WO2023244792A1 - Au and ag containing glass composition and colored glass-based articles formed therefrom - Google Patents
Au and ag containing glass composition and colored glass-based articles formed therefrom Download PDFInfo
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- WO2023244792A1 WO2023244792A1 PCT/US2023/025547 US2023025547W WO2023244792A1 WO 2023244792 A1 WO2023244792 A1 WO 2023244792A1 US 2023025547 W US2023025547 W US 2023025547W WO 2023244792 A1 WO2023244792 A1 WO 2023244792A1
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- 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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear 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
- C03C4/02—Compositions for glass with special properties for coloured 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/40—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
-
- 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
- C03C2203/00—Production processes
- C03C2203/50—After-treatment
- C03C2203/52—Heat-treatment
Definitions
- the present specification generally relates to glass compositions and glass articles and, in particular, to glass compositions that are fusion formable and ion-exchangeable, colored glass articles formed therefrom.
- a glass composition comprises: greater than or equal to 55 mol% to less than or equal to 68 mol% SiCh; greater than or equal to 8 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 5 mol% to less than or equal to 15 mol% Li2O; greater than or equal to 0.0001 mol% to less than or equal to 0.5 mol% Au; and greater than or equal to 0.001 mol% to less than or equal to 1 mol% Ag.
- a glass composition comprises: greater than or equal to 55 mol% to less than or equal to 76 mol% SiCh; greater than or equal to 8 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 0.1 mol% to less than or equal to 10 mol% Na20; greater than 0 mol% to less than or equal to 4 mol% K2O; greater than 0 mol% to less than or equal to 3 mol% ZrCh; greater than 0 ppm to less than or equal to 30 ppm Au; and greater than 0 ppm to less than or equal to 2000 ppm Ag.
- a colored glass-based article comprises the glass composition of a preceding aspect.
- a colored glass-based article comprising: greater than 0 ppm to less than or equal to 30 ppm Au; and greater than 0 ppm to less than or equal to 2000 ppm Ag, wherein the colored glass-based article has a transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of: L* greater than or equal to 50 and less than or equal to 98; a* greater than or equal to -5 and less than or equal to 20; and b* greater than or equal to 15 and less than or equal to 105.
- a method of forming a glass-based article comprises heating a glass composition to form a glass-based article, the glass composition comprising the glass composition of a preceding aspect; and subjecting the glassbased article to a heat treatment cycle at a temperature greater than or equal to 500 °C and less than or equal to 800 °C for a duration greater than or equal to 0.25 hour and less than or equal to 24 hours to produce a colored glass-based article.
- FIG. 1 is a plan view of an electronic device incorporating any of the colored glass articles according to one or more embodiments described herein;
- FIG. 2 is a perspective view of the electronic device of FIG. 1 ;
- FIG. 3 is a photograph of colored glass articles with various compositions and heat treatments according to embodiments
- FIG. 5 is a photograph of colored glass articles with various compositions after heat treatment according to embodiments
- FIG. 6 is a photograph of colored glass articles with various compositions after heat treatment according to embodiments.
- FIG. 7 is a plot of a* (x-axis) vs. b* (y-axis), as measured under F2 illumination and a 10° standard observer angle, of colored glass articles after heat treatment according to embodiments;
- FIG. 8 is a plot of a* (x-axis) vs. b* (y-axis), as measured under F2 illumination and a 10° standard observer angle, of colored glass articles after various heat treatments according to embodiments;
- FIG. 11 is an FSM image of an ion exchanged colored glass article according to embodiments.
- FIG. 12 is an FSM image of an ion exchanged colored glass article according to embodiments
- FIG. 13 is an FSM image of an ion exchanged colored glass article according to embodiments.
- Fig. 14 is an FSM image of an ion exchanged colored glass article according to embodiments.
- a glass composition includes greater than or equal to 55 mol% to less than or equal to 68 mol% SiCh; greater than or equal to 8 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 5 mol% to less than or equal to 15 mol% Li2O; greater than or equal to 0.0001 mol% to less than or equal to 0.5 mol% Au; and greater than or equal to 0.001 mol% to less than or equal to 1 mol% Ag.
- a glass composition includes greater than or equal to 55 mol% to less than or equal to 76 mol% SiCh; greater than or equal to 8 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 0.1 mol% to less than or equal to 10 mol% Na20; greater than 0 mol% to less than or equal to 4 mol% K2O; greater than 0 mol% to less than or equal to 3 mol% ZrCh; greater than 0 ppm to less than or equal to 30 ppm Au; and greater than 0 ppm to less than or equal to 2000 ppm Ag.
