrograph of FIG. 19 A.
  • EDS electron dispersive spectroscopy
  • the term "and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed.
  • the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
  • relational terms, such as first and second, top and bottom, and the like, are used solely to distinguish one entity or action from another entity or action, without necessarily requiring or implying any actual such relationship or order between such entities or actions.
  • Coupled in all of its forms: couple
  • coupling, coupled, etc. generally means the joining of two components (electrical or mechanical) directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two components (electrical or mechanical) and any additional intermediate members being integrally formed as a single unitary body with one another or with the two components. Such joining may be permanent in nature, or may be removable or releasable in nature, unless otherwise stated.
  • substantially is intended to note that a described feature is equal or approximately equal to a value or description.
  • a “substantially planar” surface is intended to denote a surface that is planar or approximately planar.
  • substantially is intended to denote that two values are equal or approximately equal.
  • substantially may denote values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.
  • melt constituents e.g., fluorine, alkali metals, boron, etc.
  • volatilization e.g., as a function of vapor pressure, melt time and/or melt temperature
  • the term "about,” in relation to such constituents is intended to encompass values within about 0.2 mol% when measuring final articles as compared to the as-batched compositions provided herein.
  • the terms "bulk,” “bulk composition” and/or “overall compositions” are intended to include the overall composition of the entire article, which may be differentiated from a “local composition” or “localized composition” which may differ from the bulk composition owing to the formation of crystalline and/or ceramic phases.
  • the terms “article,” “glass-article,” “ceramic-article,” “glass- ceramics,” “glass elements,” “glass-ceramic article” and “glass-ceramic articles” may be used interchangeably, and in their broadest sense, to include any object made wholly or partly of glass and/or glass-ceramic material.
  • a “glass state” refers to an inorganic amorphous phase material within the articles of the disclosure that is a product of fusion that has cooled to a rigid condition without crystallizing.
  • a “glass-ceramic state” refers to an inorganic material within the articles of the disclosure which includes both the glass state and a "crystalline phase” and/or “crystalline precipitates” as described herein.
  • CTE coefficients of thermal expansion
  • transmission and transmittance refer to external transmission or transmittance, which takes absorption, scattering and reflection into consideration. Fresnel reflection is not factored out of the transmission and transmittance values reported herein.
  • optical density units As used herein, "optical density units”, “OD” and “OD units” are used
  • OD/mm or "OD/cm” used in this disclosure are normalized measures of absorbance, as determined by dividing the optical density units (i.e., as measured by an optical spectrometer) by the thickness of the sample (e.g., in units of millimeters or centimeters).
  • any optical density units referenced over a particular wavelength range e.g., 3.3 OD/mm to 24.0 OD/mm in UV wavelengths from 280 nm to 380 nm
  • any optical density units referenced over a particular wavelength range e.g., 3.3 OD/mm to 24.0 OD/mm in UV wavelengths from 280 nm to 380 nm
  • haze refers to the percentage of transmitted light scattered outside an angular cone of ⁇ 2.5° in a sample having a transmission path of about 1 mm and measured in accordance with ASTM procedure D1003.
  • cadmium and selenium-free glass-ceramic is indicative of a glass or a glass-ceramic that is completely free, or substantially free (i.e., ⁇ 500 ppm), of the listed constituent s) and is prepared such that the listed constituent(s) are not actively, intentionally or purposefully added or batched into the glass or glass-ceramic.
  • compressive stress and depth of compression are measured by evaluating surface stress using commercially available instruments, such as the scattered light polariscope SCALP220 and accompanying software version 5 manufactured by GlasStress, Ltd. (Tallinn, Estonia), or the FSM-6000, manufactured by Orihara Co., Lt. (Tokyo, Japan), unless otherwise noted herein. Both instruments measure optical retardation which must be converted to stress via the stress optic coefficient (“SOC”) of the material being tested. Thus, stress measurements rely upon the accurate measurement of the SOC, which is related to the birefringence of the glass.
  • SOC stress optic coefficient
  • the modified Procedure C includes using a glass or glass-ceramic disc as the specimen having a thickness of 5 to 10 mm and a diameter of 12.7 mm. The disc is isotropic and homogeneous, and is core-drilled with both faces polished and parallel.
  • the modified Procedure C also includes calculating the maximum force, Fmax, to be applied to the disc. The force should be sufficient to produce at least 20 MPa compression stress. Fmax is calculated using the equation:
  • Fmax is the maximum force (N)
  • D is the diameter of the disc (mm)
  • h is the thickness of the light path (mm).
  • F is the force (N)
  • D is the diameter of the disc (mm)
  • h is the thickness of the light path (mm).
  • the terms “sharp cutoff wavelength” and “cutoff wavelength” are used interchangeably and refer to a cutoff wavelength within a range of about 350 nm to 800 nm in which the glass-ceramic has a substantially higher transmittance above the cutoff wavelength c) in comparison to its transmittance below the cutoff wavelength ( c).
  • the cutoff wavelength c) is the wavelength at the midpoint between an "absorption limit wavelength” and a “high transmittance limit wavelength” in the given spectra for the glass- ceramic.
  • the “absorption limit wavelength” is specified as the wavelength in which the transmittance is 5%; and in the "high transmittance wavelength” is defined as the wavelength in which the transmittance is 72%.
  • a “sharp UV cutoff as used herein may be a sharp cutoff wavelength of cutoff wavelength as described above which occurs within the ultraviolet band of the electromagnetic spectrum.
  • Articles of the present disclosure are composed of glass and/or glass-ceramics having one or more of the compositions outlined herein.
  • the article can be employed in any number of applications.
  • the article can be employed in the form of substrates, elements, lenses, covers and/or other elements in any number of optics related and/or aesthetic applications.
  • the article is formed from an as-batched composition and is cast in a glass state.
  • the article may later be annealed and/or thermally processed (e.g., heat treated) to form a glass- ceramic state having a plurality of ceramic or crystalline particles. It will be understood that depending on the casting technique employed, the article may readily crystalize and become a glass-ceramic without additional heat treatment (e.g., essentially be cast into the glass- ceramic state). In examples where a post-forming thermal processing is employed, a portion, a majority, substantially all or all of the article may be converted from the glass state to the glass-ceramic state.
  • compositions of the article may be described in connection with the glass state and/or the glass-ceramic state, the bulk composition of the article may remain substantially unaltered when converted between the glass and glass- ceramic states, despite localized portions of the article have different compositions (i.e., owing to the formation of the ceramic or crystalline precipitates).
  • the article may include AI2O3, S1O2, B2O3, WO3,
  • R2O where R2O is one or more of L12O, Na20, K2O, Rb20 and CS2O, RO where RO is one or more of MgO, CaO, SrO, BaO and ZnO and a number of dopants. It will be understood that a number of other constituents (e.g., F, As, Sb, Ti, P, Ce, Eu, La, CI, Br, etc.) without departing from the teachings provided herein.
  • other constituents e.g., F, As, Sb, Ti, P, Ce, Eu, La, CI, Br, etc.
  • the article may include S1O2 from about 58.8 mol% to about 77.58 mol%, AI2O3 from about 0.66 mol% to about 13.69 mol%, B2O3 from about 4.42 mol% to about 27 mol%, R2O from about 0 mol% to about 13.84 mol%, RO from about 0 mol% to about 0.98 mol%, WO3 from about 1.0 mol% to about 13.24 mol% and Sn02 from about 0 mol% to about 0.4 mol%.
  • Such examples of the article may be generally related to Examples 1-109 of Table 1.
  • the article may include S1O2 from about 65.43 mol% to about 66.7 mol%, AI2O3 from about 9.6 mol% to about 9.98 mol%, B2O3 from about 9.41 mol% to about 10.56 mol%, R2O from about 6.47 mol% to about 9.51 mol%, RO from about 0.96 mol% to about 3.85 mol%, WO3 from about 1.92 mol% to about 3.85 mol%, M0O3 from about 0 mol% to about 1.92 mol% and Sn02 from about 0 mol% to about 0.1 mol%.
  • Such examples of the article may be generally related to Examples 110-122 of Table 2.
  • the article may include S1O2 from about 60.15 mol% to about 67.29 mol%, AI2O3 from about 9.0 mol% to about 13.96 mol%, B2O3 from about 4.69 mol% to about 20 mol%, R2O from about 2.99 mol% to about 12.15 mol%, RO from about 0.00 mol% to about 0.14 mol%, WO3 from about 0 mol% to about 7.03 mol%, M0O3 from about 0 mol% to about 8.18 mol%, Sn0 2 from about 0.05 mol% to about 0.15 mol% and V2O5 from about 0 mol% to about 0.34 mol%.
  • Such examples of the article may be generally related to Examples 123-157 of Table 3.
  • the article may include S1O2 from about 54.01 mol% to about 67.66 mol%, AI2O3 from about 9.55 mol% to about 1 1.42 mol%, B2O3 from about 9.36 mol% to about 15.34 mol%, R2O from about 9.79 mol% to about 13.72 mol%, RO from about 0.00 mol% to about 0.22 mol%, WO3 from about 1.74 mol% to about 4.48 mol%, M0O3 from about 0 mol% to about 1.91 mol%, Sn0 2 from about 0.0 mol% to about 0.21 mol%, V2O5 from about 0 mol% to about 0.03 mol%, Ag from about 0 mol% to about 0.48 mol% and Au from about 0 mol% to about 0.01 mol%.
  • Such examples of the article may be generally related to Examples 158-31 1 of Table 4.
  • the article may include S1O2 from about 60.01 mol% to about 77.94 mol%, AI2O3 from about 0.3 mol% to about 10.00 mol%, B2O3 from about 10 mol% to about 20 mol%, R2O from about 0.66 mol% to about 10 mol%, WO3 from about 1.0 mol% to about 6.6 mol% and Sn0 2 from about 0.0 mol% to about 0.1 mol%.
  • Such examples of the article may be generally related to Examples 312-328 of Table 5.
  • the article may have from about 1 mol% to about 99 mol% S1O2, or from about 1 mol% to about 95 mol% S1O2, or from about 45 mol% to about 80 mol% S1O2, or from about 60 mol% to about 99 mol% S1O2, or from about 61 mol% to about 99 mol% S1O2, or from about 30 mol% to about 99 mol% S1O2, or from about 58 mol% to about 78 mol% S1O2, or from about 55 mol% to about 75 mol% S1O2, or from about 50 mol% to about 75 mol% S1O2, or from about 54 mol% to about 68 mol% S1O2, or from about 60 mol% to about 78 mol% S1O2, or from about 65 mol% to about 67 mol% S1O2, or from about 60 mol% to about 68 mol% S1O2, or from about 56 mol% to about 72 mol% S1O2, or from about
  • the article may include from about 0 mol% to about 50 mol% AI2O3, or from about
  • AI2O3 may function as a conditional network former and contributes to a stable article with low CTE, article rigidity, and to facilitate melting and/or forming.
  • the article may include WO3 and/or M0O3.
  • WO3 plus M0O3 may be from about 0.35 mol% to about 30 mol%.
  • M0O3 may be about 0 mol% and WO3 is from about 1.0 mol% to about 20 mol%, or M0O3 may be about 0 mol% and WO3 is from about 1.0 mol% to about 14 mol%, or M0O3 is from about 0 mol% to about 8.2 mol% and WO3 is from about 0 mol% to about 16 mol%, or M0O3 is from about 0 mol% to about 8.2 mol% and WO3 is from about 0 mol% to about 9 mol%, or M0O3 is from about 1.9 mol% to about 12.1 mol% and WO3 is from about 1.7 mol% to about 12 mol%, or M0O3 is from about 0 mol% to about 8.2 mol% and WO3 is from about 0 1.9
  • the glass composition may have from about 0.35 mol% to about 30 mol% M0O3, or from about 1 mol% to about 30 mol% M0O3, or from about 0.9 mol% to about 30% M0O3, or from about 0.9 mol% to about 20% M0O3, or from about 0 mol% to about 1.0 mol% M0O3, or from about 0 mol% to about 0.2 mol% M0O3.
  • the glass composition may have from about 0.35 mol% to about 30 mol% WO3, or from about 1 mol% to about 30 mol% WO3, or from about 1 mol% to about 17 mol% WO3, or from about 1.9 mol% to about 10 mol% WO3, or from about 0.35 mol% to about 1 mol% WO3, or from about 1.9 mol% to about 3.9 mol% WO3, or from about 2 mol% to about 15 mol% WO3, or from about 4 mol% to about 10 mol% of WO3, or from about 5 mol% to about 7 mol% WO3. It will be understood that any and all values and ranges between the above noted ranges of WO3 and/or M0O3 are contemplated.
  • the article may include from about 2 mol% to about 40 mol% of B2O3, or from about
  • B2O3 may be a glass-forming oxide that is used to reduce CTE, density, and viscosity making the article easier to melt and form at low temperatures.
  • the article may include at least one alkali metal oxide.
  • the alkali metal oxide may be represented by the chemical formula R2O where R2O is one or more of L12O, Na20, K2O, Rb20, CS2O and/or combinations thereof.
  • the article may have an alkali metal oxide composition of from about 0.1 mol% to about 50 mol% R2O, or from about 0 mol% to about 14 mol% R2O, or from about 3 mol% to about 14 mol% R2O, or from about 5 mol% to about 14 mol% R2O, or from about 6.4 mol% to about 9.6 mol% R2O, or from about 2.9 mol% to about 12.2 mol% R2O, or from about 9.7 mol% to about 12.8 mol% R2O, or from about 0.6 mol% to about 10 mol% R2O, or from about 0 mol% to about 15 mol% R2O, or from about 3 mol% to about 12 mol% R2O, or from about 7 mol% to about 10 mol% R2O.
  • Alkali oxides e.g., L12O, Na20, K2O, Rb20, and CS2O
  • Alkali oxides may be incorporated into the article for multiple reasons including: (i) reducing the melting temperature, (ii) increasing formability, (iii) enabling chemical strengthening by ion exchange and/or (iv) as a specie to partition into certain crystallites.
