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
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
  • C03C23/002—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ultraviolet light
• • 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
  • C03C3/089—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
  • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
• • 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

Definitions

• the present disclosure relates generally to glass articles and natively colored glass housings and methods of making the same and, more particularly, to glass articles and natively colored glass housings comprising a CIE L* value of 50 or more and methods of making the same.
• Glass articles are commonly used, for example, in display devices, for example, liquid crystal displays (LCDs), electrophoretic displays (EPD), organic light-emitting diode displays (OLEDs), plasma display panels (PDPs), or the like. Glass articles can form part of a housing as well as covering the display.
• LCDs liquid crystal displays
• EPD electrophoretic displays
• OLEDs organic light-emitting diode displays
• PDPs plasma display panels
• Aluminosilicate glass articles may exhibit superior ion-exchangeability and drop performance.
• Various industries including the consumer electronics industry, desire colored materials with the same or similar strength and fracture toughness properties as existing, non-colored, ion-exchange strengthened glasses.
• a color of glass articles may change over time. Accordingly, a need exists for an alternative colored glass article with minimal change in color.
• glass articles and natively colored glass housings including the same that are resistant to color change from ultraviolet (e.g., UV-C) light exposure.
• the glass articles can exhibit a high brightness (e.g., CIE L* value greater than 50 or greater than 70 and less than 96.5) color that can be consistent through UV-C exposure.
• the glass article can comprise a surface layer where any photodarkening can be restricted to, for example, even after repeated and/or extended UV-C exposure.
• Providing the surface layer can reduce a color change of the glass article such that it may not be discernable to a user that intermittently exposes the glass article to UV-C light.
• Providing a saturated surface layer can prevent the glass article from changing color as a result of subsequent (e.g., frequent or extended) UV-C exposure.
• the glass-based material of the glass article can provide good dimensional stability, good impact resistance, good crack resistance, good puncture resistance, and/or good flexural strength.
• the glass article can include a compressive stress region (e.g., be chemically strengthened), which can provide improved crack resistance, puncture resistance, impact resistance, and/or improved flexural strength.
• Providing the glass article with ZrCL e.g., from 0.2 mol% to 0.5 mol%) can provide enhanced resistance to color change from UV-C exposure.
• forming the glass article with a precursor material comprising nitrates can provide enhanced resistance to color change from UV-C exposure.
• minimizing the combination of R 2 O, CaO, MgO, and ZnO in the glass composition may provide the resultant colored glass article with a desirable dielectric constant, for example when the colored glass article is used as a portion of a housing for an electronic device.
• Providing a dielectric constant for frequencies from 10 GHz to 60 GHz from 5.6 to 6.4 can allow wireless communication through the glass article.
• the glass articles and housings of the present disclosure can absorb a large portion (e.g., majority) of ultraviolet light in a first half of the thickness of the glass article, which can reduce an amount of ultraviolet light incident on the other half of the glass article and reduce (e.g., prevent) changes in the CIE coordinates associated with the other half of the glass article.
• Providing a natively colored glass housing with a colored glass article can eliminate the need for an additional layer to impart color to the housing, which can simplify assembly and provide a more consistent color. Consequently, the natively colored glass housing including the glass article can provide an aesthetically pleasing appearance (e.g., color) while simultaneously protecting an electronic device from damage and/or permitting wireless communication therethrough.
• a glass article comprising: a thickness defined between a first major surface and a second major surface opposite the first major surface; a surface layer extending from the first major surface to a first depth; and a bulk region including the second major surface; wherein the glass article, including the surface layer, exhibits a CIE L* value of about 50 or more, the surface layer corresponds to a different color than a color associated with the bulk region, and the first depth is about 90 micrometers or less.
• Aspect 2 The glass article of aspect 1, wherein the glass article exhibits a CIE L* value of about 70 or more.
• Aspect 3 The glass article of any one of aspects 1-2, wherein a CIE L* value corresponding to the surface layer is less than the CIE L* value of the glass article on a thickness adjusted basis by 0. 1 or more.
• Aspect 4 The glass article of any one of aspects 1-3, wherein an absolute value of a CIE a* value of the glass article is about 0.3 or more, and an absolute of the CIE b* value of the glass article is about 0.2 or more.
• Aspect 5 The glass article of aspect 4, wherein the CIE a* value of the glass article is about 1 or more.
• Aspect 6 The glass article of any one of aspects 4-5, wherein the CIE b* value of the glass article is about 1 or more.
• Aspect 7 The glass article of any one of aspects 1-6, wherein after the first major surface of the glass article is impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, a color associated with the saturated bulk region is substantially the same as the color associated with the bulk region, the second depth is about 500 micrometers or less, and the saturated surface layer corresponds to a different color than the color of the saturated bulk region.
• Aspect 8 The glass article of aspect 7, wherein a transition between a color associated with the saturated surface layer and the color associated with the saturated bulk region is about 400 micrometers or less.
• Aspect 9 The glass article of any one of aspects 7-8, wherein a CIE L* value of the saturated glass article is less than the CIE L* value by about 2 or less on a thickness adjusted basis.
• Aspect 10 The glass article of any one of aspects 1-9, wherein a composition of the surface layer is substantially the same as the composition of the bulk region.
• Aspect 11 A glass article comprising a thickness defined between a first major surface and a second major surface opposite the first major surface, wherein the glass article exhibits a CIE L* value of about 50 or more, an absolute value of a CIE a* value is about 0.3 or more, and an absolute value of a CIE b* value is about 0.2 or more.
• Aspect 12 The glass article of any one of aspects 1-11, wherein an instantaneous CIE L* value of the glass article monotonically increases as a depth from the first major surface increases.
• Aspect 13 The glass article of any one of aspects 1-11, wherein a maximum absolute value of a gradient of an instantaneous CIE L* value of the glass article is about 0.01 or more per 100 pm.
• Aspect 14 The glass article of any one of aspects 12-13, wherein after the first major surface of the glass article is impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, a profile of the instantaneous CIE L* value of the saturated glass article comprises a region with a first slope abutting a region with a second slope, wherein an absolute value of the first slope is less than an absolute value of the second slope by about 0.01 or more per 100 micrometers.
• Aspect 15 The glass article of any one of aspects 1-6 or 11-13 inclusive, wherein after the first major surface of the glass article is impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, the CIE L* value of the saturated glass article is less than the CIE L* value of the glass article by 0.25 or less.
• Aspect 16 The glass article of any one of aspects 4-6 or 11-13 inclusive, wherein after the first major surface of the glass article is impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, the CIE a* value of the saturated glass article is less than the CIE a* value of the glass article by 0.25 or less.
• Aspect 18 The glass article of aspect 16, wherein an absolute value of a difference between the CIE b* value of the saturated glass article and the CIE b* value of the glass article is about 0.2 or less.
• Aspect 19 The glass article of any one of aspects 7-9 or 14-18 inclusive, wherein the saturated glass article is measured after the first major surface of the glass article is impinged with UV-C radiation with the fluence of 3 milliwatts per centimeter squared of the surface area of the first major surface for 25 hours or more.
• Aspect 20 The glass article of any one of aspects 7-10 or 14-18 inclusive, wherein the saturated glass article is measured after the first major surface of the glass article is impinged with UV-C radiation with the fluence of 3 milliwatts per centimeter squared of the surface area of the first major surface for 50 hours.
• Aspect 21 The glass article of any one of aspects 1-20, wherein the glass article comprises an average absorptivity for optical wavelengths from 360 nm to 400 nm of about 0. 1 mm' 1 or more.
• Aspect 22 The glass article of any one of aspects 1-20, wherein the glass article comprises an average absorptivity for optical wavelengths from 200 nm to 280 nm of about 0. 1 mm' 1 or more.