- a method of forming a glass-based article includes heating a glass composition to form a glass-based article, the glass composition including: greater than or equal to 55 mol% to less than or equal to 76 mol% SiCh; greater than or equal to 8 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 0.1 mol% to less than or equal to 10 mol% Na20; greater than 0 mol% to less than or equal to 4 mol% K2O; greater than 0 mol% to less than or equal to 3 mol% ZrCh; greater than 0 ppm to less than or equal to 30 ppm Au; and greater than 0 ppm to less than or equal to 2000 ppm Ag; and subjecting the glass-based article to a heat treatment cycle at a temperature greater than or equal to 500 °C and less than or equal to 800 °C for a duration greater than or equal to 0.25 hour and less than or equal to 24 hours to produce a colored glass
- Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
- the concentration of Au, Ag, and Pt is specified in mole percent (mol%) and parts per million (ppm), unless otherwise specified.
- Mol% refers to the concentration of respective atoms in the glass composition in any form.
- Ppm refers to the number of units of mass of the respective constituent component per million units of total mass of the glass composition.
- the term “substantially free,” when used to describe the concentration and/or absence of a particular constituent component in a glass composition and the resultant colored glass article, means that the constituent component is not intentionally added to the glass composition and the resultant colored glass article.
- the glass composition and the resultant colored glass article may contain traces of the constituent component as a contaminant or tramp in amounts of less than 0.1 mol%.
- DOC depth of compression
- CIELAB color space refers to a color space defined by the International Commission on Illumination (CIE) in 1976. It expresses color as three values: L* for the lightness from black (0) to white (100), a* from green (-) to red (+), and b* from blue (-) to yellow (+).
- color gamut as used herein, r&rs to the pallet of colors that may be achieved by the colored glass articles within the CIELAB color space.
- Colorants may be added to aluminosilicate glass compositions to achieve a colored glass article having a desired color and improved mechanical properties.
- gold (Au) and silver (Ag) doped glass-based articles of the type described herein may appear orange, among other colors.
- the glass compositions and colored glass articles described herein may be described as alkali aluminosilicate glass compositions and colored glass-based articles and comprise SiCh, AI2O3, and Li2O.
- the glass compositions and colored glass articles described herein include Au and Agto produce colored glass articles having the desired color.
- the combination of Au and Ag may help to produce colored glass articles have a relatively high b* value (e.g., greater than or equal to 15, as measured under F2 illumination and a 10° standard observer angle).
- alkali oxides such as Li2O, Na20, and K2O, in the glass compositions enable the ion-exchangeability of the colored glass articles.
- SiCh is the primary glass former in the glass compositions described herein and may function to stabilize the network structure of the colored glass articles.
- concentration of SiCh in the glass compositions and resultant colored glass articles should be sufficiently high to enhance the chemical durability of the glass composition and, in particular, the resistance of the glass composition to degradation upon exposure to acidic solutions, basic solutions, and in water.
- the amount of SiCh may be limited to control the melting point of the glass composition, as the melting point of pure SiCh or high SiCh glasses is undesirably high. Thus, limiting the concentration of SiCh may aid in improving the meltability and the formability of the resultant colored glass article.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 55 mol% and less than or equal to 68 mol% SiCh.
- the concentration of SiCh in the glass composition and the resultant colored glass article may be greater than or equal to 58 mol%, greater than or equal to 60 mol%, greater than or equal to 62 mol%, greater than or equal to 64 mol%, greater than or equal to 66 mol%, or more.
- the concentration of SiCh in the glass composition and the resultant colored glass article may be greater than or equal to 55 mol% and less than or equal to 68 mol%, greater than or equal to 56 mol% and less than or equal to 67 mol%, greater than or equal to 57 mol% and less than or equal to 66 mol%, greater than or equal to 58 mol% and less than or equal to 65 mol%, greater than or equal to 59 mol% and less than or equal to 64 mol%, greater than or equal to 60 mol% and less than or equal to 63 mol%, greater than or equal to 61 mol% and less than or equal to 62 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 55 mol% and less than or equal to 76 mol% SiCh.
- the concentration of SiCh in the glass composition and the colored resultant glass article may be greater than or equal to 55 mol%, greater than or equal to 57 mol%, greater than or equal to 59 mol%, greater than or equal to 61 mol%, or more.
- the concentration of SiCh in the glass composition and the colored resultant glass article may be less than or equal to 76 mol%, less than or equal to 73 mol%, less than or equal to 70 mol%, or even less than or equal to 67 mol%.
- the concentration of SiCh in the glass composition and the resultant colored glass article may be greater than or equal to 55 mol% and less than or equal to 76 mol%, greater than or equal to 57 mol% and less than or equal to 73 mol%, greater than or equal to 59 mol% and less than or equal to 70 mol%, greater than or equal to 62 mol% and less than or equal to 67 mol%, or any and all sub-ranges formed from any of these endpoints.
- AI2O3 may also stabilize the glass network and additionally provides improved mechanical properties and chemical durability to the glass composition and the resultant colored glass article.
- the amount of AI2O3 may also be tailored to control the viscosity of the glass composition.