  • R2O minus AI2O3 ranges from about from about -35 mol% to about 7 mol%, or from about -12 mol% to about 2.5 mol%, or from about -6% to about 0.25%, or from about -3.0 mol% to about 0 mol%. It will be understood that any and all values and ranges between the above noted ranges of R2O minus AI2O3 are contemplated.
  • the article may include at least one alkaline earth metal oxide.
  • the alkaline earth metal oxide may be represented by the chemical formula RO where RO is one or more of MgO, CaO, SrO, BaO and ZnO.
  • the article may include RO from about 0.02 mol% to about 50 mol% RO, or from about 0.01 mol% to about 5 mol% RO, or from about 0.02 mol% to about 5 mol% RO, or from about 0.05 mol% to about 10 mol% RO, or from about 0.10 mol% to about 5 mol% RO, or from about 0.15 mol% to about 5 mol% RO, or from about 0.05 mol% to about 1 mol% RO, or from about 0.5 mol% to about 4.5 mol% RO, or from about 0 mol% to about 1 mol% RO, or from about 0.96 mol% to about 3.9 mol% RO, or from about 0.2 mol% to about 2 mol% RO, or from about 0.01 mol% to about 0.5 mol
  • R2O may be greater than RO.
  • the article may be free of RO.
  • Alkaline earth oxides e.g., MgO, CaO, SrO, and BaO
  • other divalent oxides such as ZnO may improve the melting behavior of the article and can also act to increase CTE, Young's modulus, and shear modulus of the article.
  • the article may include from about 0.01 mol% to about 5 mol% of Sn0 2 , or from about 0.01 mol% to about 0.5 mol% of Sn0 2 , or from about 0.05 mol% to about 0.5 mol% Sn0 2 , or from about 0.05 mol% to about 2 mol% Sn0 2 , or from about 0.04 mol% to about 0.4 mol% Sn0 2 , or from about 0.01 mol% to about 0.4 mol% Sn0 2 , or from about 0.04 mol% to about 0.16 mol% Sn0 2 , or from about 0.01 mol% to about 0.21 mol% Sn0 2 , or from about 0 mol% to about 0.2 mol% Sn0 2 , or from about 0 mol% to about 0.1 mol% Sn0 2 .
  • the article may also include Sn0 2 as a fining agent (e.g., other fining agents may include Ce0 2 , AS2O3, Sb 2 0 3 , C1-, F- or the like) in small concentrations to aid in the elimination of gaseous inclusions during melting.
  • Certain fining agents may also act as redox couples, color centers, and or species that nucleate and or intercalate into crystallites formed in the article.
  • composition of certain constituents of the article may depend on the presence and/or composition of other constituents.
  • the article further includes Fe 2 0 3 of about 0.9 mol% or less or S1O2 is from about 60 mol% to about 99 mol%.
  • the article includes Sn0 2 from about 0.01 mol% to about 5.0 mol%.
  • Mo0 3 is from about 1 mol% to about 30 mol%
  • S1O2 is from about 61 mol% to about 99 mol% or Fe 2 0 3 is about 0.4 mol% or less and R2O is greater than RO.
  • Mo0 3 is from about 0.9 mol% to about 30% and S1O2 is from about 30 mol% to about 99 mol%
  • the article includes Sn0 2 from about 0.01 mol% to about 5 mol%.
  • the article may be substantially cadmium and substantially selenium free.
  • the article can further include at least one dopant selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, Se, Ta, Bi, Ag, Ce, Pr, Nd, and Er to alter the ultraviolet, visual, color and/or near-infrared absorbance.
  • the dopants may have concentration of from about 0.0001 mol% to about 1.0 mol% within the article.
  • the article may include at least one of Ag from about 0.01 mol% to about 0.48 mol%, Au from about 0.01 mol% to about 0.13 mol%, V2O5 from about 0.01 mol% to about 0.03 mol%, Fe 2 0 3 from about 0 mol% to about 0.2 mol%, Fe 2 03 from about 0 mol% to about 0.2 mol%, and CuO from about 0.01 mol% to about 0.48 mol%.
  • the article may include at least one of Ag from about 0.01 mol% to about 0.75 mol%, Au from about 0.01 mol% to about 0.5 mol%, V2O5 from about 0.01 mol% to about 0.03 mol%, and CuO from about 0.01 mol% to about 0.75 mol%.
  • the article may include fluorine in the range of about 0 mol% to about 5 mol% to soften the glass.
  • the article may include phosphorus from about 0 mol% to about 5 mol% to further modify physical properties of the article and modulate crystal growth.
  • the article may include Ga 2 0 3 , ln 2 0 3 and/or Ge0 2 to further modify physical and optical (e.g., refractive index) properties of the article.
  • the following trace impurities may be present in the range of about 0.001 mol% to about 0.5 mol% to further modify the ultraviolet, visible (e.g., 390 nm to about 700 nm), and near-infrared (e,g., about 700 nm to about 2500 nm) absorbance and/or make the article fluoresce: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Te, Ta, Re, Os, Ir, Pt, Au, Ti, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Further, small additions of P2O5 may be made to certain compositions to further modify the physical properties and viscosity of the article.
  • S1O2, Al 2 03, W0 3 , Mo0 3 , WO3 plus Mo0 3 , B 2 0 3 , R2O, RO, V2O5, Ag, Au, CuO, Sn0 2 , and dopants may be used with any other composition and/or composition range of the other constituents of the article as outlined herein.
  • tungsten-molybdenum containing alkali glasses has been hampered by the separation of the melt constituents during the melting process.
  • the separation of the glass constituents during the melting process resulted in a perceived solubility limit of alkali tungstate within the molten glass, and therefore of articles cast from such melts.
  • the melted borosilicate glass formed both a glass and a dense liquid second phase.
  • the concentration of the alkali tungstate second phase could be reduced by thorough mixing, melting at a high temperature, and employing a small batch size ( ⁇ 1000 g), it could not be fully eliminated leading to a deleterious second crystalline phase forming. It is believed that the formation of this alkali tungstate phase occurs in the initial stages of the melt, where tungsten and/or molybdenum oxide reacts with "free" or "unbound” alkali carbonates. Due to the high density of alkali tungstate and/or alkali molybdate relative to the borosilicate glass that is formed, it rapidly segregates and/or stratifies, pooling at the bottom of the crucible and does not rapidly solubilize in the glass due to the significant difference in density. As the R2O constituents may provide beneficial properties to the glass composition, simply decreasing the presence of the R2O constituents within the melt may not be desirable.
  • a homogenous single-phase W or Mo-containing peralkaline melt may be obtained through the use of "bound” alkalis.
  • bound alkalis are alkali elements which are bonded to alumina, bona and/or silica while “free” or “unbound” alkalis are alkali carbonates, alkali nitrates and/or alkali sulfates in which the alkali are not bound to silica, boria or alumina.
  • Exemplary bound alkalis may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali-alumino-silicates, alkali silicates and/or other naturally occurring and artificially created minerals containing an alkali and one or more aluminum, boron and/or silicon atoms.
  • the alkalis may not react with the W or Mo present in the melt to form the dense alkali tungstate and/or alkali molybdate liquid.
  • This has also allowed melt temperature and mixing method to be varied and still produce a single- phase homogenous glass. It will be understood that as the alkali tungstate phase and the borosilicate glass are not completely immiscible, prolonged stirring may also allow mixing of the two phases to cast a single phase article.
  • the article may be annealed, heat treated or otherwise thermally processed to form the crystalline phase within the article. Accordingly, the article may be transformed from the glass state to the glass- ceramic state.
  • the crystalline phase of the glass-ceramic state may take a variety of morphologies. According to various examples, the crystalline phase is formed as a plurality of precipitates within the heat treated region of the article. As such, the precipitates may have a generally crystalline structure.
  • a crystalline phase refers to an inorganic material within the articles of the disclosure that is a solid composed of atoms, ions or molecules arranged in a pattern that is periodic in three dimensions.
  • a crystalline phase as referenced in this disclosure, unless expressly noted otherwise, is determined to be present using the following method. First, powder x-ray diffraction ("XRD”) is employed to detect the presence of crystalline precipitates. Second, Raman spectroscopy (“Raman”) is employed to detect the presence of crystalline precipitates in the event that XRD is unsuccessful (e.g., due to size, quantity and/or chemistry of the precipitates).
  • XRD powder x-ray diffraction
  • Raman spectroscopy Raman spectroscopy
  • TEM transmission electron microscopy
  • the quantity and/or size of the precipitates may be low enough that visual confirmation of the precipitates proves particularly difficult.
  • the larger sample size of XRD and Raman may be advantageous in sampling a greater quantity of material to determine the presence of the precipitates.
  • the crystalline precipitates may have a generally rod-like or needle-like morphology.
  • the precipitates may have a longest length dimension of from about 1 nm to about 500 nm, or from about 1 nm to about 400 nm, or from about 1 nm to about 300 nm, or from about 1 nm to about 250 nm, or from about 1 nm to about 200 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about 75 nm, or from about 1 nm to about 50 nm, or from about 1 nm to about 25 nm or from about 1 nm to about 20 nm or from about 1 nm to about 10 nm.
  • the size of the precipitates may be measured using Electron Microscopy.
  • the term "Electron Microscopy” means visually measuring the longest length of the precipitates first by using a scanning electron microscope, and if unable to resolve the precipitates, next using a transmission electron microscope.
  • the crystalline precipitates may generally have a rod-like or needle-like morphology
  • the precipitates may have a width of from about 2 nm to about 30 nm, or from about 2 nm to about 10 nm or from about 2 nm to about 7 nm. It will be understood that the size and/or morphology of the precipitates may be uniform, substantially uniform or may vary.
  • peraluminous compositions of the article may produce precipitates having a needle-like shape with a length of from about 100 nm to about 250 nm and a width of from about 5 nm to about 30 nm.
  • compositions of the article may produce needle-like precipitates having a length of from about 10 nm to about 30 nm and a width of from about 2 nm to about 7 nm.
  • Ag, Au and/or Cu containing examples of the article may produce rod-like precipitates having a length of from about 2 nm to about 20 nm and a width, or diameter, of from about 2 nm to about 10 nm.
  • a volume fraction of the crystalline phase in the article may range from about 0.001% to about 20%, or from about 0.001% to about 15%, or from about 0.001% to about 10% or from about 0.001% to about 5%, or from about 0.001% to about 1%.
  • the relatively small size of the precipitates may be advantageous in reducing the amount of light scattered by the precipitates leading to high optical clarity of the article when in the glass-ceramic state.
  • the size and/or quantity of the precipitates may be varied across the article such that different portions of the article may have different optical properties. For example, portions of the article where the precipitates are present may lead to changes in the absorbance, color, reflectance and/or transmission of light, as well as the refractive index as compared to portions of the article where different precipitates (e.g., size and/or quantity) and/or no precipitates are present.
  • the precipitates may be composed of tungsten oxide and/or molybdenum oxide.
  • the crystalline phase includes an oxide, from about 0.1 mol% to about 100 mol% of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.
  • thermal processing e.g., heat treating
  • tungsten and/or molybdenum cations agglomerate to form crystalline precipitates thereby transforming the glass state into the glass-ceramic state.
  • the molybdenum and/or tungsten present in the precipitates may be reduced, or partially reduced.
  • the molybdenum and/or tungsten within the precipitates may have an oxidation state of between 0 and about +6.
  • the molybdenum and/or tungsten may have a +6 oxidation state.
  • the precipitates may have the general chemical structure of WCb and/or MoCb.
  • tungsten and or molybdenum in the +5 oxidation state there can also be a significant fraction of tungsten and or molybdenum in the +5 oxidation state and the precipitates may be known as non-stoichiometric tungsten suboxides, non- stoichiometric molybdenum suboxides, "molybdenum bronzes" and/or "tungsten bronzes.”
  • One or more of the above-noted alkali metals and/or dopants may be present within the precipitates to compensate the +5 charge on the W or Mo.
  • MxWCb and MxMoCb are considered to be a solid state defect structure in which holes (i.e.
  • vacancies or channels in crystal lattice) in a reduced WCb or MoCb network are randomly occupied by M atoms, which are dissociated into M+ cations and free electrons.
  • M concentration of "M”
  • the material properties can range from metallic to semi-conducting, thereby allowing a variety of optical absorption and electronic properties to be tuned.
  • Tungsten bronzes are non-stoichiometric compounds generally of formula MxWCb, where M is a cation dopant, such as some other metal, most commonly an alkali, and x is a variable less than 1. For clarity, though called a 'bronze', these compounds are not structurally or chemically related to metallic bronze, which is an alloy of copper and tin. Tungsten bronzes are a spectrum of solid phases where homogeneity varies as a function of x. Depending on dopant M and corresponding concentration x, material properties of a tungsten bronze may range from metallic to semi-conducting, and exhibit tunable optical absorption. The structure of these bronzes is a solid-state defect structure in which M' cations intercalate into holes or channels of binary oxide hosts and disassociate into M+ cations and free electrons.
  • MxWCb is a naming convention for a complex system of non- stoichiometric or 'sub-stoichiometric' compounds, with varying crystal structures that can be hexagonal, tetragonal, cubic, or pyrochlore, where M can one or a combination of certain elements on the periodic table, where x varies from 0 ⁇ x ⁇ 1, where the oxidation state of the bronze forming specie (in this case W) is a mixture of the specie in its highest oxidation state (W 6+ ) and a lower oxidation state (e.g., W 5+ ), and where the number three ("3") in WCb represents the number of oxygen anions that may be between 2 and 3 .