• Aspect 23 The glass article of any one of aspects 1-22, wherein the glass article comprises titanium oxide, zirconia, iron oxide, cerium oxide, or combinations thereof.
• Aspect 24 The glass article of any one of aspects 1-23, wherein the glass article comprises from 5 parts-per-million to 15 parts-per-million gold in the glass article.
• Aspect 25 The glass article of any one of aspects 1-24, wherein the glass article comprises, as a mol% of the glass article: from about 50 mol% to about 75 mol% SiO 2 ; from about 7 mol% to about 20 mol% Al 2 O 3 ; from about 13 mol% to about 20 mol% of at least one alkali metal oxide, alkali metal oxides including Li 2 O, Na 2 O, and K 2 O; and at least one of B2O 3 or P 2 O 5 .
• Aspect 26 The glass article of any one of aspects 1-21, wherein the glass article comprises, as a mol% of the glass article: from 60 mol% to 65 mol% SiO 2 ; from 12 mol% to 17 mol% Al 2 O 3 ; from 3 mol% to 6 mol% B2O 3 ; from 13 mol% to 20 mol% of at least one alkali metal oxide, alkali metal oxides including Li 2 O, Na 2 O, and K 2 O; from 0.5 mol% to 4 mol% CaO; from 0 mol% to 1 mol% ZnO; from 0 mol% to 1 mol% ZrCT; and from 0.01 mol% to 0.25 mol% SnO 2 .
• Aspect 27 The glass article of any one of aspects 25-26, wherein the glass article comprises, as a mol% of the glass article, from 0.2 mol% to 0.5 mol% ZrO 2 .
• Aspect 28 The glass article of any one of aspects 1-27, wherein the glass article comprises a dielectric constant at frequencies from 10 GigaHertz to 60 GigaHertz of from about 5.6 to about 6.4.
• Aspect 29 The glass article of any one of aspects 1-28, wherein the glass article exhibits a fracture toughness of 0.60 MPam 1/2 or more, and a Young’s modulus from about 50 GigaPascals to about 100 GigaPascals.
• Aspect 30 The glass article of any one of aspects 1-29, wherein the thickness of the glass article is from about 30 micrometers to about 5 millimeters.
• Aspect 31 The glass article of any one of aspects 1-30, wherein a total transmittance of at least one 10 nm band within a wavelength range of 380 nm to 750 nm through the first thickness is from 3% to 80%.
• Aspect 32 The glass article of any one of aspects 1-30, wherein average transmittance of greater than or equal to 10% and less than or equal to 92% over a wavelength range of 400 nm to 700 nm.
• Aspect 33 The glass article of any one of aspects 1-32, wherein the glass article comprises a colorant selected from the group consisting of silver, gold, chromium, cobalt, titanium, nickel, cerium, copper, and combinations thereof.
• Aspect 34 The glass article of any one of aspects 1-33, wherein the glass article comprises at least one crystalline phase.
• Aspect 35 The glass article of aspect 34, wherein a crystallinity of the glass article is 10 wt% or less.
• Aspect 36 The glass article of any one of aspects 1-35, further comprising a first compressive stress region extending to a first depth of compression from the first compressive stress region.
• Aspect 37 The glass article of aspect 36, wherein a maximum compressive stress of the first compressive stress region is about 400 MegaPascals or more.
• a consumer electronic product comprising: a housing comprising a front surface, a back surface, and side surfaces; electrical components at least partially within the housing, the electrical components comprising a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display, wherein at least one of a portion of the housing comprises the glass article of any one of aspects 1-37.
• a natively colored glass housing for a consumer electronic device comprising: the glass article of any one of aspects 1-37; and a reflector layer disposed on the glass article, the reflector layer is opaque and has a CIE L* value of 70 or more.
• Aspect 40 The natively colored glass housing of aspect 39, further comprising: circuitry comprising an antenna that transmits signals within a range of 26 GHz to 40 GHz; the natively colored glass housing at least partially surrounding the circuitry; and a structure formed as an integral portion of the glass article, wherein the structure comprises a perimeter demarcating a second thickness of the structure that differs from the thickness of the glass article by at least 150 pm, wherein the antenna is positioned and oriented such that the signals are transmitted through the structure of the glass sheet of the panel of the housing.
• a method of forming a glass article comprising: melting precursor materials together to form a glass article; and impinging a first major surface of the glass article with ultraviolet light to form a surface layer extending to a first depth from a first major surface, the glass article comprising a bulk region including a second major surface opposite the first major surface, wherein the glass article, including the surface layer, exhibits a CIE L* value of about 50 or more, the surface layer corresponds to a different color than a color associated with the bulk region, and the first depth is about 90 micrometers or less.
• Aspect 42 The method of aspect 37, wherein after the first major surface of the glass article is further impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, a color associated with the saturated bulk region is substantially the same as the color associated with the bulk region, the second depth is about 500 micrometers or less, and the saturated surface layer corresponds to a different color than the color of the saturated bulk region.
• Aspect 43 The method of aspect 42, wherein a transition between a color associated with the saturated surface layer and the color associated with the saturated bulk region is about 400 micrometers or less.
• Aspect 44 The method of any one of aspects 42-43, wherein a CIE L* value of the saturated glass article is less than the CIE L* value by about 2 or less on a thickness adjusted basis.
• Aspect 45 The method of any one of aspects 41-44, wherein a composition of the surface layer is substantially the same as the composition of the bulk region.
• a method of forming a glass article comprising: melting precursor materials together to form a glass article; and impinging a first major surface of the glass article with ultraviolet light, wherein the glass article exhibits a CIE L* value of about 50 or more, an absolute value of a CIE a* value is about 0.3 or more, and an absolute value of a CIE b* value is about 0.2 or more.
• Aspect 47 The method of any one of aspects 41-46, wherein an instantaneous CIE L* value of the glass article monotonically increases as a depth from the first major surface increases.
• Aspect 48 The method of any one of aspects 41-46, wherein a maximum absolute value of a gradient of an instantaneous CIE L* value of the glass article is about 0.01 or more per 100 pm.
• Aspect 49 The glass article of any one of aspects 47-48, wherein after the first major surface of the glass article is further impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, a profile of the instantaneous CIE L* value of the saturated glass article comprises a region with a first slope abutting a region with a second slope, wherein an absolute value of the first slope is less than an absolute value of the second slope by about 0.01 or more per 100 micrometers.
• Aspect 50 The method of aspect 41 or 46, wherein after the first major surface of the glass article is further impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, the CIE L* value of the saturated glass article is less than the CIE L* value of the glass article by 0.25 or less.
• Aspect 51 The method of aspect 41 or 46, wherein after the first major surface of the glass article is further impinged with UV-C radiation with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface for 10 hours or more as a saturated glass article, the saturated glass article comprises a saturated surface layer extending from the first major surface to a second depth and a saturated bulk region, the CIE a* value of the saturated glass article is less than the CIE a* value of the glass article by 0.25 or less.
• Aspect 52 The method of aspect 51, wherein the CIE b* value of the glass article is about 1 or more, and an absolute value of a difference between the CIE b* value of saturated glass article and the CIE b* value of the glass article, as a percentage of the CIE b* value of the glass article, is about 33% or less.
• Aspect 53 The method of aspect 51, wherein an absolute value of a difference between the CIE b* value of the saturated glass article and the CIE b* value of the glass article is about 0.2 or less.
• Aspect 54 The method of any one of aspects 42-44 or 49-53 inclusive, wherein the further impinging occurs for 25 hours or more.
• Aspect 55 The method of any one of aspects 42-44 or 49-53 inclusive, wherein the further impinging occurs for 50 hours.
• Aspect 56 The method of any one of aspects 42-46 inclusive, wherein an absolute value of a CIE a* value of the glass article is about 0.3 or more, and an absolute of the CIE b* value of the glass article is about 0.2 or more.