- AI2O3 may be included such that the resultant glass composition has the desired fracture toughness (e.g., greater than or equal to 0.7 MPa m 1/2 ). However, if the amount of AI2O3 is too high (e.g., greater than 20 mol%), the viscosity of the glass melt may increase, thereby diminishing the formability of the colored glass article.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 8 mol% and less than or equal to 18 mol% AI2O3.
- the concentration of AI2O3 in the glass composition and the resultant colored glass article may be greater than or equal to 8 mol%, greater than or equal to 9 mol%, greater than or equal to 10 mol%, greater than or equal to 11 mol%, greater than or equal to 12 mol%, greater than or equal to 13 mol%, greater than or equal to 14 mol%, greater than or equal to 15 mol%, greater than or equal to 16 mol%, greater than or equal to 17 mol%, or more.
- the concentration of AI2O3 in the glass composition and the resultant colored glass article may be greater than or equal to 8 mol% and less than or equal to 18 mol%, greater than or equal to 9 mol% and less than or equal to 17 mol%, greater than or equal to 10 mol% and less than or equal to 16 mol%, greater than or equal to 11 mol% and less than or equal to 15 mol%, greater than or equal to 12 mol% and less than or equal to 14 mol%, greater than or equal to 8 mol% and less than or equal to 13 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass compositions described herein may include B2O3.
- B2O3 helps improve the damage resistance of the resultant colored glass article.
- B2O3 reduces the formation of non-bridging oxygen, the presence of which may reduce fracture toughness.
- B2O3 is too high (e.g., greater than 10 mol%), the annealing point and strain point may decrease, which increases stress relaxation and reduces the overall strength of the colored glass article.
- the concentration of B2O3 in the glass composition and the resultant colored glass article may be less than or equal to 10 mol%, less than or equal to 9 mol%, less than or equal to 8 mol%, less than or equal to 7 mol%, less than or equal to 6 mol%, less than or equal to 5 mol%, less than or equal to 4 mol%, less than or equal to 3 mol%, less than or equal to 2 mol%, less than or equal to 1 mol%, or less.
- the concentration of B2O3 in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 10 mol%, greater than 0 mol% and less than or equal to 9 mol%, greater than or equal to 0.1 mol% and less than or equal to 8 mol%, greater than or equal to 1 mol% and less than or equal to 7 mol%, greater than or equal to 2 mol% and less than or equal to 6 mol%, greater than or equal to 3 mol% and less than or equal to 5 mol%, greater than or equal to 0 mol% and less than or equal to 4 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may be substantially free or free of B2O3.
- the glass compositions and the resultant colored glass articles contain alkali oxides, such as Li2O, Na20, and K2O, to enable the ion-exchangeability of the colored glass articles.
- alkali oxides such as Li2O, Na20, and K2O
- Li2O aids in the ion-exchangeability of the colored glass article and also reduces the softening point of the glass composition, thereby increasing the formability of the colored glass articles.
- Li2O decreases the melting point of the glass composition, which may help improve Au retention.
- the concentration of Li2O in the glass compositions and resultant colored glass articles should be sufficiently high to reduce the melting point of the glass composition and achieve the desired maximum central tension following ion-exchange. However, if the amount of Li2O is too high (e.g., greater than 15 mol%), the liquidus temperature may increase, thereby diminishing the manufacturability of the colored glass article.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 5 mol% and less than or equal to 15 mol% Li2O.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be greater than or equal to 5 mol%, greater than or equal to 7 mol%, greater than or equal to 9 mol%, greater than or equal to 11 mol%, greater than or equal to 13 mol%, or more.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be less than or equal to 15 mol%, less than or equal to 14 mol%, less than or equal to 13 mol%, less than or equal to 12 mol%, less than or equal to 11 mol%, less than or equal to 10 mol%, less than or equal to 9 mol%, or less.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be greater than or equal to 5 mol% and less than or equal to 15 mol%, greater than or equal to 6 mol% and less than or equal to 14 mol%, greater than or equal to 7 mol% and less than or equal to 13 mol%, greater than or equal to 8 mol% and less than or equal to 12 mol%, greater than or equal to 9 mol% and less than or equal to 11 mol%, greater than or equal to 10 mol% and less than or equal to 15 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may comprise greater than 0 mol% and less than or equal to 20 mol% Li2O.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol%, greater than or equal to 3 mol%, greater than or equal to 5 mol%, greater than or equal to 7 mol%, greater than or equal to 10 mol%, or more.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be less than or equal to 20 mol%, less than or equal to 18 mol%, less, than or equal to 16 mol%, less than or equal to 14 mol%, less than or equal to 12 mol%, or less.