  • MxWCb may alternatively be expressed as the chemical form MxWOz, where 0 ⁇ x ⁇ 1, and 2 ⁇ z ⁇ 3, or as MxWCb-z where 0 ⁇ x ⁇ 1 and 0 ⁇ z ⁇ 1.
  • MxWCb is utilized for this family of non-stoichiometric crystals.
  • 'bronze' in general applies to a ternary metal oxide of formula M' x M" y Oz where (i) M" is a transition metal, (ii) M" y O z is its highest binary oxide, (iii) M' is some other metal, (iv) x is a variable falling in the range 0 ⁇ x ⁇ 1.
  • a portion, a majority, substantially all or all of the article may be thermally processed to form the precipitates.
  • Thermal processing techniques may include, but are not limited to, a furnace (e.g., a heat treating furnace), a microwave, a laser and/or other techniques of locally and/or bulk heating of the article.
  • the crystalline precipitates While undergoing thermal processing, the crystalline precipitates internally nucleate within the article in a homogenous manner where the article is thermally processed to transform the glass state into the glass-ceramic state.
  • the article may include both the glass state and the glass-ceramic state.
  • the precipitates may homogenously form throughout the article.
  • the precipitates may exist from an exterior surface of the article throughout the bulk of the article (i.e., greater than about 10 ⁇ from the surface).
  • the precipitates may only be present where the thermal processing reaches a sufficient temperature (e.g., at the surface and into the bulk of the article proximate the heat source).
  • the article may undergo more than one thermal processing to produce the precipitates.
  • thermal processing may be utilized to remove and/or alter precipitates which have already been formed (e.g., as a result of previous thermal processing). For example, thermal processing may result in the decomposition of precipitates.
  • the article may be optically transparent in the visible region of the electromagnetic spectrum (i.e., from about 400 nm to about 700 nm) both where the precipitates are present and where the precipitates are not present (i.e., in portions which are in the glass state or the glass-ceramic state).
  • the term "optically transparent” refers to a transmittance of greater than about 1% over a 1 mm path length (e.g., in units of %/mm) over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
  • the article has a transmittance of about 5%/mm or greater, about 10%/mm or greater, about 15%/mm or greater, about 20%/mm or greater, about 25%/mm or greater, about 30%/mm or greater, about 40%/mm or greater, about 50%/mm or greater, about 60%/mm or greater, about 70%/mm or greater, about 80%/mm or greater and greater than all lower limits between these values, all over at least one 50 nm-wide wavelength band of light in the visible region of the spectrum.
  • the glass-ceramic state of the article absorbs light in the ultraviolet ("UV") region (i.e., wavelengths of less than about 400 nm) based on the presence of the precipitates without the use of additional coatings or films.
  • UV ultraviolet
  • the glass-ceramic state of the article is characterized by a transmittance of less than 10%/mm, less than 9%/mm, less than 8%/mm, less than 7%/mm, less than 6%/mm, less than 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, and even less than 1%/mm, for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum (e.g., about 200 nm to about 400 nm).
  • the glass-ceramic state absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or even at least 99%/mm for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum.
  • the glass-ceramic state may have a sharp UV cutoff wavelength from about 320 nm to about 420 nm.
  • the glass-ceramic state may have a sharp UV cutoff at about 320 nm, about 330 nm, about 340 nm, about 350 nm, about 360 nm, about 370 nm, about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm or any value therebetween.
  • the glass-ceramic state of the article has a transmittance of greater than about 5%/mm, greater than about 10%/mm, greater than about 15%/mm, greater than about 20%/mm, greater than about 25%/mm, greater than about 30%/mm, greater than about 40%/mm, greater than about 50%/mm, greater than about 60%/mm, greater than about 70%/mm, greater than about 80%/mm, greater than about 90%/mm and greater than all lower limits between these values, all over at least one 50 nm-wide wavelength band of light in the near-infrared region (NIR) of the spectrum (e.g., from about 700 nm to about 2700 nm).
  • NIR near-infrared region
  • the glass-ceramic state of the article has a transmittance of less than about 90%/mm, less than about 80%/mm, less than about 70%/mm, less than about 60%/mm, less than about 50%/mm, less than about 40%/mm, less than about 30%/mm, less than about 25%/mm, less than about 20%/mm, less than about 15%/mm, less than about 10%/mm, less than about 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, less than 1%/mm and even less than 0.1%/mm and less than all upper limits between these values, all over at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum.
  • the glass-ceramic state of the article absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or at least 99%/mm, or even at least 99.9%/mm for light in at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum.
  • compositions may exhibit a low coefficient of thermal expansion ("CTE").
  • CTE coefficient of thermal expansion
  • the article may have a coefficient of thermal expansion of from about lOxlO "7 °C _1 and about 60xl0 "7 °C _1 over a temperature range of from about 0° C to about 300° C.
  • Such a low CTE may allow the article to withstand large and rapid fluctuations in temperature, making such articles suitable for operating in harsh environments.
  • the article may exhibit a less than 1% transmittance at wavelengths of about 368 nm or less, optical transparency in the visible regime (e.g., from about 500 nm to about 700 nm), and strong attenuation (e.g., blocking) of NIR wavelengths (e.g., from about 700 nm to about 1700 nm).
  • Such articles may be advantageous over conventional NIR management solutions in that the article does not employ a coating or film (e.g., which may be
  • the article As the article is impervious to oxygen, moisture, and ultraviolet wavelengths (i.e., owing to its glass or glass-ceramic nature), the NIR absorbing precipitates may be protected from harsh environmental conditions (e.g., moisture, caustic acids, bases and gases) and rapid changes in temperature. Further, a UV cutoff wavelength and a refractive index change of the glass-ceramic state of the article may be modulatable by thermal treatment post forming. The glass-ceramic state of the article may exhibit a UV cutoff or a change in its refractive index as a result of its crystalline precipitates.
  • the glass state of the article may have a refractive index of about between about 1.505 and about 1.508 while the glass-ceramic state of the article may have a refractive index of from about 1.520 to about 1.522.
  • the thermally modulatable UV cutoff and refractive index may enable one tank of glass to meet multiple UV cutoff glass specifications on the fly by varying the thermal processing conditions post forming of the article.
  • the thermally modulated refractive index can produce a large refractive index delta (10 "2 ). Because the thermal treatment required to modulate the UV absorbance is done at high viscosity (e.g., between 10 8 and 10 12 poise) finished articles can be thermally processed without marring the surface or causing deformation.
  • compositions may offer a novel family of non-toxic, cadmium and selenium-free articles that exhibit an optical extinction with a sharp and tunable cutoff wavelength. Unlike the Cd-free alternatives to CdSe filter glasses, which contain Se, these articles contain no Resource and Recovery Act ("RCRA") metals or other harmful agents. Additionally, the article may be composed of lower cost elements, unlike the Cd-free alternatives that contain indium and or gallium. With respect to optical properties, articles made of these compositions may offer high transparency (e.g., greater than about 90%) over the NIR out to 2.7 microns.
  • RCRA Resource and Recovery Act
  • the article may exhibit a sharp visible cutoff wavelength ranging from about 320 nm to 525 nm, which is tunable by thermal processing conditions (e.g., time and temperature), and by composition.
  • thermal processing conditions e.g., time and temperature
  • articles of these exemplary compositions may use molybdenum in lieu of tungsten which may be advantageous in that molybdenum is generally less expensive than tungsten.
  • articles made of these compositions may be thermally processed into the glass-ceramic state which may offer a variety of optical properties.
  • the transmittance of the article of such compositions can range from about 4% to about 30% in the visible spectrum (e.g., about 400 nm to about 700 nm), about 5% to about 15% in the NIR (e.g., about 700 nm to about 1500 nm), a UV transmittance of about 1% or less at wavelengths below about 370 nm and about 5% or less at wavelengths of from about 370 nm to about 390 nm.
  • mixed molybdenum-tungsten examples of the article are capable of absorbing 92.3% of the solar spectrum. Such optical properties may be visually perceived as a tint to the article.
  • the optical properties are generated via the growth of the precipitates and as such the tint may be varied across the article based on thermal processing.
  • This thermally variable tint can be used to create gradients of tint within the article such as the creation of shaded edges or boarders within windshield or moonroof applications of the article. Such a feature may be advantageous in the elimination of frits which are baked onto the surface of conventional windshields and moonroofs.
  • This thermally tunable tint can also be used to create a gradient absorption across the article.
  • articles created from these compositions are bleachable and patternable by lasers (e.g., operating at wavelengths of 355 nm, 810 nm, and 10.6 ⁇ ).
  • the exposed region of the article Upon laser exposure to these wavelengths, the exposed region of the article will turn from a blue or grey color (e.g., the color being due to the precipitates) to a transparent water white or faint yellow-tint due to the thermal decomposition of the UV and NIR absorbing precipitates.
  • rastering the laser along the surface of the article to selectively bleach desired regions patterns can be created within the article.
  • the resulting glass state is no longer absorptive in the NIR such that the bleaching process is self-limiting (i.e., because the NIR absorbing precipitates have been decomposed).
  • selective laser exposure may not only create patterns, but also variable UV & NIR absorbance across the article.
  • the article may be pulverized to a sufficiently small size and functionalized to be used as a photothermal susceptor agent for cancer treatment (i.e., due to its NIR absorbing optical properties).
  • articles made of these compositions may be capable of being thermally treated after formation (e.g., to form the glass-ceramic state) to both modulate the optical absorbance and to produce a large range of colors from a single composition. Further, such examples may be capable of fusion formation and/or ion- exchanging.
  • Conventional colored glass compositions which utilize Ag, Au and/or Cu generally rely on the formation of nanoscale metallic precipitates to generate colors. As discovered by the inventors of the present disclosure, Ag 1+ cations can intercalate into tungsten and molybdenum oxide forming silver tungsten bronzes and/or silver molybdenum bronzes which may provide the article with a polychromatic nature.
  • molybdenum oxide precipitates arising from the concentration of intercalated of alkali cations and Ag 1+ , Au and/or Cu cations into the precipitates to form a pure alkali, pure metal and/or mixed alkali-metal, tungsten and/or molybdenum bronzes of varying stoichiometry. Changes in the band gap energy of the precipitates are due to its stoichiometry and in-turn is largely independent of precipitate size and/or shape.
  • doped MxWCb or MxMoCb precipitates can remain the same size and/or shape, yet could be many different colors depending on the dopant "M" identity and concentration "x.”
  • Thermally treating such articles may produce a nearly complete rainbow of colors within a single article. Further, gradients of color can be stretched or compressed over some physical distance by a thermal gradient being applied to the article.
  • the article can be laser patterned to locally alter the color of the article.
  • Such articles may be advantageous for the production of colored sunglass lens blanks, phone and/or tablet covers and/or other products which may be composed of a glass-ceramic and may be aesthetically colored.
  • the precipitates are positioned within the glass-ceramic, scratch resistance and environmental durability are greater than the conventional metal and polymeric coloring layers applied to provide coloring.
  • the colors of the article may be altered based on thermal treatment, one tank of glass melt may be used to continuously produce blanks that can be heat treated to the specific color as customer demand dictates. Additionally, articles manufactured from these glass compositions may absorb UV and/or IR radiation similar to the other compositions disclosed herein.
  • the article may be amenable to various fusion formation processes.
  • the various compositions of the present disclosure may be utilized in a single or double fusion laminate where a transparent tungsten, molybdenum, mixed tungsten molybdenum, and/or titanium glass is employed as a clad material around a substrate to form the laminate article.
  • the glass state cladding may be transformed to the glass-ceramic state.
  • the glass-ceramic state cladding of the fusion laminate article may have a thickness of from about 50 ⁇ to about 200 ⁇ and may have a strong UV and IR attenuation with high average visible
  • compositions as a cladding to form the article provides a novel process to fully leverage the tunable optical properties while simultaneously producing a strengthened monolithic glass ply.
  • the present disclosure may be powdered or granulated and added to a variety of materials.
  • the powdered article may be added to a paint, binder, polymeric material (e.g., polyvinyl butyral), sol-gels and/or combinations thereof.