• Aspect 57 The method of any one of aspects 46 or 56 inclusive, wherein the CIE a* value of the glass article is about 1 or more.
• Aspect 58 The method of any one of aspects 45 or 56-57 inclusive, wherein the CIE b* value of the glass article is about 1 or more.
• Aspect 59 The method of any one of aspects 41-58, wherein the raw materials comprise, as a mol% of the raw materials: from about 50 mol% to about 75 mol% SiO 2 ; from about 7 mol% to about 20 mol% Al 2 O 3 ; from about 13 mol% to about 20 mol% of at least one alkali metal oxide, alkali metal oxides including Li 2 O, Na 2 O, and K 2 O; and at least one of B2O 3 or P 2 O 5 .
• Aspect 60 The method of any one of aspects 41-59, wherein the raw materials comprise, as a mol% of the raw materials: from 60 mol% to 65 mol% SiO 2 ; from 12 mol% to 17 mol% Al 2 O 3 ; from 3 mol% to 6 mol% B2O 3 ; from 13 mol% to 20 mol% of at least one alkali metal oxide, alkali metal oxides including Li 2 O, Na 2 O, and K 2 O; from 0.5 mol% to 4 mol% CaO; from 0 mol% to 1 mol% of ZnO; from 0 mol% to 1 mol% ZrO 2 ; and from 0.01 mol% to 0.25 mol% SnO 2 .
• Aspect 61 The method of any one of aspects 41-60, where the raw materials comprise nitrate from about 1.5 wt% to about 5 wt% of the raw materials.
• Aspect 62 The method of any one of aspects 41-61, wherein the raw materials comprise, as a mol% of the raw materials, from 0.2 mol% to 0.5 mol% ZrO 2 .
• Aspect 63 The method of any one of aspects 41-62, wherein the glass article comprises titanium oxide, zirconia, iron oxide, cerium oxide, or combinations thereof.
• Aspect 64 The method of any one of aspects 41-62, wherein the glass article comprises from 5 parts-per-million to 15 parts-per-million gold in the glass article.
• Aspect 65 The method of any one of aspects 41-64, wherein the raw materials comprises a colorant selected from the group consisting of silver, gold, chromium, cobalt, titanium, nickel, cerium, copper, and combinations thereof.
• Aspect 66 The method of any one of aspects 41-65, further comprising chemically strengthening the glass article to form a first compressive stress region extending to a first depth of compression from the first compressive stress region.
• Aspect 67 The method of aspect 66, wherein a maximum compressive stress of the first compressive stress region is about 400 MegaPascals or more.
• Aspect 68 The method of any one of aspects 41-67, wherein the glass article exhibits a CIE L* value of about 70 or more.
• Aspect 69 The method of any one of aspects 41-68, wherein a CIE L* value corresponding to the surface layer is less than the CIE L* value of the glass article on a thickness adjusted basis by 0. 1 or more.
• Aspect 70 The method of any one of aspects 41-69, wherein the glass article comprises an average absorptivity for optical wavelengths from 360 nm to 400 nm of about 0.1 mm' 1 or more.
• Aspect 71 The method of any one of aspects 41-69, wherein the glass article comprises an average absorptivity for optical wavelengths from 200 nm to 280 nm of about 0.1 mm' 1 or more.
• Aspect 72 The method of any one of aspects 41-71, wherein the glass article comprises a dielectric constant at frequencies from 10 GigaHertz to 60 GigaHertz of from about 5.6 to about 6.4.
• Aspect 73 The method of any one of aspects 41-72, wherein a total transmittance of at least one 10 nm band within a wavelength range of 380 nm to 750 nm is from 3% to 80%.
• Aspect 74 The method of any one of aspects 41-73, wherein average transmittance of greater than or equal to 10% and less than or equal to 92% over a wavelength range of 400 nmto 700 nm.
• Aspect 75 The method of any one of aspects 41-74, wherein the glass article comprises at least one crystalline phase.
• Aspect 76 The method of aspect 75, wherein a crystallinity of the glass article is 10 wt% or less.
• Aspect 77 The method of any one of aspects 41-76, wherein the glass article exhibits a fracture toughness of 0.60 MPam 1/2 or more, and a Young’s modulus from about 50 GigaPascals to about 100 GigaPascals.
• Aspect 78 The method of any one of aspects 41-77, wherein the thickness of the glass article is from about 30 micrometers to about 5 millimeters.
• Aspect 79 A method of making a consumer electronic device comprising: the method of any one of aspects 41-78; and positioning electronic components within a housing at least partially defined by the glass article.
• a method of making a natively color housing comprising: the method of any one of aspects 37-71; and disposing the second major surface of the glass article on a reflector layer, the reflector layer is opaque and has an CIE L* value of 70 or more.
• FIG. 1 is a schematic plan view of an example consumer electronic device according to aspects of the disclosure.
• FIG. 2 is a schematic perspective view of the example consumer electronic device of FIG. 1;
• FIG. 3 is a conceptual diagram from a back view of a communicating device, more specifically of a cellular phone, according to an aspect of the disclosure
• FIG. 4 is a simplified conceptual view of the device of FIG. 3 in a slightly exploded cross-section taken along line 4-4 of FIG. 3; [0096] FIG. 4A shows an enlarged view 4A of FIG. 4;
• FIG. 4B shows an enlarged view 4B of FIG. 4
• FIG. 5 is a cross-sectional view of a natively colored glass housing including a glass article in accordance with aspects of the disclosure
• FIG. 6 is a cross-sectional view of a natively colored glass housing including a saturated glass article in accordance with aspects of the disclosure
• FIG. 7 illustrates a flow chart of methods of making glass articles and/or natively colored glass housings in accordance with aspects of the disclosure
• FIG. 8 illustrates a step in a method of making glass articles and/or natively colored glass housings comprising heating the glass article
• FIG. 9 illustrates a step in a method of making glass articles and/or natively colored glass housings comprising ion exchange
• FIG. 10 illustrates a step in a method of making glass articles and/or natively color glass housings comprising impinging ultraviolet radiation on the first major surface of the glass article
• FIGS. 11-12 show changes in CIE coordinates as material is removed from a saturated glass article in accordance with aspects of the disclosure.
• FIGS. 3-6 illustrate views of natively colored glass housings 322, 500, or 600 including glass articles 511 that can be incorporated to consumer electronic products (e.g., display devices), for example, those shown in FIGS. 1-4.
• consumer electronic products e.g., display devices
• FIGS. 1-4 illustrate consumer electronic products (e.g., display devices), for example, those shown in FIGS. 1-4.
• a discussion of features of aspects of one foldable apparatus can apply equally to corresponding features of any aspects of the disclosure.
• identical part numbers throughout the disclosure can indicate that, in some aspects, the identified features are identical to one another and that the discussion of the identified feature of one aspect, unless otherwise noted, can apply equally to the identified feature of any of the other aspects of the disclosure.
• aspects of the disclosure can comprise a consumer electronic product.
• the consumer electronic product can comprise a front surface, a back surface, and side surfaces.
• the consumer electronic product can further comprise electrical components at least partially within the housing.
• the electrical components can comprise a controller, a memory, and a display.
• the display can be at or adjacent to the front surface of the housing.
• the display can comprise liquid crystal display (LCD), an electrophoretic displays (EPD), an organic light-emitting diode (OLED) display, or a plasma display panel (PDP).
• the consumer electronic product can comprise a cover substrate disposed over the display. In aspects, at least one of a portion of the housing or the cover substrate comprises the foldable apparatus discussed throughout the disclosure.
• the consumer electronic product can comprise a portable electronic device, for example, a smartphone, a tablet, a wearable device, or a laptop.