- the concentration of Li2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 20 mol%, greater than or equal to 3 mol% and less than or equal to 18 mol%, greater than or equal to 5 mol% and less than or equal to 16 mol%, greater than or equal to 7 mol% and less than or equal to 14 mol%, greater than or equal to 10 mol% and less than or equal to 12 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may be substantially free or free of Li2O.
- Na2O improves diffusivity of alkali ions in the glass and thereby reduces ionexchange time and helps achieve the desired surface compressive stress. Na2O also improves the formability of the colored glass article. However, if too much Na2O is added to the glass composition, the melting point may be too low. As such, in embodiments, the concentration of Li2O present in the glass composition and the resultant colored glass article may be greater than the concentration of Na2O present in the glass composition and the resultant colored glass article.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 10 mol% Na2O.
- the concentration of Na2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol%, greater than 0 mol%, greater than or equal to 0.1 mol%, greater than or equal to 1 mol%, greater than or equal to 2 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 5 mol%, greater than or equal to 6 mol%, greater than or equal to 7 mol%, greater than or equal to 8 mol%, greater than or equal to 9 mol%, or more.
- the concentration of Na2 ⁇ in the glass composition and the resultant colored glass article may be less than or equal to 10 mol%, less than or equal to 9 mol%, less than or equal to 8 mol%, less than or equal to 7 mol%, less than or equal to 6 mol%, less than or equal to 5 mol%, less than or equal to 4 mol%, less than or equal to 3 mol%, less than or equal to 2 mol%, less than or equal to 1 mol%, or less.
- the concentration of Na20 in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 10 mol%, greater than or equal to 0.1 mol% and less than or equal to 9 mol%, greater than or equal to 1 mol% and less than or equal to 8 mol%, greater than or equal to 2 mol% and less than or equal to 7 mol%, greater than or equal to 3 mol% and less than or equal to 6 mol%, greater than or equal to 4 mol% and less than or equal to 5 mol%, or any and all sub-ranges formed from any of these endpoints.
- K2O promotes ion-exchange and may increase the depth of compression and decrease the melting point to improve the formability of the colored glass article. However, adding too much K2O may cause the surface compressive stress and melting point to be too low. Accordingly, in embodiments, the amount of K2O added to the glass composition may be limited.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 4 mol% K2O.
- the concentration of K2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol%, greater than 0 mol%, greater than or equal to 0.1 mol%, greater than or equal to 1 mol%, greater than or equal to 2 mol%, greater than or equal to 3 mol%, or more.
- the concentration of K2O in the glass composition and the resultant colored glass article may be less than or equal to 4 mol%, less than or equal to 3 mol%, less than or equal to 2 mol%, less than or equal to 1 mol%, less than or equal to 0.5 mol%, less than or equal to 0.25 mol%, or less.
- the concentration of I O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 4 mol%, greater than or equal to 0.1 mol% and less than or equal to 3 mol%, greater than or equal to 0.2 mol% and less than or equal to 2 mol%, greater than or equal to 0.5 mol% and less than or equal to 1 mol%, greater than or equal to 0 mol% and less than or equal to 0.5 mol%, greater than 0.1 mol% and less than or equal to 0.25 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may be substantially free or free of K2O.
- IGO refers to the sum of Li2O, Na2O, and K2O (i.e., IGO (mol%) + Na2O (mol%) + K2O (mol%)) in the glass composition and the resultant colored glass article.
- RO refers to the sum of MgO, ZnO, CaO, BaO, and SrO (i.e., MgO (mol%) + ZnO (mol%) + CaO (mol%) + BaO (mol%) + SrO (mol%)) in the glass composition and the resultant colored glass article.
- AI2O3 - R2O - RO in the glass composition and the resultant colored glass article may be less than or equal to 0 mol%, such as less than or equal to -0.5 mol%, less than or equal to - 1 mol%, or even less than or equal to -3 mol%.
- the glass compositions and the resultant colored glass articles described herein may further comprise P2O5.
- P2O5 may improve the ion exchange efficiency of the glass composition.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 3 mol% P2O5, such as greater than or equal to 0.1 mol% and less than or equal to 2 mol%, greater than or equal to 0.5 mol% and less than or equal to 1 mol%, or any and all sub-ranges formed from any of these endpoints.
- the glass composition and the resultant colored glass article may be substantially free or free of P2O5.
- the glass compositions and the resultant colored glass articles described herein may further comprise Fe2O3.
- Fe2O3 may also act as a colorant in addition to Au.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 1 mol% Fe2O3, such as greater than or equal to 0.01 mol% and less than or equal to 0.1 mol%.
- the glass composition and the resultant colored glass article may be substantially free or free of Fe2O3.
- the glass compositions and the resultant colored glass articles described herein may further comprise one or more fining agents.
- the fining agents may include, for example, SnCh.
- the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 1 mol% SnCh, such as greaterthan or equal to 0.01 mol% and less than or equal to 0.1 mol%.
- the glass composition and the resultant colored glass article may be substantially free or free of SnCh.