  • a paint, binder, polymeric material e.g., polyvinyl butyral
  • sol-gels sol-gels and/or combinations thereof.
  • Such a feature may be advantageous in imparting one or more of the characteristics of the article to the above mentioned material.
  • the article may include T1O2.
  • the article may include
  • T1O2 in a concentration of about 0.25 mol%, or about 0.50 mol%, or about 0.75 mol%, or about 1.0 mol%, or about 2.0 mol%, or about 3.0 mol%, or about 4.0 mol%, or about 5.0 mol%, or about 6.0 mol%, or about 7.0 mol%, or about 8.0 mol%, or about 9.0 mol%, or about 10.0 mol%, or about 11.0 mol%, or about 12.0 mol%, or about 13.0 mol%, or about 14.0 mol%, or about 15.0 mol%, or about 16.0 mol%, or about 17.0 mol%, or about 18.0 mol%, or about 19.0 mol%, or about 20.0 mol%, or about 21.0 mol%, or about 22.0 mol%, or about 23.0 mol%, or about 24.0 mol%, or about 25.0 mol%, or about 26.0 mol%, or about 27.0 mol%, or about 28.0 mol
  • the article may include T1O2 in a concentration of from about 0.25 mol% to about 30 mol%, or from about 1 mol% to about 30 mol% TiCh, or from about 1.0 mol% to about 15 mol% T1O2, or from about 2.0 mol% to about 15 mol% T1O2, or from about 2.0 mol% to about 15.0 mol% T1O2. It will be understood that any and all values and ranges between the above noted ranges of T1O2 are contemplated.
  • the article may include one or more metal sulfides.
  • the metal sulfides may include MgS, Na2S, and/or ZnS.
  • the article may include one or more metal sulfides.
  • the metal sulfides may include MgS, Na2S, and/or ZnS.
  • the article may include metal sulfides in a
  • the examples of the article including titanium may also produce a crystalline phase composed of precipitates of titanium oxide.
  • the crystalline phase includes an oxide, from about 0.1 mol% to about 100 mol% of the crystalline phase, of Ti and an alkali metal cation.
  • titanium cations agglomerate to form crystalline precipitates near and or on the metal sulfides thereby transforming the glass state into the glass-ceramic state.
  • the metal sulfide may serve a dual role in both functioning as a nucleating agent (i.e., as the metal sulfide may have a higher melting temperature than the melt thereby serving as a seed crystal onto which the titanium may agglomerate) and as a reducing agent (i.e., metal sulfides are high reducing agents and as such the agglomerated titanium may be reduced to a 3+ state).
  • the titanium present in the precipitates may be reduced, or partially reduced due to the metal sulfides.
  • the titanium within the precipitates may have an oxidation state of between 0 and about +4.
  • the precipitates may have the general chemical structure of T1O2.
  • Ti 3+ cations may be charge stabilized by species intercalated into channels in the titania crystal lattice, forming compounds known as non-stoichiometric titanium suboxides, "titanium bronzes,” or “bronze-type” titanium crystals.
  • species intercalated into channels in the titania crystal lattice forming compounds known as non-stoichiometric titanium suboxides, "titanium bronzes,” or “bronze-type” titanium crystals.
  • One or more of the above- noted alkali metals and/or dopants may be present within the precipitates to compensate the +3 charge on the Ti.
  • the structure MxTiCh is considered to be a solid state defect structure in which holes (i.e.
  • vacancies or channels in crystal lattice) in a reduced TiCh network are randomly occupied by M atoms, which are dissociated into M+ cations and free electrons.
  • M concentration of "M”
  • the material properties can range from metallic to semiconducting, thereby allowing a variety of optical absorption and electronic properties to be tuned.
  • titanium bronzes are non-stoichiometric
  • M is a cation dopant, such as some other metal, most commonly an alkali
  • x is a variable less than 1.
  • metallic bronze which is an alloy of copper and tin.
  • Titanium bronzes are a spectrum of solid phases where homogeneity varies as a function of x. Depending on dopant M and corresponding concentration x, material properties of a titanium bronze may range from metallic to semiconducting, and exhibit tunable optical absorption.
  • the structure of these bronzes is a solid- state defect structure in which M' dopant cations intercalate (i.e., occupy) into holes or channels of binary oxide hosts and disassociate into M+ cations and free electrons.
  • MxTiC is a naming convention for a complex system of non- stoichiometric or 'sub-stoichiometric' compounds, with varying crystal structures that can be monoclinic, hexagonal, tetragonal, cubic, or pyrochlore, where M can one or a combination of certain elements on the periodic table, where x varies from 0 ⁇ x ⁇ 1, where the oxidation state of the bronze forming specie (in this case Ti) is a mixture of the specie in its highest oxidation state (Ti 4+ ) and a lower oxidation state (e.g., Ti 3+ ), and where the number two ("2") in T1O2 represents the number of oxygen anions that may be between 1 and 2 .
  • MxTiCh may alternatively be expressed as the chemical form MxTiOz, where 0 ⁇ x ⁇ 1, and 1
  • MxTiCh is utilized for this family of non-stoichiometric crystals.
  • 'bronze' in general applies to a ternary metal oxide of formula M' x M" y Oz where (i) M" is a transition metal, (ii) M" y O z is its highest binary oxide, (iii) M' is some other metal, (iv) x is a variable falling in the range 0 ⁇ x
  • the glass-ceramic article including titanium may be substantially free of W, Mo, and rare earth elements.
  • the ability for titanium to form its own suboxides may eliminate the need for tungsten and molybdenum and the titanium suboxides may not need rare earth elements.
  • the glass-ceramic article may have a low
  • the article may include about 1 mol% or less of Fe, or about 0.5 mol% or less of Fe, or about 0.1 mol% or less of Fe, or 0.0 mol% Fe or any and all values and ranges therebetween.
  • the glass-ceramic article may have a low
  • the article may include about 1 mol% or less of Li, or about 0.5 mol% or less of Li, or about 0.1 mol% or less of Li, or 0.0 mol% Li or any and all values and ranges therebetween.
  • the glass-ceramic article may have a low
  • the article may include about 1 mol% or less of Zr, or about 0.5 mol% or less of Zr, or about 0.1 mol% or less of Zr, or 0.0 mol% Zr or any and all values and ranges therebetween.
  • articles including titanium may be formed by a method including steps of: melting together constituents including silica and titanium to form a glass melt; solidifying the glass melt to form a glass; and precipitating, within the glass, bronze-type crystals including the titanium to form the glass-ceramic.
  • the precipitating of the bronze- type crystals may be performed via one or more thermal treatments.
  • the thermal treatment, for titanium bronze-type crystals may be performed at a temperature of from about 400° C to about 900° C, or from about 450° C to about 850° C, or from about 500° C to about 800° C, or from about 500° C to about 750° C, or from about 500° C to about 700° C or any and all values and ranges therebetween.
  • precipitating the bronze-type crystals is performed at a temperature of from about 450° C to about 850° C or precipitating the bronze- type crystals is performed at a temperature of from about 500° C to about 700° C.
  • the thermal treatment may be carried out for a time period of from about 15 minutes to about 240 minutes, or from about 15 minutes to about 180 minutes, or from about 15 minutes to about 120 minutes, or from about 15 minutes or about 90 minutes, or from about 30 minutes to about 90 minutes, or from about 60 minutes to about 90 minutes or any and all values and ranges therebetween.
  • precipitating the bronze-type crystals is performed for a time period of from about 15 minutes to about 240 minutes or precipitating the bronze-type crystals is performed for a time period of from about 60 minutes to about 90 minutes.
  • the thermal treatment may be carried out in ambient air, in an inert atmosphere or in a vacuum.
  • Formation of the titanium suboxides in titanium containing examples of the article may result in a difference in absorption and transmittance of different wavelength bands of light.
  • a ultraviolet (UV) band of light e.g., from about 200 nm to about 400 nm
  • the article in the glass-state, prior to precipitation of the titanium suboxides may have an average UV transmittance of about 18% to about 30%>.
  • the average UV transmittance of the article in the glass-state may be about 18%>, or about 19%, or about 20%, or about 21%, or about 22%, or about 23%, or about 24%, or about 25%, or about 26%, or about 27%, or about 28%o, or about 29%, or about 30% or any and all values and ranges therebetween.
  • the article in the glass-ceramic state may have an average UV transmittance of about 0.4% to about 18%.
  • the average UV transmittance of the article in the glass-ceramic state may be about 0.4%, or about 0.5%, or about 1%), or about 2%, or about 3%, or about 4%, or about 5%, or about 6%, or about 7%, or about 8%), or about 9%, or about 10%, or about 11% or about 12% or about 13% or about 14%) or about 15% or about 16% or about 17% or about 18% or any and all values and ranges therebetween.
  • the above-noted transmittance values may exist in articles having a thickness, or path length of the light, of from about 0.4 mm to about 1.25 mm.
  • the article in the glass-state, prior to precipitation of the titanium suboxides may have an average visible transmittance of about 60% to about 85%.
  • the average visible transmittance of the article in the glass-state may be about 60%, or about 61%, or about 62%, or about 63%, or about 64%), or about 65%, or about 66%, or about 67%, or about 68%, or about 69%, or about 70%, or about 71%, or about 72%, or about 73%, or about 74%, or about 75%, or about 76%, or about 77%, or about 78%, or about 79%, or about 80%, or about 81%, or about 82%, or about 83%, or about 84%> , or about 85%> or any and all values and ranges therebetween.
  • the article in the glass-ceramic state may have an average visible transmittance of about 4% to about 85%>.
  • the average UV transmittance of the article in the glass-ceramic state may be about 4%, or about 5%, or about 10%, or about 20%, or about 30%, or about 40%, or about 50%, or about 60%, or about 70%, or about 80%>, or about 85%> or any and all values and ranges therebetween. It will be understood that the above-noted transmittance values may exist in articles having a thickness, or path length of the light, of from about 0.4 mm to about 1.25 mm.
  • the article in the glass-state, prior to precipitation of the titanium suboxides may have an average NIR transmittance of about 80%> to about 90%.
  • the average NIR transmittance of the article in the glass-state may be about 80%, or about 81%, or about 82%, or about 83%, or about 84%, or about 85%, or about 86%, or about 87%, or about 88%, or about 89%, or about 90% or any and all values and ranges therebetween.
  • the article in the glass-ceramic state may have an average NIR transmittance of about 0.1% to about 10%.
  • the average UV transmittance of the article in the glass-ceramic state may be about 1%, or about 2%, or about 3%), or about 4%, or about 5%, or about 6%, or about 7%, or about 8%, or about 9%, or about 10%) or any and all values and ranges therebetween.
  • the above- noted transmittance values may exist in articles having a thickness, or path length of the light, of from about 0.4 mm to about 1.25 mm.
  • the article in the glass-state may have an average optical density per mm (i.e., a first near-infrared absorbance) of about 0.4 or less, or about 0.35 or less, or about 0.3 or less, or about 0.25 or less, or about 0.2 or less, or about 0.15 or less, or about 0.1 or less, or about 0.05 or less or any and all values and ranges therebetween.
  • a first near-infrared absorbance i.e., a first near-infrared absorbance
  • the article in the glass- ceramic state, with the titanium suboxides may have an optical density per mm (i.e., a second near-infrared absorbance) of about 6.0 or less, or about 5.5 or less, or about 5.0 or less, or about 4.5 or less, or about 4.0 or less, or about 3.5 or less, or about 3.0 or less, or about 2.5 or less, or about 2.0 or less, or about 2.0 or less, or about 1.5 or less, or about 1.0 or less, or about 0.5 or less or any and all values and ranges therebetween.
  • a second near-infrared absorbance i.e., a second near-infrared absorbance
  • a ratio of the second average near-infrared absorbance to the first average near-infrared absorbance may be about 1.5 or greater, or about 2.0 or greater, or about 2.5 or greater, or about 3.0 or greater, or about 5.0 or greater, or about 10.0 or greater.
  • the average optical density per mm at visible wavelengths of the article in the glass-ceramic state with the titanium suboxides may be 1.69 or less.
  • the article may exhibit a low haze.
  • the article may exhibit a haze of about 20% or less, or about 15%> or less, or about 12% or less, or about 11%) or less, or about 10.5% or less, or about 10%> or less, or about 9.5% or less, or about 9%) or less, or about 8.5%> or less, or about 8%> or less, or about 7.5% or less, or about 7%) or less, or about 6.5%> or less, or about 6%> or less, or about 5.5% or less, or about 5% or less, or about 4.5% or less, or about 4% or less, or about 3.5% or less, or about 3% or less, or about 2.5%) or less, or about 2% or less, or about 1.5% or less, or about 1% or less, or about 0.5%) or less, or about 0.4% or less, or about 0.3% or less, or about 0.2% or less, or about 0.1%) or less or any and all values and ranges therebetween.
  • the haze of the article is measured on a 1 mm thick sample and in accordance with the procedure outlined above in connection with haze measurement.
  • the haze of the article may be lower than conventional glass-ceramics due to the absence of beta-quartz (i.e.
  • the glass-ceramic article may be free of a beta-quartz crystalline phase.
  • the haze of the article may be due to the low quantity or absence of large crystallites (e.g., about ⁇ 100 nm, or about ⁇ 60 nm, or about ⁇ 40 nm) which tend to scatter light.
  • large crystallites e.g., about ⁇ 100 nm, or about ⁇ 60 nm, or about ⁇ 40 nm
  • MxTiCte or nonstoichiometric titanium bronzes may provide a number of advantages.
  • thermal processing times to produce titanium suboxides may be shorter than production of other glass-ceramics. Further, thermal processing temperatures may be below the softening points of the article. Such features may be advantageous in decreasing manufacturing complexity and cost.