• the foldable apparatus disclosed herein may be incorporated into another article, for example, an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches), and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that may benefit from some transparency, scratch-resistance, abrasion resistance or a combination thereof.
• FIGS. 1-2 An exemplary article incorporating any of the foldable apparatus disclosed herein is shown in FIGS. 1-2. Specifically, FIGS. 1-2 show a consumer electronic device 100 including a housing 102 having front 104, back 106, and side surfaces 108.
• the consumer electronic device can comprise electrical components that are at least partially inside or entirely within the housing.
• electrical components include at least a controller, a memory, and a display.
• the display 110 can be at or adjacent to the front surface of the housing 102.
• the consumer electronic device can comprise a cover substrate 112 at or over the front surface of the housing 102 such that it is over the display 110.
• at least a portion of the housing 102 may include the glass article and/or the natively colored glass housing disclosed herein.
• a communicating device 310 i.e., electronic device with wireless signal communication capability; e.g., broadband communicating device, cellular phone, smartphone, control panel, console, dashboard, tablet, handheld computer, electronic tool
• circuitry 312 see FIG. 4
• the consumer electronic device 100 shown in FIGS. 1-2 is an example of the communicating device 310.
• the circuitry 312 includes an antenna 314.
• the circuitry 312 may further include other components, for example a camera 316 (FIG. 3), printed circuit board, processor, memory, display 110 (FIG. 3), battery, connector port, and other componentry.
• the antenna 314 can comprise a patterned metal wire or layer, or other such device (e.g., transceiver, receiver, transmitter, antenna array, communication module) configured to transmit and/or receive communication signals at or over a frequency range.
• a surface area of the antenna is defined as an area within a perimeter 338 surrounding the antenna.
• the surface area of the antenna can be 25 cm 2 or less, 15 cm 2 or less, 10 cm 2 or less, 100 pm 2 or more, 1 mm 2 or more, 25 mm 2 or more, or 100 mm 2 or more.
• the antenna 314 can be configured for wireless communication (e.g., transmitting, receiving, operating, and/or otherwise communicating) with transmission of signals at a frequency of 100 MHz or more, 1 GHz or more, 10 GHz or more, 24 GHz or more, 24.25 GHz or more, GHz or more, 26 GHz or more, 28 GHz or more, 100 GHz or less, 60 GHz or less, 50 GHz or less, 47 GHz or less, or 40 GHz or less.
• the antenna may operate in a frequency range from 26 GHz to 40 GHz or from 60 GHz to 80 GHz.
• the antenna 314 can be positioned and/or oriented such that signals are transmitted through the structure 326 (e.g., directly facing the structure 326, the structure 326 may overlay at least a portion of the antenna 314).
• a minimum distance between the antenna 314 to a portion of the glass article defining the structure 326 can be 5 mm or less, 3 mm or less, 2 mm or less, or 0.6 mm or less.
• the antenna 314 and the portion of the glass article defining the structure 326 may be in direct contact or separated only by a thickness of the coating 328.
• the communicating device 310 includes a housing 102 enclosing some or all of the circuitry 312.
• the housing 102 may include a frame 320, for example a metallic (e.g., aluminum, steel) sidewall, a natively colored glass housing 322 (e.g., back), and a display 110 (e.g., see FIGS. 1- 2).
• the housing 102 may include alternative structures as well, for example a panel integral with frame forming a back with sidewalls within which circuitry 312 and other components may be located, and/or such as having the housing 102 integrated with a keyboard, touch panel, or other features in addition to or instead of the display.
• the natively colored glass housing 322 may comprise (e.g., include, mostly consist of by weight or volume, be) a glass article 350.
• the glass article 350 may be flat, may have curved edges, may be bowed, or otherwise.
• the natively colored glass housing 322 may include layer(s) 328, for example a scratch-resistant coating, an anti-reflective, or other coatings on a surface of the glass article 350 (e.g., first major surface 332, second major surface 330 of the glass article 350), and may further include decorative ink and/or other layers on a surface thereof as well.
• the coating 328 on the second major surface 330 of the glass article can comprise any of the aspects and/or be the same as the reflector 501 discussed below with reference to FIG. 5.
• the natively colored glass housing may simply consist of a sheet of glass, where layers, coatings, etc. are unneeded for the corresponding device.
• the glass article 350 includes a structure 326.
• the structure 326 may be an integral portion of the glass article 350 such that glass of the glass article 350 continuously extends throughout the glass article 350, including defining the structure 326.
• the structure 326 may be a recess, trench, bump, plateau, or other feature formed in or on the glass article 350.
• the glass article 350 may have more than one such structure 326.
• Such a structure may be formed in many conceivable ways, for example, by etching away a portion of the glass article 350, milling away a portion of the glass article 350, pressing the glass of the glass article 350 in a mold, welding additional glass onto the glass article 350.
• glass forming the structure 326 may have the same composition as the glass of the glass article 350 outside of the structure 326.
• the glass of the structure 326 may also share a common microstructure with the glass of the glass article 350 outside of the structure 326, such as having the same types and distributions of crystals, for example if the glass is a glass-ceramic, and/or the same types and distributions of colorants.
• the structure 326 is formed as a recess relative to a major surface (e.g., second major surface 330) of the glass article 350.
• the “major surfaces” of the glass article 350 sheet are sides of the sheet having the most surface area (e.g., front and back sides).
• a major surface may be surrounded by edges of a sheet that extend between the major surfaces.
• major surfaces may have areas defined by perimeters of edges, where the major surfaces have surface areas substantially greater than other surfaces of the body (e.g., sidewalls), for example at least 50% greater.
• the glass article 350 comprises a thickness 337, which is defined as an average distance between the second major surface 330 and the first major surface 332 opposite the first major surface excluding any portion of the glass article 350 including the structure 326 described above.
• the thickness 337 can be within one or more of the ranges discussed below for the thickness 517 with reference to FIG. 5.
• the thickness 337 can be substantially uniform across the second major surface 330 and/or more than 50% of the glass article can comprise a local thickness within 10% of the thickness 337.
• the structure 326 comprises a perimeter 340 on a major surface (e.g., second major surface 330) of the glass article 350, where the perimeter 340 demarcates a second thickness 327 of the structure 326 that differs from the thickness 337, for example, by 50 pm or more, by 100 pm or more, by 150 pm or more, by 200 pm or more, by 300 pm or more, by 500 pm or more (e.g., located at comer 336 as shown in FIG. 4B).
• a major surface e.g., second major surface 330
• the perimeter 340 demarcates a second thickness 327 of the structure 326 that differs from the thickness 337, for example, by 50 pm or more, by 100 pm or more, by 150 pm or more, by 200 pm or more, by 300 pm or more, by 500 pm or more (e.g., located at comer 336 as shown in FIG. 4B).
• the second thickness 327 of the structure 326 may be 600 pm or less, 500 pm or less, or 400 pm or less, while the thickness 337 of the glass article 350 may be 600 pm or more, 700 pm or more, 800 pm or more (or any of the ranges described herein for the thickness 517).
• the second thickness 327 may be greater than the thickness 337 by 50 pm or more, by 100 pm or more, by 150 pm or more, by 200 pm or more, by 300 pm or more, by 500 pm or more. As shown in FIGS.
• the perimeter 340 forms a closed loop on the major surface (e.g., second major surface 330), where a shape of the perimeter 340 may be rectilinear, curved, or curvilinear and can comprise any shape (e.g., square, blocky, ziggurat-shaped with rectangular rows of diminishing length overlaying one another, triangular, oval, or even more complex geometries).
• the perimeter 340 of the structure 326 may be shaped as a silhouette of a logo and/or registered trademark or other recognizable design or shape.
• a surface area of the structure is defined as the surface area within the perimeter of the structure projected onto the first major surface of the glass article.