- the glass composition and the resultant colored glass article may include alkaline earth oxides, such as MgO, CaO, SrO, and BaO, and may also include ZnO.
- the concentration of Ti(h in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 1 mol%. In embodiments, the concentration of Ti(h in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0.1 mol% and less than or equal to 0.5 mol%, or any and all sub-ranges formed from any of these endpoints. In embodiments, the glass composition and the resultant colored glass article may be substantially free or free of TiCh.
- the concentration of Y2O3 in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 0.5 mol%. In embodiments, the concentration of Y2O3 in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol% and less than or equal to 0.5 mol%, greater than or equal to 0.01 mol% and less than or equal to 0.1 mol%, or any and all sub-ranges formed from any of these endpoints. In embodiments, the glass composition and the resultant colored glass article may be substantially free or free of Y2O3.
- the concentration of Au in the glass composition and the resultant colored glass article may be greater than or equal to 0.0001 mol%, greater than or equal to 0.0002 mol%, greater than or equal to 0.0003 mol%, greater than or equal to 0.0004 mol%, greater than or equal to 0.0005 mol%, greater than or equal to 0.0006 mol%, greater than or equal to 0.0007 mol%, greater than or equal to 0.0008 mol%, greater than or equal to 0.0009 mol%, greater than or equal to 0.001 mol%, greater than or equal to 0.002 mol%, greater than or equal to 0.003 mol%, greater than or equal to 0.004 mol%, greater than or equal to 0.005 mol%, greater than or equal to 0.006 mol%, greater than or equal to 0.007 mol%, greater than or equal to 0.008 mol%, greater than or equal to 0.009 mol%, greaterthan or equal to 0.01 mol%, ormore.
- the concentration of Au in the glass composition and the resultant colored glass article may be greater than or equal to 0.0001 mol% and less than or equal to 0.5 mol%, greater than or equal to 0.0001 mol% and less than or equal to 0.1 mol%, greater than or equal to 0.0002 mol% and less than or equal to 0.09 mol%, greater than or equal to 0.0003 mol% and less than or equal to 0.08 mol%, greater than or equal to 0.0003 mol% and less than or equal to 0.07 mol%, greater than or equal to 0.0004 mol% and less than or equal to 0.06 mol%, greater than or equal to 0.0005 mol% and less than or equal to 0.05 mol%, greater than or equal to 0.0006 mol% and less than or equal to 0.04 mol%, greater than or equal to 0.0007 mol% and less than or equal to 0.03 mol%, greater than or equal to 0.0008 mol% and less than or equal to 0.02 mol%, greater than or equal to 0.000
- the concentration of Au in the glass composition and the resultant colored glass article may be greater than 0 ppm and less than or equal to 30 ppm, greater than or equal to 0.5 ppm and less than or equal to 20 ppm, greater than or equal to 1 ppm and less than or equal to 10 ppm, greater than or equal to 3 ppm and less than or equal to 5 ppm, or any and all subranges formed from any of these endpoints.
- the glass compositions and the resultant colored glass articles described herein include Ag as an additional colorant to achieve the desired color.
- the glass composition and the resultant colored glass article may include Ag in a concentration greater than or equal to 0.001 mol% and less than or equal to 1 mol%, such as greater than or equal to 0.001 mol% and less than or equal to 0.1 mol%.
- the concentration of Ag in the glass composition and the resultant colored glass article may be greater than or equal to 0.001 mol%, greater than or equal to 0.01 mol%, greater than or equal to 0.02 mol%, greater than or equal to 0.03 mol%, greater than or equal to 0.04 mol%, greater than or equal to 0.05 mol%, greater than or equal to 0.06 mol%, greater than or equal to 0.07 mol%, greater than or equal to 0.08 mol%, greater than or equal to 0.09 mol%, greater than or equal to 0.10 mol%, greater than or equal to 0.11 mol%, greater than or equal to 0.12 mol%, greater than or equal to 0.13 mol%, greater than or equal to 0.14 mol%, greater than or equal to 0.15 mol%, greater than or equal to 0.16 mol%, greater than or equal to 0.17 mol%, greater than or equal to 0.18 mol%, greater than or equal to 0.19 mol%, or more.
- the concentration of Ag in the glass composition and the resultant colored glass article may be less than or equal to 1 mol%, less than or equal to 0. 1 mol%, less than or equal to 0.09 mol%, less than or equal to 0.08 mol%, less than or equal to 0.07 mol%, less than or equal to 0.06 mol%, less than or equal to 0.05 mol%, less than or equal to 0.04 mol%, less than or equal to 0.03 mol%, less than or equal to 0.01 mol%, or less.