  • color packages e.g., TiCte + ZnS
  • melt compositions including those with ion exchange capabilities. Additionally, because a relatively low concentration of the color package is needed, the addition of such color packages may have less effect on chemical durability and other relevant properties of the article.
  • articles including the titanium suboxides when molted or in the as-cast state (i.e., green state before thermal treatment), are highly transparent at visible and NIR wavelengths, unlike Fe 2+ - doped glasses, which strongly absorb in the near infrared even when molten.
  • the article may have S1O2 from about 58.8 mol% to about
  • AI2O3 from about 0.66 mol% to about 13.69 mol%
  • B2O3 from about 4.42 mol% to about 27 mol%
  • R2O from about 0 mol% to about 13.84 mol%
  • RO from about 0 mol% to about 0.98 mol%
  • WO3 from about 1.0 mol% to about 13.24 mol%
  • Sn02 from about 0 mol% to about 0.4 mol%.
  • any of the exemplary compositions of Table 1 may include MnC from about 0 mol% to about 0.2 mol%, Fe2Cb from about 0 mol% to about 0.1 mol%, T1O2 from about 0 mol% to about 0.01 mol%, AS2O5 from about 0 mol% to about 0.17 mol% and/or EmCb from about 0 mol% to about 0.1 mol%.
  • the compositions of Table 1 are provided in an as-batched state within a crucible.
  • the article may have S1O2 from about 65.43 mol% to about
  • compositions of Table 2 are provided in an as-batched state within a crucible.
  • the article may have S1O2 from about 60.15 mol% to about
  • AI2O3 from about 9.0 mol% to about 13.96 mol%
  • B2O3 from about 4.69 mol% to about 20 mol%
  • R2O from about 2.99 mol% to about 12.15 mol%
  • RO from about 0.00 mol% to about 0.14 mol%
  • WO3 from about 0 mol% to about 7.03 mol%
  • M0O3 from about 0 mol% to about 8.18 mol%
  • SnCh from about 0.05 mol% to about 0.15 mol%
  • V2O5 from about 0 mol% to about 0.34 mol%.
  • compositions of Table 3 may include Fe2Cb from about 0 mol% to about 0.0025 mol%.
  • the compositions of Table 3 are provided in an as-batched state within a crucible.
  • the article may have S1O2 from about 54.01 mol% to about
  • AI2O3 from about 9.55 mol% to about 11.42 mol%
  • B2O3 from about 9.36 mol% to about 15.34 mol%
  • R2O from about 9.79 mol% to about 13.72 mol%
  • RO from about 0.00 mol% to about 0.22 mol%
  • WO3 from about 1.74 mol% to about 4.48 mol%
  • M0O3 from
  • any of the exemplary compositions of Table 4 may include CeCh from about 0 mol% to about 0.1 mol%, CuO from about 0 mol% to about 0.48 mol%, Br- from about 0 mol% to about 0.52 mol%, Cl- from about 0 mol% to about 0.2 mol%, T1O2 from about 0 mol% to about 0.96 mol% and/or Sb203 from about 0 mol% to about 0.29 mol%.
  • the compositions of Table 4 are provided in an as-batched state within a crucible.
  • the article may have SiC from about 60.01 mol% to about
  • any of the exemplary compositions of Table 5 may include Sb203 from about 0 mol% to about 0.09 mol%.
  • the compositions of Table 5 are provided in an as-batched state within a crucible.
  • compositions that, when melted using unbound alkali batch materials (e.g., alkali carbonates) instead of bound alkalis (e.g., nepheline), form a liquid alkali tungstate which separates during the melting process.
  • unbound alkali batch materials e.g., alkali carbonates
  • bound alkalis e.g., nepheline
  • the second, liquid, alkali tungstate phase may solidify as a separate crystal which may opalize substrates manufactured therefrom.
  • CdSe glasses may be characterized by their toxicity, as they possess appreciable quantities of cadmium and selenium.
  • Some efforts have been made to develop non-toxic or less toxic substitutes for CdSe glasses.
  • some conventional alternatives include Cd-free glass compositions. Yet these compositions still contain selenium and other costly dopants, such as indium and gallium.
  • conventional Cd-free, selenium-containing glasses have been characterized with inferior cut-off wavelengths relative to CdSe glasses and/or viewing angle dependency.
  • these materials possess a tunable bandgap and a sharp cut-off as a nontoxic alternative to CdSe glasses.
  • non-toxic CdSe glass alternatives characterized by low coefficients of thermal expansion (CTE), durability, thermal stress resistance and/or relatively simple and low cost manufacturing and processing requirements.
  • a glass-ceramic includes an alumino-boro-silicate glass; WO3 from about 0.7 to about 15 mol%; at least one alkali metal oxide from about 0.2 to about 15 mol%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%.
  • a glass-ceramic includes an alumino-boro-silicate glass; WO3 from about 0.7 to about 15 mol%; at least one alkali metal oxide from about 0.2 to about 15 mol%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%. Further, the glass-ceramic comprises an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • a glass-ceramic includes an alumino-boro-silicate glass; WO3 from about 0.7 to about 15 mol%; at least one alkali metal oxide from about 0.2 to about 15 mol%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%. Further, the glass-ceramic comprises at least one of an alkaline earth, alkali and mixed alkaline earth-alkali tungstate crystalline phase, the crystalline phase in stoichiometric or non-stoichiometric form.
  • the alumino- boro-silicate glass includes S1O2 from about 55 to about 80 mol%, AI2O3 from about 2 to about 20 mol%, and B2O3 from about 5 to about 40 mol% S1O2 from 68 to 72 mol%, AI2O3 from 8 to 12 mol% and B2O3 from 5 to 20 mol%.
  • the at least one alkaline earth metal oxide can include MgO from 0.1 to 5 mol%.
  • the at least one alkali metal oxide can include Na20 from 5 to 15 mol%.
  • the glass- ceramic can be substantially cadmium free and substantially selenium free.
  • the glass-ceramic can further include at least one dopant selected from the group consisting of F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi.
  • the glass-ceramic can further include M0O3 from 0% to about 50% of the WO3 present in the glass-ceramic.
  • an article includes a substrate comprising a primary surface and a glass-ceramic composition comprising: an alumino-boro-silicate glass; WO3 from about 0.7 to about 15 mol%; at least one alkali metal oxide from about 0.2 to about 15 mol%; and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%.
  • the substrate further comprises a compressive stress region, the compressive stress region extends from the primary surface to a first selected depth in the substrate and is derived from an ion- exchange process.
  • the substrate can comprise an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • a method of making a glass- ceramic includes: mixing a batch comprising an alumino-boro-silicate glass, WO3 from about 0.7 to about 15 mol%, at least one alkali metal oxide from about 0.2 to about 15 mol%, and at least one alkaline earth metal oxide from about 0.1 to about 5 mol%; melting the batch between about 1500°C and about 1700°C to form a melt; annealing the melt between about 500°C and about 600°C to define an annealed melt; and heat treating the annealed melt between about 500°C and about 1000°C from about 5 minutes to about 48 hours to form the glass-ceramic.
  • the heat treating comprises heat treating the annealed melt between about 600°C and about 800°C from about 5 minutes to about 24 hours to form the glass-ceramic. Further, the heat treating can comprise heat treating the annealed melt between about 650°C and about 725°C from about 45 minutes to about 3 hours to form the glass-ceramic. In some embodiments of the method, the glass-ceramic can comprise an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • cadmium and selenium-free glass-ceramic materials are provided with comparable or improved optical properties relative to conventional CdSe glasses.
  • these materials possess a tunable bandgap and a sharp cut-off as a non-toxic alternative to CdSe glasses.
  • Embodiments of these materials can also be characterized by low coefficients of thermal expansion (CTE), durability, thermal stress resistance and/or relatively simple and low cost manufacturing and processing requirements.
  • alumino-boro-silicate glass a tungsten oxide, at least one alkali metal oxide and at least one alkaline earth metal oxide.
  • These glass-ceramic materials can be characterized by an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm. Further, these materials can include at least one alkaline earth tungstate crystalline phase, as developed, for example, by particular heat treatment conditions after formation of the glass-ceramic. In addition, embodiments of these glass-ceramic materials are characterized by cutoffs that are tunable by selection of particular heat treatment conditions. As such, these glass-ceramic materials offer a non-toxic, cadmium and selenium-free glass-ceramic as an alternative to conventional CdSe glasses.
  • security and surveillance filters configured to suppress visible light for infrared illumination; airport runway lamps; laser eye protection lenses; light barriers for motion control in electrical machines; barcode readers; atomic force microscopes;
  • nanoindenters laser interferometer metrology solutions; laser-based dynamic calibration systems; lithography solutions for integrated circuit fabrication; photonic bit error ratio test solutions; photonic digital communication analyzers; photonic jitter generation and analysis systems; optical modulation analyzers; optical power meters; optical attenuators; optical sources; lightwave component analyzers; gas chromatographs; spectrometers; fluorescence microscopes; traffic monitoring cameras; environmental waste, water and exhaust gas monitoring equipment; spectral filters for photographic cameras; radiation thermometers; imaging luminance colorimeters; industrial image processing; controlled wavelength light sources used for counterfeit detection; scanners for digitizing color images; astronomy filters; Humphrey field analyzers in medical diagnostic equipment; and optical filters for ultra-short pulsed lasers.
  • Embodiments of these glass-ceramic materials are also suitable for use in various artistic endeavors and applications that make use of colored glass, glass-ceramics and ceramics, such as glassblowers, flameworkers, stained glass artists, etc.
  • the glass-ceramic materials, and the articles containing them offer various advantages over conventional glass, glass-ceramic and ceramic materials in the same field, including over CdSe glasses.
  • the glass-ceramic materials of the disclosure are cadmium and selenium-free, while offering sharp, visible extinctions that are analogous to orange-colored, conventional CdSe filter glasses.
  • the glass-ceramic materials of the disclosure also offer visible extinctions that are sharper in comparison to semiconductor- doped glasses, a conventional alternative to a CdSe glass. Further, the glass-ceramic materials of the disclosure are formulated with lower cost materials in comparison to conventional alternatives to CdSe glass that employ indium, gallium and/or other high-cost metals and constituents. Another advantage of these glass-ceramic materials is that they can be characterized by a cutoff wavelength that is tunable through selection of heat treatment temperature and time conditions. A further advantage of these glass-ceramics is that they are transparent in the near-infrared (" R") spectrum and do not exhibit a decrease in
  • these glass-ceramic materials can be produced with conventional melt quench processes, unlike other conventional CdSe glass alternatives, such as indium and gallium-containing semiconductor-doped glasses that require additional semiconductor synthesis and milling steps.
  • an article 100 is depicted that includes a substrate 10
  • the substrate 10 in some embodiments, can be characterized by an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • the substrate 10 comprises a pair of opposing primary surfaces 12, 14.
  • the substrate 10 comprises a compressive stress region 50. As shown in FIG. 1, the compressive stress region 50 of the article 110 is exemplary, and extends from the primary surface 12 to a first selected depth 52 in the substrate.
  • Some embodiments of the article 100 include an additional, comparable compressive stress region 50 that extends from the primary surface 14 to a second selected depth (not shown). Further, some embodiments of the article 100 (not shown) include multiple compressive stress regions 50 extending from the primary surfaces 12, 14 of the substrate 10. Still further, some embodiments of the article 100 (not shown) include multiple compressive stress regions 50 that extend from respective primary surfaces 12, 14 and compressive stress regions that also extend from the short edges of the substrate 10 (i.e., the edges that are normal to the primary surfaces 12, 14).
  • various combinations of compressive stress region(s) 50 can be incorporated within the article 100, depending on processing conditions employed to generate these compressive stress region(s) 50 (e.g., complete immersion of the substrate 10 in a molten salt ion-exchange bath, partial immersion of the substrate 10 in a molten salt ion-exchange bath, full immersion of the substrate 10, with certain edges and/or surfaces masked, etc.).
  • a "selected depth,” (e.g., selected depth 52) "depth of compression” and “DOC” are used interchangeably to define the depth at which the stress in a substrate 10, as described herein, changes from compressive to tensile.
  • DOC may be measured by a surface stress meter, such as an FSM-6000, or a scattered light polariscope (SCALP) depending on the ion exchange treatment.
  • a surface stress meter is used to measure DOC.
  • SCALP is used to measure DOC.
  • the DOC is measured by SCALP, since it is believed the exchange depth of sodium indicates the DOC and the exchange depth of potassium ions indicates a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile); the exchange depth of potassium ions in such glass substrates is measured by a surface stress meter.
  • the "maximum compressive stress” is defined as the maximum compressive stress within the compressive stress region 50 in the substrate 10. In some embodiments, the maximum compressive stress is obtained at or in close proximity to the one or more primary surfaces 12, 14 defining the compressive stress region 50. In other embodiments, the maximum compressive stress is obtained between the one or more primary surfaces 12, 14 and the selected depth 52 of the compressive stress region 50.