• a surface area of the structure 326 may be 100 cm 2 or less, 50 cm 2 or less, 25 cm 2 or less, 25 pm 2 or more, 100 pm 2 or more, 1 mm 2 or more, 25 mm 2 or more, or 4 cm 2 or more.
• the glass article can comprise a housing of a communicating device and the glass article may have more than one such structure, as shown in FIG. 3, where the structure 326 overlays the antenna 314 while another structure 342 forms a portion of a camera or sensor encasement (e.g., camera 316).
• the structure 326 and/or 342 can overlay at least a portion and/or all of the surface area corresponding to the antenna 314 and/or the camera 316.
• Forming the structure 326 and/or 342 in a middle or interior portion of the glass article 350, spaced inward from outside edges 344 of the glass article 350 may help mitigate structural weaknesses or stress concentrations of the glass article 350 that may be associated forming the structure 326 and/or 342.
• Forming edges or corners 334 and/or 336 (see FIGS. 4A-4B) or the perimeter 340 of the structure 326 with a geometry that reduces concentration of stress at the edges or comers 334 and/or 336 may also help strengthen the glass article 350 when forming the structure 326.
• Such a geometry may include rounding or dulling vertices or comers 334 and/or 336 of the structure 326, as may be done through etching or localized melting/heating (e.g., with a laser).
• the glass article 350 may smoothly transition between the thickness 337 and the second thickness 327 at comer 334 and/or 336 over a distance “D” (see FIG. 4A) from 5 pm to 700 pm, from 10 pm to 500 pm, about 20 pm to 500 pm, from 100 pm to 500 pm, or any range or subrange therebetween, as measured in a direction perpendicular to a direction of the thickness 337.
• CIE color coordinates describe the CIELAB 1976 color space established by the International Commission on Illumination (CIE). Unless otherwise indicated, CIE color coordinates are measured in transmission through the glass article using an F02 illuminant and an observer angle of 10°.
• the CIELAB 1976 color space 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 (+).
• FIGS. 5-6 illustrate natively colored glass housings 500 or 600 comprising the glass article 511 and the reflector 501.
• the reflector 501 comprises an opaque material.
• opaque means than an average transmittance in the wavelength range of 400 nm to 700 nm through a 1.0 mm thick piece of the material is 10% or less.
• the average transmittance in the wavelength range of 400 nm to 700 nm is calculated by measuring the transmittance of whole number wavelengths from about 400 nm to about 700 nm and averaging the measurements.
• the reflector comprises a CIE L* value of about 70 or more.
• An exemplary material for the reflector is aluminum.
• the glass article 511 can be disposed on and/or contact a surface 503 of the reflector 501 can contact the glass article 511. Providing the reflector can increase a perceived brightness of the glass article.
• transmittance data (total transmittance and diffuse transmittance) in the visible spectrum is measured with a Lambda 950 UV/Vis/NIR Spectrophotometer manufactured by PerkinElmer Inc. (Waltham, Massachusetts USA).
• the Lambda 950 apparatus was fitted with a 150 mm integrating sphere. Data was collected using an open beam baseline and a Spectralon® reference reflectance disk. For total transmittance (Total Tx), the sample is fixed at the integrating sphere entry point.
• the “average transmittance” with respect to the visible spectrum is reported over the wavelength range from 380 nm to 750 nm (inclusive of endpoints). Unless otherwise specified, the average transmittance is indicated for article thicknesses from 0.4 mm to 5 mm, inclusive of endpoints. Unless otherwise specified, when average transmittance is indicated, this means that each thickness within the range of thicknesses from 0.4 mm to 5 mm has an average transmittance as specified.
• colored glass articles having average transmittances of 10% to 92% over the wavelength range from 380 nm to 750 nm means that each thickness within the range of 0.4 mm to 5 mm (e.g., 0.6 mm, 0.9 mm, 2 mm, etc.) has an average transmittance in the range of 10% to 92% for the wavelength range from 380 nm to 750 nm.
• first layer and/or component is described as “disposed over” a second layer and/or component, other layers may or may not be present between the first layer and/or component and the second layer and/or component.
• “disposed over” does not refer to a relative position with reference to gravity.
• a first layer and/or component can be considered “disposed over” a second layer and/or component, for example, when the first layer and/or component is positioned underneath, above, or to one side of a second layer and/or component.
• a first layer and/or component described as “bonded to” a second layer and/or component means that the layers and/or components are bonded to each other, either by direct contact and/or bonding between the two layers and/or components or via an adhesive layer.
• a first layer and/or component described as “contacting” or “in contact with” a second layer and/or components refers to direct contact and includes the situations where the layers and/or components are bonded to each other.
• the glass article 511 comprises a first major surface 513 and a second major surface 515 opposite the first major surface 513.
• the first major surface 513 and/or the second major surface 515 can comprise planar surfaces, although other shapes and designs are possible in other aspects.
• a thickness 517 of the glass article 511 is defined as an average distance between the first major surface 513 and the second major surface 515.
• the thickness 517 can be about 30 micrometers (pm) or more, about 50 pm or more, about 80 pm or more, about 90 pm or more, about 100 pm or more, about 150 pm or more, about 200 pm or more, about 400 pm or more, about 500 pm or more, about 600 pm or more, about 5 millimeters (mm) or less, about 3 mm or less, about 2 mm or less, about 1 mm or less, about 800 pm or less, about 700 pm or less, about 600 pm or less, about 550 pm or less, about 500 pm or less, or about 300 pm or less.
• mm millimeters
• the thickness 517 can be in a range from about 30 pm to about 5 mm, from about 50 pm to about 3 mm, from about 80 pm to about 2 mm, from about 90 pm to about 1 mm, from about 100 pm to about 800 pm, from about 150 pm to about 700 pm, from about 200 pm to about 600 pm, from about 400 pm to about 500 pm, or any range or subrange therebetween.
• the glass article 511 and/or 350 comprises a glass-based material.
• the glass-based material can comprise a pencil hardness of 8H or more, for example, 9H or more.
• pencil hardness is measured using ASTM D 3363-20 with standard lead graded pencils.
• an elastic modulus e.g., Young’s modulus
• a Poisson’s ratio is measured using ISO 527- 1 :2019.
• the glass article 511 and/or 350 can comprise an elastic modulus in a range from about 40 GPa to about 140 GPa, from about 50 GPa to about 100 GPa, from about 60 GPa to about 80 GPa, or any range or subrange therebetween.
• glass-based includes both glasses and glassceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase.
• a glass-based material may comprise an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramic).
• Amorphous materials and glass-based materials may be strengthened.
• the term “strengthened” may refer to a material that has been chemically strengthened, for example, through ion exchange of larger ions for smaller ions in the surface of the glass article, as discussed below.
• glass-based materials which may be free of lithia or not, comprise soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali- containing aluminoborosilicate glass, alkali-containing phosphosilicate glass, and alkali-containing aluminophosphosilicate glass.
• glass-based material can comprise an alkali-containing glass or an alkali- free glass, either of which may be free of lithia or not.
• the glass material can be alkali-free and/or comprise a low content of alkali metals (e.g., R 2 O of about 10 mol% or less, wherein R 2 O comprises Li 2 O Na 2 O, K 2 O, or the more expansive list provided below).
• R 2 O alkali metals
• a glass-based material may comprise, in mole percent (mol%): SiO 2 in a range from about 40 mol% to about 80 mol%, Al 2 O 3 in a range from about 5 mol% to about 30 mol%, B2O 3 in a range from 0 mol% to about 10 mol%, ZrO 2 in a range from 0 mol% to about 5 mol%, P 2 O 5 in a range from 0 mol% to about 15 mol%, TiO 2 in a range from 0 mol% to about 2 mol%, R 2 O in a range from 0 mol% to about 20 mol%, and RO in a range from 0 mol% to about 15 mol%.