- the concentration of Ag in the glass composition and the resultant colored glass article may be greater than or equal to 0.001 mol% and less than or equal to 1 mol%, greater than or equal to 0.001 mol% and less than or equal to 0.1 mol%, greater than or equal to 0.01 mol% and less than or equal to 0.09 mol%, greater than or equal to 0.02 mol% and less than or equal to 0.08 mol%, greater than or equal to 0.03 mol% and less than or equal to 0.07 mol%, greater than or equal to 0.04 mol% and less than or equal to 0.06 mol%, greater than or equal to 0.01 mol% and less than or equal to 0.05 mol%, or any and all sub-ranges formed from any of these endpoints.
- the amount of Ag in the glass composition and the resultant colored glass article may be greater than 0 ppm and less than or equal to 2000 ppm.
- the concentration of Ag in the glass composition and the resultant colored glass article may be greater than 0 ppm, greater than or equal to 50 ppm, greater than or equal to 100 ppm, greater than or equal to 200 ppm, or more.
- the concentration of Ag in the glass composition and the resultant colored glass article may be less than or equal to 2000 ppm, less than or equal to 1500 ppm, less than or equal to 1000 ppm, less than or equal to 500 ppm, or less.
- the colored glass article may have a transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of b* greater than or equal to -25 and less than or equal to 45, such as greater than or equal to -21 and less than or equal to 41, greater than or equal to -15 and less than or equal to 40, greater than or equal to -10 and less than or equal to 45, greater than or equal to -5 and less than or equal to 40, greater than or equal to 0 and less than or equal to 35, greater than or equal to 5 and less than or equal to 30, greater than or equal to 10 and less than or equal to 25, greater than or equal to -20 and less than or equal to 20, or any and all sub-ranges formed from any of these endpoints.
- b* greater than or equal to -25 and less than or equal to 45, such as greater than or equal to -21 and less than or equal to 41, greater than or equal to -15 and less than or equal to 40, greater than or equal to -10 and less than or equal
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of b* greater than or equal to 15 and less than or equal to 105, greater than or equal to 25 and less than or equal to 95, greater than or equal to 35 and less than or equal to 85, greater than or equal to 45 and less than or equal to 75, greater than or equal to 55 and less than or equal to 105, greater than or equal to 65 and less than or equal to 95, or any and all sub-ranges formed from any of these endpoints.
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of a* greater than or equal to -5 and less than or equal to 20, greater than or equal to -3 and less than or equal to 15, greater than or equal to -1 and less than or equal to 10, greater than or equal to 1 and less than or equal to 20, greater than or equal to 3 and less than or equal to 15, greater than or equal to 5 and less than or equal to 10, greater than or equal to -5 and less than or equal to 5, or any and all subranges formed from any of these endpoints.
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of L* greater than or equal to 50 and less than or equal to 98.
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, of L* greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or more.
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, of L* less than or equal to 98, less than or equal to 95, less than or equal to 90, less than or equal to 85, or less.
- the colored glass-based article has a transmittance color coordinate in the CIELAB color space, of L* greater than or equal to 50 and less than or equal to 98, greater than or equal to 60 and less than or equal to 95, greater than or equal to 70 and less than or equal to 90, greater than or equal to 80 and less than or equal to 85, or any and all sub-ranges formed from any of these endpoints.
- Different color coordinates within the color gamut may be achieved by altering the heat treatment cycle used to produce the resultant colored glass articles.
- the heat treatment cycle is characterized by the temperature of the environment (i.e., the oven) and the duration of the cycle (i.e., the time the glass article is exposed to the heated environment).
- the phrase “temperature of the heat treatment cycle” refers to the temperature of the environment (i.e., the oven).
- glass articles formed from the glass compositions described herein are heat treated in an isothermal oven to produce the resultant colored glass articles.
- the temperature of the heat treatment cycle may be greater than or equal to 500 °C, greater than or equal to 550 °C, greater than or equal to 575 °C, greater than or equal to 600 °C, greater than or equal to 625 °C, greater than or equal to 650 °C, greater than or equal to 675 °C, greater than or equal to 700 °C, greater than or equal to 725 °C, greater than or equal to 750 °C, greater than or equal to 775 °C, or more.
- the temperature of the heat treatment cycle may be greater than or equal to 500 °C and less than or equal to 800 °C, greater than or equal to 525 °C and less than or equal to 775 °C, greater than or equal to 550 °C and less than or equal to 750 °C, greater than or equal to 575 °C and less than or equal to 725 °C, greater than or equal to 600 °C and less than or equal to 700 °C, greater than or equal to 625 °C and less than or equal to 675 °C, greater than or equal to 500 °C and less than or equal to 650 °C, or any and all sub-ranges formed from any of these endpoints.
- the duration of the heat treatment cycle may be less than or equal to 24 hours, less than or equal to 18 hours, less than or equal to 16 hours, less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, less than or equal to 8 hours, less than or equal to 7 hours, less than or equal to 6 hours, less than or equal to 5 hours, less than or equal to 4 hours, less than or equal to 3 hours, less than or equal to 2 hours, less than or equal to 1 hour, less than or equal to 0.5 hours, or less.