  • the substrate 10 of the article 100 can be characterized by a glass-ceramic composition.
  • the glass-ceramic composition of the substrate 10 is given by: WO3 from 0.7 to 15 mol%, at least one alkali metal oxide from 0.2 to 15 mol%, at least one alkaline earth metal oxide from 0.1 to 5 mol% and a balance of a silicate- containing glass.
  • These silicate-containing glasses include alumino-boro-silicate glass, boro- silicate glass, alumino-silicate glass, soda-lime glass, and chemically-strengthened versions of these silicate-containing glasses.
  • the substrate 10 may have a selected length and width, or diameter, to define its surface area.
  • the substrate 10 may have at least one edge between the primary surfaces 12, 14 of the substrate 10 defined by its length and width, or diameter.
  • the substrate 10 may also have a selected thickness.
  • the substrate has a thickness of from about 0.2 mm to about 1.5 mm, from about 0.2 mm to about 1.3 mm, and from about 0.2 mm to about 1.0 mm.
  • the substrate has a thickness of from about 0.1 mm to about 1.5 mm, from about 0.1 mm to about 1.3 mm, or from about 0.1 mm to about 1.0 mm.
  • the substrate 10 is selected from a chemically strengthened alumino-boro-silicate glass.
  • the substrate 10 can be selected from chemically strengthened alumino-boro-silicate glass having a compressive stress region 50 extending to a first selected depth 52 of greater than 10 ⁇ , with a maximum compressive stress of greater than 150 MPa.
  • the substrate 10 is selected from a chemically strengthened alumino-boro- silicate glass having a compressive stress region 50 extending to a first selected depth 52 of greater than 25 ⁇ , with a maximum compressive stress of greater than 400 MPa.
  • the substrate 10 of the article 100 may also include one or more compressive stress regions 50 that extend from one or more of the primary surfaces 12, 14 to a selected depth 52 (or depths) having a maximum compressive stress of greater than about 150 MPa, greater than 200 MPa, greater than 250 MPa, greater than 300 MPa, greater than 350 MPa, greater than 400 MPa, greater than 450 MPa, greater than 500 MPa, greater than 550 MPa, greater than 600 MPa, greater than 650 MPa, greater than 700 MPa, greater than 750 MPa, greater than 800 MPa, greater than 850 MPa, greater than 900 MPa, greater than 950 MPa, greater than 1000 MPa, and all maximum compressive stress levels between these values.
  • the maximum compressive stress is 2000 MPa or lower.
  • the depth of compression (DOC) or first selected depth 52 can be set at 10 ⁇ or greater, 15 ⁇ or greater, 20 ⁇ or greater, 25 ⁇ or greater, 30 ⁇ or greater, 35 ⁇ or greater, and to even higher depths, depending on the thickness of the substrate 10 and the processing conditions associated with generating the compressive stress region 50.
  • the DOC is less than or equal to 0.3 times the thickness (t) of the substrate 10, for example 0.3 t, 0.28 t, 0.26 t, 0.25 t, 0.24 t, 0.23 t, 0.22 t, 0.21 t, 0.20 t, 0.19 t, 0.18 t, 0.15 t, or 0.1 1.
  • t the thickness of the substrate 10
  • the glass-ceramic materials of the disclosure including the substrate 10 employed in the article 100 (see FIG.
  • the glass-ceramic composition are characterized by the following glass-ceramic composition: WCb from 0.7 to 15 mol%, at least one alkali metal oxide from 0.2 to 15 mol%, at least one alkaline earth metal oxide from 0.1 to 5 mol% and a balance of a silicate-containing glass, e.g., an alumino-boro-silicate glass.
  • the glass- ceramic material can be characterized by an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • the glass-ceramic material can be further characterized by the presence of at least one alkaline earth tungstate crystalline phase and/or at least one alkali metal tungstate crystalline phase.
  • the alkaline earth tungstate crystalline phase can be given by MxWCb, where M is at least one of Be, Mg, Ca, Sr, Ba, and Ra, and where 0 ⁇ x ⁇ 1.
  • the at least one alkaline earth tungstate crystalline phase is one or both of a MgWCb crystalline phase (see, e.g., FIG. 5 and its corresponding description) and a MgW 2 Cb crystalline phase (see, e.g., FIGS.
  • the alkali tungstate crystalline phase can be given by MxWCb, where M is at least one of Li, Na, K, Cs, Rb, and where 0 ⁇ x ⁇ 1.
  • the tungstate crystalline phase can be given by MxWCb, where M is a combination of an alkaline earth from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra and an alkali metal from the group consisting of Li, Na, K, Cs, Rb, and where 0 ⁇ x ⁇ 1.
  • the glass-ceramics of the disclosure are optically transparent in the visible region of the spectrum (i.e., from about 400 nm to about 700 nm).
  • the term "optically transparent” refers to a transmittance of greater than about 1% over a 1 mm path length (e.g., in units of %/mm) over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
  • the glass-ceramic has a transmittance of at least greater than about 5%/mm, greater than about 10%/mm, greater than about 15%/mm, greater than about 20%/mm, greater than about 25%/mm, greater than about 30%/mm, greater than about 40%/mm, greater than about 50%/mm, greater than about 60%/mm, greater than about 70%/mm, and greater than all lower limits between these values, all over at least one 50 nm-wide wavelength band of light in the visible region of the spectrum.
  • Embodiments of the glass-ceramics of the disclosure absorb light in the ultraviolet (“UV”) region (i.e., wavelengths of less than about 370 nm) and/or in the near infrared (“MR”) region (i.e., wavelengths from about 700 nm to about 1700 nm) of the spectrum without the use of additional coatings or films.
  • UV ultraviolet
  • MR near infrared
  • the glass-ceramic is characterized by a transmittance of less than 10%/mm, less than 9%/mm, less than 8%/mm, less than 7%/mm, less than 6%/mm, less than 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, and even less than 1%/mm, for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum.
  • the glass-ceramic absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or even at least 99%/mm for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum.
  • the glass-ceramic is characterized by a transmittance of less than 10%/mm, less than 9%/mm, less than 8%/mm, less than 7%/mm, less than 6%/mm, less than 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, and even less than 1%/mm, for light in at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum.
  • the glass-ceramic absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or even at least 99%/mm for light in at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum.
  • Embodiments of the glass-ceramic materials of the disclosure comprise an alumino- boro-silicate glass (e.g., as containing SiCh, AI2O3 and B2O3), WO3, at least one alkali metal oxide, and at least one alkaline earth metal oxide.
  • the alumino-boro- silicate glass includes from about 55 mol% to about 80 mol% S1O2, from about 60 mol% to about 74 mol% S1O2, or from about 64 mol% to about 70 mol% S1O2.
  • the alumino- boro-silicate glass of the glass-ceramic can include from about 2 mol% to about 40 mol% B2O3, from about 5 mol% to about 16 mol% B2O3, or from about 6 mol% to about 12 mol% B2O3.
  • the alumino-boro-silicate glass of the glass-ceramic can include from about 0.5 mol% to about 16 mol% AI2O3, from about 2 mol% to about 20 mol% AI2O3, or from about 6 mol% to about 14 mol% AI2O3.
  • the glass-ceramic materials of the disclosure include from about 0.7 mol% to about 15 mol% WO3. In some embodiments, the glass-ceramic materials include from about 1 mol% to about 6 mol% WO3, or from about 1.5 mol% to about 5 mol% WO3. In some implementations, the glass-ceramic can further comprise M0O3 from about 0% to about 50% of the WO3 present in the composition (i.e., M0O3 from about 0% to 5 mol%). In some embodiments, the glass-ceramic further comprises M0O3 from about 0 mol% to about 3 mol%, or from about 0 mol% to about 2 mol%.
  • the glass-ceramic materials of the disclosure include at least one alkali metal oxide.
  • the glass-ceramic materials include at least one alkali metal oxide from about 0.2 mol% to about 15 mol%.
  • the at least one alkali metal oxide can be selected from the group including L12O, Na 2 0, K2O, Rb 2 0 and Cs 2 0.
  • a difference in the amount of the at least one alkali metal oxide and the AI2O3 in the alumino- boro-silicate glass ranges from -6 mol% to +2 mol%.
  • the glass-ceramic materials of the disclosure also include at least one alkaline earth metal oxide.
  • the glass-ceramic includes at least one alkaline earth metal oxide from about 0.1 mol% to about 5 mol%.
  • the at least one alkaline earth metal oxide can be selected from the group including MgO, SrO and BaO.
  • the glass-ceramic materials of the disclosure include Sn0 2 from about 0 mol% to about 0.5 mol%, from about 0 mol% to about 0.25 mol%, or from about 0 mol% to about 0.15 mol%.
  • implementations are substantially cadmium and substantially selenium free.
  • the glass-ceramic can further comprise at least one dopant selected from the group consisting of F, P, S, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, Sb, Te and Bi.
  • the at least one dopant is present in the glass-ceramic from about 0 mol% to about 0.5 mol% as the oxide.
  • the glass-ceramic materials of the disclosure can be made by employing a melt quench process. Appropriate ratios of the constituents may be mixed and blended by turbulent mixing and/or ball milling.
  • Batch materials can include but are not limited to one or more of sand, spodumene, petalite, nepheline syenite, alumina, borax, boric acid, alkali and alkaline earth carbonates and nitrates, tungsten oxide and ammonium tungstate.
  • the batched material is then melted at temperatures ranging from about 1500°C to about 1700°C for a predetermined time.
  • the predetermined time ranges from about 6 to about 12 hours, after which time the resulting melt can be cast or formed and then annealed, as understood by those with skill in the field of the disclosure.
  • the melt can be annealed between about 500°C and about 600°C to define an annealed melt.
  • the annealed melt is heat treated between about 500°C to about 1000°C from about 5 minutes to about 48 hours to form the glass-ceramic.
  • the heat treating step is conducted at or slightly above the annealing point of the glass-ceramic, and below its softening point, to develop one or more crystalline tungstate phases.
  • the annealed melt is heat treated between about 600°C and about 800°C from about 5 minutes to about 24 hours to form the glass-ceramic.
  • the annealed melt is heat treated between about 650°C and about 725°C from about 45 minutes to about 3 hours to form the glass-ceramic.
  • another step is conducted at or slightly above the annealing point of the glass-ceramic, and below its softening point, to develop one or more crystalline tungstate phases.
  • the annealed melt is heat treated between about 600°C and about 800°C from about 5 minutes to about 24 hours to form the glass-ceramic.
  • the annealed melt is heat treated between
  • the annealed melt is heat treated according to a temperature and time to obtain particular optical properties, e.g., an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • optical properties e.g., an optical transmittance of at least 90% from 700 nm to 3000 nm and a sharp cutoff wavelength from about 320 nm to about 525 nm.
  • additional heat treatment temperatures and times can be employed to obtain glass-ceramic materials
  • FIGS. 2A and 2B a plot of transmittance vs. wavelength of a
  • FIG. 2B is the plot in FIG. 2A, as rescaled to show the cutoff wavelength of the comparative CdSe glass and heat-treated glass-ceramic samples.
  • the comparative CdSe glass, Comp. Ex. 1 the comparative CdSe glass, Comp. Ex.
  • the heat-treated glass-ceramic has the same composition as indicated in Tables 1 A and IB for the Ex. 1 sample.
  • the glass-ceramic depicted in FIGS. 2 A and 2B was prepared according to a method of making glass-ceramic materials, as noted earlier in the disclosure, including a heat treating step that comprised heating the annealed melt for about 1 hour at 700°C.
  • both samples depicted in FIGS. 2A and 2B have a normalized path length of 4 mm.
  • the glass-ceramic sample (Ex. 1) heat treated at 700°C for 1 hour, exhibits a sharp cutoff at about the same wavelength range and sharpness as the CdSe glass sample (Comp. Ex. 1).
  • FIGS. 3 A and 3B a plot of transmittance vs. wavelength of a
  • the comparative CdSe glass (“Comp. Ex. 1") and a heat-treated glass-ceramic (“Exs. 1A-1K”) is provided.
  • FIG. 3B is the plot in FIG. 3 A, as rescaled to show the cutoff wavelength of the comparative CdSe glass and the heat-treated glass-ceramic samples.
  • the comparative CdSe glass, Comp. Ex. 1 has a conventional CdSe glass composition according to the following: 40-60% S1O2, 5-20% B2O3, 0-8% P2O5, 1.5-6% AI2O3, 4-8%
  • the heat-treated glass-ceramic samples each have the same composition as indicated in Tables 1 A and IB for the Ex. 1 sample.
  • the glass-ceramics depicted in FIGS. 3 A and 3B were each prepared according to a method of making glass-ceramic materials, as noted earlier in the disclosure, including the following heat treatment steps after annealing: 525°C for 1 hour and 40 minutes (Ex. 1A); 525°C for 10 hours and 39 minutes (Ex. IB); 550°C for 3 hours and 10 minutes (Ex. 1C); 600°C for 6 hours and 24 minutes (Ex.
  • FIG. 4A is a plot of transmittance vs. wavelength of the comparative CdSe glass ("Comp. Ex. 1") and the glass-ceramic samples heat treated at 700°C and 800°C according to various conditions (Exs. IK and 2A).
  • FIG. 4B is the plot in FIG. 4A, as rescaled to show the cutoff wavelength of the comparative CdSe glass and the glass-ceramic samples heat treated according to various conditions.
  • these magnesium tungsten glass-ceramic compositions can be employed to vary and tune the cutoff wavelength and its sharpness within the range of about 320 nm to about 525 nm. It is also apparent that the higher magnesium content in the Ex. 2A glass-ceramic (-3.84 mol%) compared to that of the Ex. IK glass- ceramic (-0.95 mol%) may contribute to its lower cutoff wavelength and perhaps, its higher transmittance in the NIR range. Accordingly, and without being bound by theory, varying magnesium content in these glass-ceramic compositions, along with varying heat treatment conditions, can have the effect of changing the spectra and cutoff wavelength of the glass- ceramic.