• R 2 O can refer to an alkali-metal oxide, including Li 2 O, Na 2 O, and K 2 O.
• RO can refer to MgO, CaO, SrO, BaO, and ZnO.
• the glass-based material may comprise (in mol%) from about 50 mol% to about 75 mol% SiO 2 , from about 7 mol% to about 20 mol% Al 2 O 3 , from about 13 mol% to about 20 mol% of at least one alkali metal oxide (R 2 O), and at least one of B2O 3 or P 2 O 5 .
• the glassbased material may comprise (in mol%) from 60 mol% to 65 mol% SiO 2 , from 12 mol% to 17 mol% Al 2 O 3 , from 3 mol% to 6 mol% B2O 3 , from 13 mol% to 20 mol% of at least one alkali metal oxide (R 2 O), from 0.5 mol% to 4 mol% CaO, from 0 mol% to 1 mol% ZnO, from 0 mol% to 1 mol% ZrO 2 , and from 0.01 mol% to 0.25 mol% SnO 2 .
• the glass-based material can comprise from 0.2 mol% to 0.5 mol% ZrO 2 .
• a glass-based material may optionally further comprise in a range from 0 mol% to about 2 mol% of each of Na2SO4, NaCl, NaF, NaBr, K 2 SO 4 , KC1, KF, KBr, As 2 O 3 , Sb 2 O 3 , SnO 2 , Fe 2 O 3 , MnO, MnO 2 , MnO 3 , Mn 2 O 3 , Mn 3 O 4 , Mn 2 O?.
• the glass-based material can comprise a colorant selected from a group consisting of silver, gold, chromium, cobalt, titanium, nickel, cerium, copper, and combinations thereof.
• the glass-based material can comprise titanium oxide, zirconia, iron oxide, cerium oxide, or combinations thereof.
• the glass-based material can comprise from 5 parts-per-million (ppm) to 15 ppm gold.
• compositions are specified in mole percent (mol%).
• mol% mole percent
• free when used to describe the concentration and/or absence of a particular constituent component in a glass composition, means that the constituent component is not present in the glass composition.
• 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 200 ppm unless specified otherwise herein.
• substantially free is exclusive of gold (Au) which may be intentionally added to the glass composition in relatively small amounts, for example and without limitation, amounts less than 200 ppm (or the equivalent in mol%) to achieve a desired color in the resultant colored glass article.
• Glass-ceramics include materials produced through controlled crystallization of glass. In aspects, glass-ceramics have about 1% to about 99% crystallinity. Examples of suitable glass-ceramics may include Li 2 O-Al 2 O 3 -SiO 2 system (i.e., LAS-System) glass-ceramics, MgO-Al 2 O 3 -SiO 2 system (i.e., MAS- System) glass-ceramics, ZnO x A1 2 O 3 x nSiO 2 (i.e., ZAS system), and/or glassceramics that include a predominant crystal phase including [3-quartz solid solution ⁇ - spodumene, cordierite, petalite, and/or lithium disilicate.
• LAS-System Li 2 O-Al 2 O 3 -SiO 2 system
• MgO-Al 2 O 3 -SiO 2 system i.e., MAS- System
• the glass-ceramic materials may be strengthened using the chemical strengthening processes.
• MAS-System glass-ceramic materials may be strengthened in Li 2 SO 4 molten salt, whereby an exchange of 2Li + for Mg 2+ can occur.
• the glass article 511 and/or 350 can be a glass-ceramic comprising one or more crystalline phases.
• a total amount of the one or more crystalline phases, as a weight% (wt%) of the glass article 511 and/or 350 can be about 10 wt% or less, about 8 wt% or less, about 6 wt% or less, about 4 wt% or less, about 4 wt% or less, about 2 wt% or less, about 1 wt% or less, about 0.1 wt% or more, about 0.5 wt% or more, or about 1 wt% or more.
• the glass articles described herein may be described as aluminoborosilicate glass compositions and colored glass articles and comprise SiO 2 , Al 2 O 3 , and B2O 3 . Additionally, the glass articles described herein include one or more colorants in a colorant package to impart a desired color to the resultant colored glass article. The glass articles described herein also include alkali oxides (e.g., Li 2 O and Na 2 O) to enable the ion-exchangeability of the colored glass articles. In aspects, the glass articles described herein may further include other components to improve colorant retention and produce colored glass articles having the desired color. In aspects, the difference between R 2 O and Al 2 O 3 (i.e.
• R 2 O (mol%) - Al 2 O 3 (mol%)) in the glass articles described herein may be adjusted to produce a desired observable color (e.g., pink, purple, red, orange, or blue).
• the viscosity of the glass composition may be adjusted to prevent devitrification of the glass composition.
• SiO 2 is the primary glass former in the glass articles described herein and may function to stabilize the network structure of the colored glass articles.
• concentration of SiO 2 in the glass articles should be sufficiently high (e.g., 40 mol% or more) 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 SiCT may be limited (e.g., 80 mol% or less) to control the melting point of the glass composition, as the melting point of pure S i O2 or high SiO 2 glasses is undesirably high. Thus, limiting the concentration of SiCT may aid in improving the meltability and the formability of the resultant colored glass article.
• the glass article may comprise from 40 mol% to 80 mol% SiO 2 or from 50 mol% to 80 mol% SiO 2 . In aspects, the glass article may comprise from about 45 mol% to about 67 mol% SiCT or from 53 mol% to 67 mol% SiO 2 .
• the concentration of SiO 2 in the glass article may be 40 mol% or more, 45 mol% or more, 50 mol% or more, 52 mol% or more, 53 mol% or more, 54 mol% or more, 55 mol% or more, 56 mol% or more, 57 mol% or more, 58 mol% or more, 60 mol% or more, 80 mol% or less, 75 mol% or less, 73 mol% or less, 71 mol% or less 70 mol% or less, 68 mol% or less, 67 mol% or less, 66 mol% or less, 65 mol% or less 64 mol% or less, 63 mol% or less, 62 mol% or less, 61 mol% or less,
• the concentration of SiO 2 in the glass article may be from 40 mol% to 70 mol%, 45 mol% to 70 mol%, from 50 mol% to about 68 mol%, from about 52 mol% to about 68 mol%, from about 53 mol% to about
• A1 2 O 3 may also stabilize the glass network and additionally provides improved mechanical properties and chemical durability to the glass article.
• the amount of A1 2 O 3 may also be tailored to control the viscosity of the glass composition.
• A1 2 O 3 may be included such that the resultant glass article has the desired fracture toughness (e.g., greater than or equal to 0.7 MPa-m 1/2 ). However, if the amount of A1 2 O 3 is too high (e.g., 25 mol% or more), the viscosity of the glass melt may increase, thereby diminishing the formability of the glass article.
• the solubility of one or more colorants of the colorant package in the glass melt may decrease, resulting in the formation of undesirable crystal phases in the glass.
• the solubility of Cr 2 O 3 in the glass melt may decrease with increasing A1 2 O 3 concentrations (e.g., concentrations greater than or equal to 17.5 mol%), leading to the precipitation of undesirable crystal phases.
• A1 2 O 3 concentrations e.g., concentrations greater than or equal to 17.5 mol%
• the glass com article may comprise from 7 mol% to 25 mol% A1 2 O 3 , from 7 mol% to 20 mol% A1 2 O 3 , or from 8 mol% to 20 mol% A1 2 O 3 .
• the glass article may comprise from 10 mol% to 20 mol% A1 2 O 3 , from 10 mol% to about 17.5 mol% A1 2 O 3 , or from 12 mol% to about 17.25 mol% A1 2 O 3 .
• the glass article may comprise from 11 mol% to 19 mol% A1 2 O 3 or from 14 mol% to 17 mol% A1 2 O 3 .