- the duration of the heat treatment cycle may be greater than or equal to 0.25 hours and less than or equal to 24 hours, greater than or equal to 0.5 hours and less than or equal to 18 hours, greater than or equal to 1 hour and less than or equal to 16 hours, greater than or equal to 2 hours and less than or equal to 12 hours, greater than or equal to 3 hours and less than or equal to 10 hours, greater than or equal to 4 hours and less than or equal to 9 hours, greater than or equal to 5 hours and less than or equal to 8 hours, greater than or equal to 6 hours and less than or equal to 7 hours, or any and all sub-ranges formed from any of these endpoints.
- the heating rate of the heat treatment may be greater than or equal to TC/min to less than or equal to 10 °C/min. In embodiments, the heating rate of the heat treatment may be greater than or equal to TC/min, greater than or equal to 2°C/min, or more. In embodiments, the heating rate of the heat treatment may be less than or equal to 10 °C/min, less than or equal to 8 °C/min, less than or equal to 6 °C/min, less than or equal to 4 °C/min, or less.
- the heating rate of the heat treatment may be greater than or equal to TC/min and less than or equal to 10 °C/min, greater than or equal to 2°C/min and less than or equal to 8 °C/min, greater than or equal to TC/min and less than or equal to 6 °C/min, greater than or equal to 2°C/min and less than or equal to 4 °C/min, or any and all sub-ranges formed from any of these endpoints.
- the cooling rate of the heat treatment may be greater than or equal to 1 °C/min, greater than or equal to 2 °C/min, or more. In embodiments, the cooling rate of the heat treatment may be less than or equal to 10 °C/min, less than or equal to 8 °C/min, less than or equal to 6 °C/min, less than or equal to 4 °C/min, or less.
- the cooling rate of the heat treatment may be greater than or equal to TC/min and less than or equal to 10 °C/min, greater than or equal to 2°C/min and less than or equal to 8 °C/min, greater than or equal to TC/min and less than or equal to 6 °C/min, greater than or equal to 2°C/min and less than or equal to 4 °C/min, or any and all sub-ranges formed from any of these endpoints.
- the glass compositions and the resultant colored glass articles may have color stability.
- the glass compositions and the resultant colored glass articles when subjected to heat treatment at a given temperature and for a given time, may have a delta b* value of less than 1 b* unit/°C.
- the glass compositions and the resultant colored glass articles may have thermal stability.
- the colored glass-based article may have a delta b* transmittance color coordinate in the CIELAB color space, as measured under F2 illumination and a 10° standard observer angle, of greater than or equal to -1 and less than or equal to 1, when exposed to ultraviolet light for 24 hours.
- the metal ions are monovalent metal ions (e.g., Li + , Na + , K + , and the like), and ion-exchange is accomplished by immersing the glass article made from the glass composition in a bath comprising at least one molten salt of the larger metal ion that is to replace the smaller metal ion in the colored glass article .
- a bath comprising at least one molten salt of the larger metal ion that is to replace the smaller metal ion in the colored glass article .
- other monovalent ions such as Ag + , Tl + , Cu + , and the like may be exchanged for monovalent ions.
- the ion-exchange process or processes that are used to strengthen the colored glass article made from the glass composition may include contacting the colored glass article with an ionexchange medium.
- the ion-exchange medium may be a molten salt bath.
- the ion-exchange process may include, but is not limited to, immersion in a single bath or multiple baths of like or different compositions with optional washing and/or annealing steps between immersions.
- the colored glass article may be exposed to the ion exchange solution for a duration greater than or equal to 2 hours and less than or equal to 24 hours, greater than or equal to 2 hours and less than or equal to 12 hours, greater than or equal to 3 hours and less than or equal to 11 hours, greater than or equal to 4 hours and less than or equal to 10 hours, greater than or equal to 5 hours and less than or equal to 9 hours, greater than or equal to 6 hours and less than or equal to 8 hours, greater than or equal to 2 hours and less than or equal to 7 hours, or any and all sub-ranges formed from any of these endpoints.
- the colored glass article made from the glass composition described herein may have a thickness “t” and may be ion-exchanged to achieve a depth of compression greater than or equal to 0.15t and less than or equal to 0.3t, greater than or equal to 0.16t and less than or equal to 0.29t, greater than or equal to 0.17t and less than or equal to 0.28t, greater than or equal to 0.18t and less than or equal to 0.27t, greater than or equal to 0.19t and less than or equal to 0.26t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.2 It and less than or equal to 0.24t, greater than or equal to 0.22t and less than or equal to 0.23t, or any and all sub-ranges formed from any of these endpoints.