  • FIG. 4C is scaled to show the cutoff wavelength of the comparative CdSe glass, Comp. Ex. 1, the glass-ceramic samples heat treated according to various conditions (Ex. IK and Ex. 2A) and the comparative CuInSe and CuInS samples (Comp. Ex. 2 and Comp. Ex. 3). From FIG.
  • the glass-ceramic materials, Ex. IK and Ex. 2A outperform the comparative CuInSe and CuInS glasses in terms of approximating the cutoff wavelength of the comparative CdSe glass. That is, these glass-ceramics have optical properties that better approximate those of the CdSe glass relative to other semiconductor-doped glass alternatives, CuInSe and CuInS.
  • an x-ray diffraction ("XRD") plot of a heat-treated glass- ceramic, Ex. 1L (see Tables 1 A and IB), is provided according to at least one example of the disclosure.
  • This sample was heat-treated at 700°C for 17 hours and 16 minutes.
  • the Ex. 1L glass ceramic can comprise a crystalline MgW0 4 tungsten oxide phase.
  • FIGS. 6A-6C Raman spectroscopy plots are provided of splat- quenched glass-ceramic samples (i.e., FIG. 6 A, Ex. 1, no heat treatment after annealing) and glass-ceramic samples heat treated at 650°C for 5 hours and 35 minutes and 700°C for 17 hours and 16 minutes (Ex. 1H and Ex. 1L as shown in FIGS. 6B and 6C, respectively), according to examples of the disclosure.
  • all of the glass-ceramic materials subjected to the Raman spectroscopy testing possessed a glass-ceramic composition according to Ex. 1 in Tables 1 A and IB.
  • FIG. 6 A demonstrates that the splat- quenched sample with no further heat treatment (Ex. 1) exhibits various increased intensity levels indicative of non-crystalline phases (e.g., network bends Si-O, Al-0 and B-0 at 470 cm "1 ).
  • FIGS. 6B and 6C demonstrate that the heat-treated samples (Exs. 1H and 1L) have substantially higher intensity levels at the same Raman shift positions associated with lower intensity levels observed in the splat-quenched sample (Ex.
  • FIGS. 7 A and 7B demonstrate that the splat-quenched sample (Ex. 1) has substantially lower intensity levels at the same Raman shift positions associated with high intensity levels observed for the samples subjected to the specified heat treatment conditions (Exs. 1H and 1L).
  • the heat treatment conditions can result in the development of a crystalline tungsten oxide phase (e.g., MgW 2 07 as shown in both FIGS. 7 A and 7B) and/or a crystalline tungsten suboxide phase (i.e., a non-stoichiometric phase).
  • FIG. 8 a plot is provided of residual stress (MPa) vs. substrate depth (mm) for two glass-ceramic samples with compressive stress regions derived from two respective ion-exchange process conditions (Ex. 10-IOXA and Ex. 10-IOXB).
  • the y-axis is the residual stress in the substrate, with positive values referring to tensile residual stresses and negative values referring to compressive residual stresses.
  • the x- axis is the depth in each of the substrates, with values at 0 mm and 1.1 mm denoting the primary surfaces of the substrate (e.g., primary surfaces 12 and 14 of substrate 10, as shown in FIG. 1).
  • each of the glass-ceramic samples in this example, Ex. 10-IOXA and Ex. 10- IOXB, has the same composition as indicated in Tables 1 A and IB for the Ex. 10 sample. Further, each of the samples was melted and cast onto a steel table to form an optical patty, consistent with the methods outlined earlier in the disclosure. Each sample was then annealed at 570°C for one hour and then cooled at a furnace rate to ambient temperature. Samples having dimensions of 25 mm x 25 mm x -1.1 mm were then ground and polished to form an annealed optical patty. Finally, the Ex.
  • 10-IOXA sample was immersed in a 100% NaN0 3 molten salt bath at 390°C for eight (8) hours to form its compressive stress region.
  • the Ex. 10-IOXB was immersed in a 100% NaN0 3 molten salt bath at 390°C for sixteen (16) hours to form its compressive stress region. Note that the actual thickness of the Ex. 10-IOXA and 10-IOXB samples was measured at 1.10 mm and 1.06 mm, respectively.
  • the glass-ceramic sample with the shorter ion exchange duration exhibits a compressive stress region with a depth of compression (DOC) of 136.7 ⁇ , a maximum compressive stress of about -320 MPa, a central tension (CT) region given by a peak tension of 57 MPa, and a stored strain energy of 16.6 J/m 2 .
  • DOC depth of compression
  • CT central tension
  • 10-IOXB exhibits a DOC of 168.0 ⁇ , a maximum compressive stress of about -270 MPa, a CT region given by a peak tension of 72 MPa, and a stored strain energy of 25 J/m 2 .
  • the longer ion exchange duration of the Ex. 10-IOXB sample resulted in a larger DOC, a lower maximum compressive stress, a CT region given by a larger peak tension and a larger stored strain energy as compared to the Ex. 10-IOXA having the shorter ion exchange process duration.
  • the glass-ceramic samples depicted in FIG. 8 exhibited compressive stress regions developed from an immersion in a molten salt bath of 100% NaN0 3
  • the glass-ceramic can also be ion-exchanged in a bath of molten KN0 3 , a mixture of NaN0 3 and KN0 3 , or sequentially ion-exchanged first in a NaN0 3 bath and secondly in KN0 3 to increase the compressive stress level on, and in proximity to, the surface(s) of the substrate.
  • sulfates, chlorides, and other salts of ion-exchanging metal ions can also be employed in these bath(s).
  • ion-exchanging temperatures can vary from about 350°C to 550°C, while preferably ranging from 370°C to about 450°C to prevent salt decomposition and stress relaxation.
  • Crystal size was dependent on base glass composition, but could also be tuned slightly by heat-treatment time and temperature. Additionally, crystallization rate increased significantly with small additions of calcium oxide (CaO), which is believed to interact with the tungsten oxide to form nanocrystals of scheelite, or non-stoichiometric scheelite-like structures that could serve as nucleation sites.
  • CaO calcium oxide
  • the x-ray energy-dispersive x-ray spectroscopy (EDS) maps of the crystallites formed after heat treatment show that they are comprised of tungsten, oxygen, and potassium.
  • crystallites that were generally rod-like in shape with aspect ratios between 2 and 4, mostly about 2-20 nm in length, mostly about 2-10 nm in diameter, and were about 11 to 14.8 volume percent of the material glass-ceramics.
  • the sample shown in FIGS. 11 A and 1 IB was heat treated at 550° C for 4 hours, cooled to 475° C at 1° C/minute, and then to room temperature to furnace rate.
  • the cane was then placed in a gradient furnace for five minutes such that one end of the cane remained at room temperature and the other end of the cane was at 650 C.
  • the region between each end was exposed to an approximately uniform gradient in temperature between 25° and 650° C. In the region where temperatures were above approximately 575° C, color started to shift from blue, to a green, to a yellow, to an orange, and finally a red. All colors were highly transparent.
  • glass-ceramic has transmittance of about 5%/mm or greater over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
  • glass- ceramics have lower transmittance, such as those that are opaque.
  • these glass-ceramics are unique in that they strongly absorb but do not scatter light and have very low haze.
  • the glass- ceramics have optical density per millimeter (OD/mm) of at least 0.07 for at least some (e.g., most, >90%) of light with 200-400 nm wavelength, at most 25 OD/mm of the same
  • the glass-ceramics have optical density per millimeter (OD/mm) of at least 0.022 for at least some (e.g., most, >90%) of light with 400-750 nm wavelength, at most 10 OD/mm of the same wavelengths, and/or haze of less than 10%.
  • the glass-ceramics have optical density per millimeter (OD/mm) of at least 0.04 for at least some (e.g., most, >90%) of light with 750-2000 nm wavelength, at most 15 OD/mm of the same wavelengths, and/or haze of less than 10%
  • compositions for articles including titanium.
  • the as-made state of the titanium containing glass are highly transparent in the NIR regime, and largely transparent at visible wavelengths.
  • the crystalline phase i.e., titanium suboxides
  • the optical transmittance of these samples decreases and some become strongly absorbing in the NIR.
  • Powder X-ray diffraction was performed on each of the compositions of Table 8C and indicated that all compositions were X-ray amorphous in the as-made and un-annealed state.
  • Heat treated samples showed evidence of some titania-bearing crystalline phases including Anatase (889FLY) and Rutile (889FMC and 889FMD).
  • the samples exhibited low haze (i.e., about 10% or less, or about ⁇ 5% or less, or about 1% or less, or about 0.1% or less).
  • the low haze that these compositions exhibited in the as-made and post-heat treated state is due to the fact that the crystallites are quite small (i.e., about 100 nm or less) and in low abundance (i.e., due to the fact that TiCh was introduced at only about 2 mol%). Accordingly, it is believed that the species forming in these materials are below the detection limits (in size and abundance) for conventional powder XRD. This hypothesis was confirmed by TEM microscopy.
  • FIGS. 18A-D provided are TEM micrographs at four different magnifications of titania-containing crystals within a sample of glass code composition 889FMC that was heat treated at 700° C for one hour. These crystals are rod-like in appearance and have an average width of about 5 nm and an average length of about 25 nm.
  • FIGS. 19A and 19B provided is a TEM micrograph (FIG. 19A) and corresponding EDS elemental map (FIG. 19B) of a heat treated sample of glass code composition 889FMC.
  • the sample includes a plurality of crystallites.
  • the EDS map was set to detect titanium.
  • the results of the EDS mapping of titanium closely track with the crystallites indicating that the crystallites are rich in titanium. In this map, the light or 'white' regions indicate the presence of Ti.
  • Composition 196KGA was 1 mm thick and thermally treated at 550° C for 30 minutes and allowed to cool at 1° C per minute to 475° C.
  • the 889FMD sample was 5 mm thick and was thermally processed at 600° C for 1 hour.
  • the 889FMG sample was 0.5 mm thick and was thermally processed at 700° C for 2 hours.
  • the VG10 samples refer a glass sold under the trade name SGG VENUS (VG 10) by Saint-Gobain ® and differ from one another in thickness.
  • T L is the total visible light transmittance (which is the weighted- average transmission of light through a glazing at a wavelength range of 380 nm to 780 nm and is tested in accordance with ISO 9050 Section 3.3).
  • T TS is the total transmitted solar (also referred to as Solar Factor ("SF") or Total Solar Heat Transmission (“TSHT”), which is the sum of the T DS (total direct solar) plus the fraction of solar energy that is absorbed by the glazing and then re-radiated into a vehicle interior as measured by ISO 13837-2008 Annex B & ISO 9050-2003 section 3.5).
  • T TS is calculated for a parked car condition with wind speed of 4 m/s (14 km/hr)% with T TS being equal to (% T_DS)+ 0.276 * (% solar absorption).
  • T DS is the total direct solar transmittance (also referred to as "Solar Transmission” ("Ts") or "Energy Transmission", which is the weighted-average transmission of light through a glazing at a wavelength range of 300 nm to 2500 nm as measured by ISO 13837 section 6.3.2)).
  • R DS is the reflected solar component (i.e., with nominally 4% Fresnel reflection).
  • T_E is the solar direct transmittance.
  • T UV is the UV transmittance as measured under ISO 9050 and ISO 13837 A.
  • T IR is the infrared
  • glass code 196KGA has the best optical performance and is able to produce the lowest UV, VIS, and NIR transmittance at very short path lengths (0.2 mm).
  • the titanium containing compositions 889FMD and 889FMG at 0.5 mm thickness produce superior optical performance to the VG10 glass at path lengths at or below 3.85 mm.
  • the titanium containing compositions 889FMD and 889FMG had superior performance to the VG10 glass despite having shorter path lengths.
  • the glass-ceramics include an amorphous phase and crystalline phase, where the crystalline phase comprises (e.g., includes, is, mostly is) a bronze-structure as disclosed herein, such as a precipitates of formula M x Ti02, M x W0 3 , etc., as disclosed herein.
  • a volume fraction of the crystalline phase may range from about 0.001% to about 20%, or from about 1% to about 20%, or from about 5% to about 20%, or from about 10% to about 20%, or from about 10% to about 30%), or from about 0.001% to about 50%.
  • a volume fraction of the crystalline phase may range from about 0.001%) to about 20%, or from about 0.001%) to about 15%), or from about 0.001%> to about 10%> or from about 0.001%) to about 5%, or from about 0.001%> to about 1%.
  • the volume fraction of crystalline phase in the glass-ceramic may be more than 50%.
  • the glass-ceramics include an amorphous phase and crystalline phase, where the crystalline phase comprises (e.g., includes, is, mostly is) a bronze-structure as disclosed herein, such as a precipitates of formula M x Ti02, M x W0 3 , etc., as disclosed herein, where M represents dopant cations as disclosed herein, and the precipitates (e.g., crystals) are sub-oxides, where 0 ⁇ x ⁇ l, such as where 0 ⁇ x ⁇ l, such as where 0 ⁇ x ⁇ 0.9, such as where 0 ⁇ x ⁇ 0.75, such as where 0 ⁇ x ⁇ 0.5, such as where 0 ⁇ x ⁇ 0.2, and/or where 0.01 ⁇ x ⁇ l, such as where 0.01 ⁇ x ⁇ l, such as where 0.01 ⁇ x ⁇ l, such as where 0.1 ⁇ x ⁇ l, such as where 0.2 ⁇ x ⁇ l, such as where 0.5 ⁇ x ⁇ l, and/or where
  • 0.001 ⁇ x ⁇ 0.999 such as where 0.01 ⁇ x ⁇ 0.99, such as where 0.1 ⁇ x ⁇ 0.9, such as where 0.2 ⁇ x ⁇ 0.9 or where 0.1 ⁇ x ⁇ 0.8.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Une vitrocéramique comprend du verre contenant du silicate et des phases cristallines, la phase cristalline comprenant des sous-oxydes non stoechiométriques de tungstène et/ou de molybdène, ou encore du titane, formant des structures de défaut à l'état solide de type "bronze" dans lesquelles des lacunes sont occupées par des cations dopants.
EP18871435.6A 2017-10-23 2018-10-23 Vitrocéramiques et verres Pending EP3700871A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201762575763P 2017-10-23 2017-10-23
US15/840,040 US10246371B1 (en) 2017-12-13 2017-12-13 Articles including glass and/or glass-ceramics and methods of making the same
PCT/US2018/057009 WO2019083937A2 (fr) 2017-10-23 2018-10-23 Vitrocéramiques et verres