• the concentration of A1 2 O 3 in the glass article may be 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more 12 mol% or more, 12.5 mol% or more, 13 mol% or more, 13.5 mol% or more, 14 mol% or more, 14.5 mol% or more, 15 mol% or more, 15.5 mol% or more, 16 mol% or more, 25 mol% or less, 23 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17.5 mol% or less, 17.25 mol% or less, 17 mol% or less, 16.75 mol% or less, or 16 mol% or less.
• the concentration of Al 2 O 3 in the glass article may be from 7 mol% to 25 mol%, from 7 mol% to 23 mol%, from 8 mol% to 20 mol%, from 9 mol% to 19 mol%, from 10 mol% to 18 mol%, from 11 mol% to 17.5 mol%, from 12 mol% to 17.25 mol%, from 13 mol% to 17 mol%, from 14 mol% to 16.75 mol%, from 14.5 mol% to 16 mol%, or any range or subrange therebetween.
• B2O 3 decreases the melting point of the glass composition, which may improve retention of certain colorants in the glass, for example and without limitation, Au. B2O 3 may also improve the damage resistance of the resultant colored glass article. In addition, B2O 3 may be added to reduce the formation of non-bridging oxygen, the presence of which may reduce fracture toughness. The concentration of B2O 3 should be sufficiently high (e.g., 1 mol% or more) to reduce the melting point of the glass composition, improve the formability, and increase the fracture toughness of the colored glass article. However, if B2O 3 is too high (e.g., 15 mol% or more), the annealing point and strain point may decrease, which increases stress relaxation and reduces the overall strength of the colored glass article.
• the glass article may comprise from 1 mol% to 15 mol% B2O 3 , from 1 mol% to 10 mol% B2O 3 , from 3 mol% to 10 mol% B2O 3 , or from 3.5 mol% to 9 mol% B2O 3 . In aspects, the glass article may comprise from 2 mol% to 12 mol% B2O 3 or from 2 mol% to 8 mol% B2O 3 .
• the concentration of B2O 3 in the glass article may be 1 mol% or more, 2 mol% or more, 3 mol% or more, 3.5 mol% or more, 4 mol% or more, 4.5 mol% or more, 5 mol% or more, 5.5 mol% or more, 15 mol% or less, 12 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, 7.5 mol% or less, 7 mol% or less, 6.5 mol% or less, or 6 mol% or less.
• the concentration of B2O 3 in the glass article may be from 1 mol% to 15 mol%, from 2 mol% to 12 mol%, from 3 mol% to 10 mol%, from 3.5 mol% to 9 mol%, from 4 mol% to 8 mol%, from 4.5 mol% to 7.5 mol%, from 5 mol% to 7 mol%, from 5.5 mol% to 6.5 mol%, or any range or subrange therebetween.
• the glass articles may contain alkali oxides (e.g., Li 2 O, Na 2 O, and K 2 O) to enable the ion-exchangeability of the glass articles.
• alkali oxides e.g., Li 2 O, Na 2 O, and K 2 O
• Li 2 O aids in the ion-exchangeability of the glass article and also reduces the softening point of the glass composition, thereby increasing the formability of the glass articles.
• the addition of Li 2 O facilitates the exchange of both Na + and K + cations into the glass for strengthening the glass and also facilitates producing a relatively high surface compressive stress and relatively deep depth of compression, improving the mechanical characteristics of the resultant colored glass article.
• Li 2 O decreases the melting point of the glass composition, which may improve retention of colorants in the glass, for example and without limitation, Au.
• the concentration of Li 2 O in the glass articles should be sufficiently high (e.g., 1 mol% or more) to reduce the melting point of the glass composition and achieve the desired maximum central tension (e.g., 40 MPa or more) following ion exchange. However, if the amount of Li 2 O is too high (e.g., greater than 20 mol%), the liquidus temperature may increase, thereby diminishing the manufacturability of the colored glass article.
• the glass article may comprise from 1 mol% to 20 mol% Li 2 O or from 1 mol% to 20 mol% Li 2 O.
• the glass article may comprise from 3 mol% to 18 mol% Li 2 O, from 7 mol% to 18 mol% Li 2 O, from 8.8 mol% to 14 mol% Li 2 O, or from 9 mol% to 13.5 mol% Li 2 O.
• the concentration of Li 2 O in the glass article may be 1 mol% or more, 3 mol% or more, 5 mol% or more, 7 mol% or more, 7.5 mol% or more, 8 mol% or more, 8.5 mol% or more, 8.8 mol% or more, 9 mol% or more, 9.2 mol% or more, 9.4 mol% or more, 9.6 mol% or more, 9.8 mol% or more, 10 mol% or more, 11 mol% or more, 11.5 mol% or more, 12 mol% or more, 20 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13.5 mol% or less, 13 mol% or less, 12.5 mol% or less, 12 mol% or less, 11.5 mol% or less, or 11 mol% or less.
• the concentration of Li 2 O in the glass article may be from 1 mol% to 20 mol%, from 3 mol% to 18 mol%, from 5 mol% to 17 mol%, from 7 mol% to 16 mol%, from 7.5 mol% to 15 mol%, from 8 mol% to 14 mol%, from 8.5 mol% to 13.5 mol%, from 8.8 mol% to 13 mol%, from 9 mol% to 12.5 mol%, from 9.2 mol% to 12.5 mol%, from 9.4 mol% to 12 mol%, from 9.6 mol% to 12 mol%, from 9.8 mol% to 11.5 mol%, from 10 mol% to 11 mol%, or any range or subrange therebetween.
• Na 2 O improves diffusivity of alkali ions in the glass and thereby reduces ion-exchange time and helps achieve the desired surface compressive stress (e.g., 300 MPa or more).
• the addition of Na 2 O also facilitates the exchange of K + cations into the glass for strengthening and improving the mechanical characteristics of the resultant colored glass article.
• Na 2 O also improves the formability of the colored glass article.
• Na 2 O decreases the melting point of the glass composition, which may improve retention of certain colorants in the glass, for example, Au. However, if too much Na 2 O is added to the glass composition, the melting point may be too low.
• the concentration of Li 2 O present in the glass article may be greater than the concentration of Na 2 O present in the glass article.
• the glass article may comprise greater than 0 mol%, from 0.01 mol% to 15 mol% Na 2 O, from 0.5 mol% to 15 mol% Na 2 O, or from 1 mol% to 15 mol% Na 2 O. In aspects, the glass article may comprise from 1 mol% to 12 mol% Na 2 O or from 2 mol% to 10 mol% Na 2 O. In aspects, the glass article may comprise from 0.01 mol% to 4 mol% Na 2 O. In aspects, the glass article may comprise from 1.5 mol% to 8 mol% Na 2 O or from 2 mol% to 7.5 mol% Na 2 O.
• the concentration of Na 2 O in the glass article may be greater than 0 mol%, 0.01 mol% or more, 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 3 mol% or more, 3.5 mol% or more, 4 mol% or more, 4.5 mol% or more, 15 mol% or less, 12 mol% or less, 10 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7 mol% or less, 6.5 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, or 4 mol% or less.
• the concentration of Na 2 O in the glass article may be from greater than 0 mol% to 15 mol%, from 0.01 mol% to 12 mol%, from 0.5 mol% to 12 mol%, from 1 mol% to 10 mol%, from 1.5 mol% to 9 mol%, from 2 mol% to 8.5 mol%, from 2.5 mol% to 8 mol%, from 3 mol% to 7.5 mol%, from 3.5 mol% to 7 mol%, from 4 mol% to 6.5 mol%, from 4.5 mol% to 6 mol%, or any range or subrange therebetween
• the concentration of Na 2 O in the glass article may be from 0.5 mol% to 10 mol%, from 1 mol% to 9 mol%, from 1 mol% to 8 mol%, from 1 mol% to 7 mol%, from 1 mol% to 6.5 mol%, from 1 mol% to 6 mol%, from 1 mol% to 5.5 mol%, from 1 mol% to
• K 2 O when included, 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 K 2 O may cause the surface compressive stress and melting point to be too low. Accordingly, in aspects, the amount of K 2 O added to the glass composition may be limited.