- the colored glass article made from the glass composition may have a surface compressive stress after ion-exchange strengthening greater than or equal to 300 MPa, greater than or equal to 400 MPa, greater than or equal to 500 MPa, greater than or equal to 600 MPa, greater than or equal to 700 MPa, greater than or equal to 800 MPa, greater than or equal to 900 MPa, or more.
- the colored glass article made from the glass composition may have a surface compressive stress after ion-exchange strengthening greater than or equal to 300 MPa and less than or equal to 1 GPa, greater than or equal to 400 MPa and less than or equal to 900 MPa, greater than or equal to 500 MPa and less than or equal to 800 MPa, greater than or equal to 600 MPa and less than or equal to 700 MPa, or any and all sub-ranges formed from any of these endpoints.
- the colored glass article made from the glass composition may have a maximum central tension after ion-exchange strengthening less than or equal to 250 MPa, less than or equal to 225 MPa, less than or equal to 200 MPa, less than or equal to 175 MPa, less than or equal to 150 MPa, less than or equal to 125 MPa, less than or equal to 100 MPa, less than or equal to 75 MPa, or less.
- FIG. 5 a photograph of glass articles after heat treatment, with brown articles shown on the left side of the image, orange articles shown in the middle of the image, and yellow articles shown on the right side of the image.
- glass compositions including Au and Ag may be used to form glass articles having a b* greater than or equal to 15.
- glass articles formed from example glass composition 17 including about 900 ppm Ag and varying amounts of Au from 0 ppm to 5 ppm are shown.
- the glass articles were subjected to a heat treatment including heating the glass article from room temperature to 580 °C at a heating rate of 4 °C/min, holding the glass articles at the 580 °C for 6 hours, then cooling the glass article to room temperature.
- color started to be visibly observable as the Au concentration increased to 1.4 ppm.
- the presence of Au, in combination with Ag helps to achieve yellow glass articles (i.e., glass articles having a b* greater than or equal to 15).
- the CIELAB color space achieved by subjecting 2.4 mm thick glass articles formed from example glass composition 17 to heat treatment is listed and shown.
- the heat treatment included heating the glass article from room temperature to 620 °C at a heating rate of 4 °C/min, holding the glass articles at 620 °C for 6 hours, then cooling the glass article to room temperature.
- FIG. 8 the CIELAB color space achieved by subjecting glass articles formed from glass composition 17 to different heat treatments as indicated in the figure (“temperature” - “duration” - “heating rate”) is shown.
- the glass compositions described herein having a combination of Au and Ag may be subjected to various heat treatments to achieve yellow glass articles (i.e., glass articles having a b* greater than or equal to 15).
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Abstract
Description
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/873,952 US20250361171A1 (en) | 2022-06-17 | 2023-06-16 | Au and ag containing glass composition and colored glass-based articles formed therefrom |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263353238P | 2022-06-17 | 2022-06-17 | |
| US63/353,238 | 2022-06-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2023/025547 Ceased WO2023244792A1 (en) | 2022-06-17 | 2023-06-16 | Au and ag containing glass composition and colored glass-based articles formed therefrom |
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| WO (1) | WO2023244792A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120208028A1 (en) * | 2008-12-26 | 2012-08-16 | Kazuaki Hashimoto | Glass substrate and method for manufactring the same |
| US20150262605A1 (en) * | 2008-03-19 | 2015-09-17 | Hoya Corporation | Glass for magnetic recording media substrates, magnetic recording media substrates, magnetic recording media and method for preparation thereof |
| US20150307390A1 (en) * | 2010-05-31 | 2015-10-29 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 BASED CRYSTALLIZED GLASS AND PRODUCTION METHOD FOR THE SAME |
| US20160368818A1 (en) * | 2010-11-30 | 2016-12-22 | Corning Incorporated | Fusion formed and ion exchanged glass-ceramics |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201245080A (en) * | 2011-03-17 | 2012-11-16 | Asahi Glass Co Ltd | Glass for chemical strengthening |
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- 2023-06-16 WO PCT/US2023/025547 patent/WO2023244792A1/en not_active Ceased
- 2023-06-16 US US18/873,952 patent/US20250361171A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150262605A1 (en) * | 2008-03-19 | 2015-09-17 | Hoya Corporation | Glass for magnetic recording media substrates, magnetic recording media substrates, magnetic recording media and method for preparation thereof |
| US20120208028A1 (en) * | 2008-12-26 | 2012-08-16 | Kazuaki Hashimoto | Glass substrate and method for manufactring the same |
| US20150307390A1 (en) * | 2010-05-31 | 2015-10-29 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 BASED CRYSTALLIZED GLASS AND PRODUCTION METHOD FOR THE SAME |
| US20160368818A1 (en) * | 2010-11-30 | 2016-12-22 | Corning Incorporated | Fusion formed and ion exchanged glass-ceramics |
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| US20250361171A1 (en) | 2025-11-27 |
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