Publications (2)

Publication Number Publication Date
EP3700871A2 true EP3700871A2 (fr) 2020-09-02
EP3700871A4 EP3700871A4 (fr) 2021-08-04

Family

ID=66246420

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18871435.6A Pending EP3700871A4 (fr) 2017-10-23 2018-10-23 Vitrocéramiques et verres

Country Status (7)

Country Link
EP (1) EP3700871A4 (fr)
JP (2) JP7429189B2 (fr)
KR (1) KR20200062349A (fr)
CN (4) CN113185129B (fr)
NL (1) NL2021858B1 (fr)
TW (2) TWI811252B (fr)
WO (1) WO2019083937A2 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170362119A1 (en) 2016-06-17 2017-12-21 Corning Incorporated Transparent, near infrared-shielding glass ceramic
US10246371B1 (en) 2017-12-13 2019-04-02 Corning Incorporated Articles including glass and/or glass-ceramics and methods of making the same
US10450220B2 (en) 2017-12-13 2019-10-22 Corning Incorporated Glass-ceramics and glasses
US12552704B2 (en) 2017-10-23 2026-02-17 Corning Incorporated Glass-ceramics and glasses
CN113748092A (zh) * 2019-02-12 2021-12-03 康宁股份有限公司 多色玻璃和玻璃陶瓷制品及其制造方法
KR20210121257A (ko) 2019-02-20 2021-10-07 코닝 인코포레이티드 철- 및 망간-도프된 텅스텐산염 및 몰리브덴산염 유리 및 유리-세라믹 물품
CN116670089A (zh) * 2021-06-18 2023-08-29 康宁股份有限公司 具有改善的机械耐久性的着色玻璃制品
US12454479B2 (en) 2021-06-18 2025-10-28 Corning Incorporated Gold containing silicate glass
US12054422B2 (en) 2021-06-18 2024-08-06 Corning Incorporated Colored glass articles having improved mechanical durability
US20230373846A1 (en) * 2021-06-18 2023-11-23 Corning Incorporated Colored glass articles having improved mechanical durability
US12378152B2 (en) 2021-06-18 2025-08-05 Corning Incorporated Colored glass articles having improved mechanical durability
WO2022266400A1 (fr) * 2021-06-18 2022-12-22 Corning Incorporated Articles en verre coloré ayant une durabilité mécanique améliorée
KR20240023516A (ko) 2021-06-18 2024-02-22 코닝 인코포레이티드 향상된 기계적 내구성을 갖는 착색 유리 물품
US11802072B2 (en) 2021-06-18 2023-10-31 Corning Incorporated Gold containing silicate glass
US11560329B1 (en) 2021-10-04 2023-01-24 Corning Incorporated Colored glass articles having improved mechanical durability
US11634354B2 (en) 2021-06-18 2023-04-25 Corning Incorporated Colored glass articles having improved mechanical durability
WO2022266273A1 (fr) 2021-06-18 2022-12-22 Corning Incorporated Articles en verre coloré ayant une durabilité mécanique améliorée
TWI764823B (zh) * 2021-09-06 2022-05-11 富喬工業股份有限公司 具有低膨脹係數及低介電常數的玻璃組成物及玻璃纖維
CN114790082A (zh) * 2022-03-30 2022-07-26 山东国瓷功能材料股份有限公司 一种含钨酸锌晶相的荧光玻璃陶瓷
CN114605075A (zh) * 2022-03-30 2022-06-10 山东国瓷功能材料股份有限公司 一种含钨酸镉晶相的荧光玻璃陶瓷
CN114685050A (zh) * 2022-04-28 2022-07-01 电子科技大学 一种高储能效率硅铌酸盐微晶玻璃材料及制备方法
US12240782B2 (en) 2022-05-31 2025-03-04 Corning Incorporated Ion exchangeable yellow glass articles
CN116119932B (zh) * 2022-12-14 2026-03-20 湖南兆湘光电高端装备研究院有限公司 微晶玻璃及其制备方法、微晶夹层玻璃及其制备方法和应用
CN116477930B (zh) * 2023-03-17 2024-07-05 江苏师范大学 一种通过纳米金属成核剂制备大尺寸、纳米晶透明陶瓷的方法
CN119143389B (zh) * 2024-11-18 2025-01-24 山东龙光天旭太阳能有限公司 一种耐热高硼硅玻璃及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293052A (en) 1963-03-14 1966-12-20 Corning Glass Works Glass article and method of making it
WO2017218859A1 (fr) 2016-06-17 2017-12-21 Corning Incorporated Vitrocéramique transparente protégeant contre les infrarouges proches
WO2019113029A1 (fr) 2017-12-04 2019-06-13 Corning Incorporated Vitrocéramiques et articles vitrocéramiques ayant des caractéristiques de blocage des uv et nir

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3582370A (en) * 1968-11-05 1971-06-01 Corning Glass Works Glass-ceramic articles
US4009042A (en) * 1976-01-15 1977-02-22 Corning Glass Works Transparent, infra-red transmitting glass-ceramics
US4396720A (en) * 1982-07-06 1983-08-02 Corning Glass Works Transparent glass-ceramics containing mullite
JP2539214B2 (ja) * 1987-03-31 1996-10-02 川鉄鉱業株式会社 ガラスセラミツクスおよびその製造方法
JPH09241035A (ja) * 1996-03-06 1997-09-16 Central Glass Co Ltd 結晶化ガラス
JP4680347B2 (ja) * 1999-06-01 2011-05-11 株式会社オハラ 高剛性ガラスセラミックス基板
US6376399B1 (en) * 2000-01-24 2002-04-23 Corning Incorporated Tungstate, molybdate, vanadate base glasses
US6677046B2 (en) * 2001-03-27 2004-01-13 Hoya Corporation Glass ceramic
JP2006182637A (ja) * 2004-11-30 2006-07-13 Asahi Glass Co Ltd フィールドエミッションディスプレイ用結晶化ガラススペーサーおよびその製造方法、ならびにフィールドエミッションディスプレイ
JP5034272B2 (ja) * 2006-03-06 2012-09-26 住友金属鉱山株式会社 タングステン含有酸化物微粒子、およびその製造方法、ならびにそれを用いた赤外線遮蔽体
FR2909373B1 (fr) * 2006-11-30 2009-02-27 Snc Eurokera Soc En Nom Collec Vitroceramiques de beta-quartz, transparentes et incolores, exemptes de tio2 ; articles en lesdites vitroceramiques ; verres precurseurs, procedes d'elaboration.
CN101200345A (zh) * 2007-12-14 2008-06-18 邓念东 晶彩陶瓷、晶彩玻璃,晶彩彩饰层的复合材料及其工艺方法
JP5715353B2 (ja) * 2009-07-31 2015-05-07 株式会社オハラ 結晶化ガラスおよびその製造方法
WO2011013797A1 (fr) * 2009-07-31 2011-02-03 株式会社オハラ Vitrocéramique, matière vitrocéramique frittée, complexe vitrocéramique, micropoudre de vitrocéramique, mélange de type bouillie et photocatalyseur
JP2011046601A (ja) * 2009-07-31 2011-03-10 Ohara Inc ガラスセラミックス複合体及びその製造方法、光触媒機能性部材、並びに親水性部材
JP2011241092A (ja) * 2010-04-21 2011-12-01 Ohara Inc ガラスセラミックス及びその製造方法
US20120247525A1 (en) * 2011-03-31 2012-10-04 Bruce Gardiner Aitken Tungsten-titanium-phosphate materials and methods for making and using the same
US9403714B2 (en) * 2011-10-14 2016-08-02 Ivoclar Vivadent Ag Lithium silicate glass ceramic and lithium silicate glass comprising a hexavalent metal oxide
FR3004445B1 (fr) * 2013-04-15 2019-10-18 Schott Ag Surface de cuisson vitroceramique a transmission localement augmentee et procede de fabrication d'une telle surface de cuisson vitroceramique
KR20150133857A (ko) * 2013-04-15 2015-11-30 쇼오트 아게 유리 및 유리 세라믹스의 투과율 변경 방법 및 이 방법에 따라 제조될 수 있는 유리 또는 유리 세라믹 물품
CN103482872B (zh) * 2013-09-29 2016-05-18 陈锐群 一种钛合金玻璃陶瓷涂料及其制备方法
US9878940B2 (en) * 2014-02-21 2018-01-30 Corning Incorporated Low crystallinity glass-ceramics
CN105254181B (zh) * 2014-07-18 2017-08-11 长春理工大学 一种铕掺杂钨酸盐透明玻璃陶瓷及其制备方法
DE102014013528B4 (de) * 2014-09-12 2022-06-23 Schott Ag Beschichtetes Glas-oder Glaskeramiksubstrat mit beständigen multifunktionellen Oberflächeneigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung
TWI861872B (zh) * 2014-10-08 2024-11-11 美商康寧公司 具有葉長石及矽酸鋰結構的高強度玻璃陶瓷
EP3230221B1 (fr) * 2014-12-11 2023-10-11 Corning Incorporated Coloration induite par rayons x dans des articles en verre ou vitrocéramiques
CN104944471A (zh) * 2015-05-25 2015-09-30 北京航空航天大学 一种具有高红外屏蔽性能的掺杂钨青铜粉体及其合成方法
US20200230703A1 (en) * 2016-01-27 2020-07-23 Evonik Degussa Gmbh Process for producing tungsten oxide and tungsten mixed oxides
CN105948513B (zh) * 2016-05-16 2018-09-21 长春理工大学 一种铽掺杂含钼酸钙晶相透明玻璃陶瓷及其制备方法
CN106396413B (zh) * 2016-09-08 2018-11-09 长春理工大学 铒镱共掺含钨酸钡晶相上转换发光玻璃陶瓷及其制备方法
US10829408B2 (en) * 2017-12-13 2020-11-10 Corning Incorporated Glass-ceramics and methods of making the same
US11053159B2 (en) * 2017-12-13 2021-07-06 Corning Incorporated Polychromatic articles and methods of making the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293052A (en) 1963-03-14 1966-12-20 Corning Glass Works Glass article and method of making it
WO2017218859A1 (fr) 2016-06-17 2017-12-21 Corning Incorporated Vitrocéramique transparente protégeant contre les infrarouges proches
WO2019113029A1 (fr) 2017-12-04 2019-06-13 Corning Incorporated Vitrocéramiques et articles vitrocéramiques ayant des caractéristiques de blocage des uv et nir

Also Published As

Publication number Publication date
CN118702410A (zh) 2024-09-27
CN113185129A (zh) 2021-07-30
CN113185129B (zh) 2022-05-27
CN118702410B (zh) 2025-11-21
WO2019083937A2 (fr) 2019-05-02
CN111511696A (zh) 2020-08-07
WO2019083937A3 (fr) 2019-06-20
TWI811252B (zh) 2023-08-11
TW202346229A (zh) 2023-12-01
CN118666493B (zh) 2025-11-21
JP2021500299A (ja) 2021-01-07
NL2021858B1 (en) 2019-10-24
CN118666493A (zh) 2024-09-20
EP3700871A4 (fr) 2021-08-04
NL2021858A (en) 2019-04-25
TW201922660A (zh) 2019-06-16
KR20200062349A (ko) 2020-06-03
JP7429189B2 (ja) 2024-02-07
JP2024010059A (ja) 2024-01-23
TWI870937B (zh) 2025-01-21

Similar Documents

Publication Publication Date Title
US11643359B2 (en) Glass-ceramics and glasses
NL2021858B1 (en) Glass-ceramics and glasses
US11912609B2 (en) Articles including glass and/or glass-ceramics and methods of making the same
US10829408B2 (en) Glass-ceramics and methods of making the same
US20190177206A1 (en) Polychromatic articles and methods of making the same
US20200255325A1 (en) Polychromatic glass & glass-ceramic articles and methods of making the same
EP3927670A1 (fr) Tungstate dopé au fer et au manganèse et articles en verre de molybdate et en vitrocéramique
US12552704B2 (en) Glass-ceramics and glasses

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200514

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20210706

RIC1 Information provided on ipc code assigned before grant

Ipc: C03C 10/00 20060101AFI20210630BHEP

Ipc: C03C 3/118 20060101ALI20210630BHEP

Ipc: C03C 3/097 20060101ALI20210630BHEP

Ipc: C03C 3/091 20060101ALI20210630BHEP

Ipc: C03C 3/089 20060101ALN20210630BHEP

Ipc: C03C 4/08 20060101ALN20210630BHEP

Ipc: C03C 21/00 20060101ALN20210630BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20220509

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530