• the glass article may optionally comprise from greater than 0 mol% to 3 mol% K 2 O, from greater than 0 mol% to 1 mol% K 2 O, from 0.01 mol% to 1 mol% K 2 O, or from 0.1 mol% to 1 mol% K 2 O. In aspects, the glass article may optionally comprise from 0.1 mol% to 0.5 mol% K 2 O.
• the concentration of K 2 O in the glass article may be greater than 0 mol%, 0.01 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.25 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or 0.25 mol% or less.
• the concentration of K 2 O in the glass article may be from greater 0 mol% to 3 mol%, from 0.01 mol% to 2.5 mol%, from 0.1 mol% to 2 mol%, from 0.2 mol% to 1.5 mol%, from 0.25 mol% to 1 mol%, from 0.3 mol% to 0.75 mol%, from 0.4 mol% to 0.5 mol%, or any range or subrange therebetween.
• the alkali oxides aid in decreasing the softening point and molding temperature of the glass composition, thereby offsetting the increase in the softening point and molding temperature of the glass composition due to higher amounts of SiCL in the glass composition, for example.
• the softening point and molding temperature may be further reduced by including combinations of alkali oxides (e.g., two or more alkali oxides) in the glass composition, a phenomenon referred to as the “mixed alkali effect.”
• alkali oxides e.g., two or more alkali oxides
• the concentration of R 2 O in the glass article can be from 1 mol% to 35 mol%, from 6 mol% to 25 mol%, or from 8 mol% to 23 mol%.
• the concentration of R 2 O in the glass article can be 2 mol% or more, 4 mol% or more, 6 mol% or more, 8 mol% or more, 10 mol% or more, 10.3 mol% or more, 11 mol% or more, 12 mol% or more 13 mol% or more, 14 mol% or more, 35 mol% or less, 30 mol% or less, 25 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, or 15 mol% or less.
• the concentration of R 2 O in the glass article can range from 2 mol% to 35 mol%, from 4 mol% to 30 mol%, from 6 mol% to 25 mol%, from 8 mol% to 23 mol%, from 8 mol% to 22 mol%, from 10 mol% to 21 mol%, from 10.3 mol% to 20 mol%, from 11 mol% to 19 mol%, from 12 mol% to 18 mol%, from 13 mol% to 17 mol%, from 14 mol% to 16 mol%, or any range or subrange therebetween.
• a difference between R 2 O and Al 2 O 3 i.e. R 2 O (mol%) - Al 2 O 3 (mol%)
• R 2 O (mol%) - Al 2 O 3 (mol%)) in the glass article may be adjusted to produce a desired observable color (e.g., pink, purple, red, orange, or blue).
• the analyzed R 2 O - Al 2 O 3 of the glass article, along with the added colorant package, may correlate with the observable color of the colored glass article after an optional heat treatment, as discussed herein.
• R 2 O - Al 2 O 3 in the glass article may be from -5 mol% to 7 mol% or from - 3 mol% to 2 mol%.
• R 2 O - Al 2 O 3 in the glass article may be from -3 mol% to 6 mol% or from -1 mol% to 5 mol%. In aspects, R 2 O - Al 2 O 3 in the glass article may be from -5 mol% to 1.5 mol% or from -3 mol% to 1.5 mol%. In aspects, R 2 O - Al 2 O 3 in the glass article may be from 1.5 mol% to 7 mol% or from 1.5 mol% to 5 mol%.
• R 2 O - Al 2 O 3 in the glass article may be -5 mol% or more, -4 mol% or more, -3 mol% or more, -2.5 mol% or more, -2 mol% or more, -1.5 mol% or more, 0.2 mol% or more, 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 7 mol% or less, 6.5 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, or 0.5 mol% or less.
• R 2 O - Al 2 O 3 in the glass article may be from -5 mol% to 7 mol%, from -4 mol% to 6.5 mol%, from -3 mol% to 6 mol%, from -2.5 mol% to 5.5 mol% from -2 mol% to 5 mol%, from -1.5 mol% to 4.5 mol%, from 0.2 mol% to 4 mol%, from 0.5 mol% to 3.5 mol%, from 1 mol% to 3 mol%, from 1.5 mol% to 2.5 mol%, or any range or subrange therebetween.
• the glass articles described herein further include MgO and/or ZnO to improve retention of colorants in the glass, such as Au or the like, for example, by lowering the melting point of the glass composition. Decreasing the melting point of the glass composition may help improve colorant retention because the glass compositions may be melted at relatively lower temperatures and the evaporation of colorants from the glass, such as gold, may be reduced. Without wishing to be bound by theory, it is also believed that partially replacing Li 2 O and/or Na 2 O with MgO and/or ZnO may also help improve retention of the colorants. Specifically, Li 2 O and/or Na 2 O is included in the batch glass composition as lithium carbonate and sodium carbonate, respectively.
• color gamut refers to the pallet of colors that may be achieved by the colored glass articles within the CIELAB color space.
• the sum of MgO and ZnO present in the glass article may be from greater than 0 mol% to 6 mol% or 4.5 mol% or less.
• MgO (mol%) + ZnO (mol%) may be from greater than 0 mol% to 6 mol% or 4.5 mol% or less.
• the sum (in mol%) of MgO and ZnO present in the glass article may be greater than 0 mol%, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 3 mol% or more, 3.5 mol% or more, 7 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4.25 mol% or less, or 4 mol% or less.
• the sum of MgO and ZnO in the glass may be from greater than 0 mol% to 8 mol%, from 0.1 mol% to 7 mol%, from 0.1 mol% to 6 mol%, from 0.5 mol% to 6 mol%, from 1 mol% to 5.5 mol%, from 1.5 mol% to 5 mol%, from 2 mol% to 4.5 mol%, from 2.5 mol% to 4.25 mol%, from 3 mol% to 4 mol%, or any range or subrange therebetween.
• the glass article may comprise from greater than 0 mol% to 8 mol% MgO or from 0 mol% to 4.5 mol% MgO. In aspects, the glass article may comprise from 0.5 mol% to 7 mol% MgO.
• the concentration of MgO in the glass article may be greater than 0 mol%, 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, or 1 mol% or less.
• the concentration of MgO in the glass article may be from greater than or equal to 0 mol% to 8 mol%, from 0.5 mol% to 7 mol%, from 0.5 mol% to 6 mol%, from 1 mol% to 5.5 mol%, from 1 mol% to 5 mol%, from 1.5 mol% to 4.5 mol%, from 1.5 mol% to 4 mol%, from 2 mol% to 3.5 mol%, from 2.5 mol% to 3 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of MgO.
• the glass article may comprise from greater than 0 mol% to 5 mol% ZnO, from greater than 0 mol% to 4.5 mol% ZnO, from 0.
• the concentration of ZnO in the glass article may be greater than 0 mol%, 0.1 mol% or more, 0.25 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.75 mol% or less, 1.5 mol% or less, 1.25 mol% or less, or 1 mol% or less.
• the concentration of ZnO in the glass composition may be from greater than 0 mol% to 5 mol%, from 0.1 mol% to 4.5 mol%, from 0.25 mol% to 4 mol%, from 0.5 mol% to 3.5 mol%, from 0.75 mol% to 3 mol%, from 1 mol% to 2.5 mol%, from 1.5 mol% to 2 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of ZnO.
• CaO, SrO, and BaO Like ZnO and the alkaline earth oxide MgO, other alkaline earth oxides, for example CaO, SrO and BaO, decrease the melting point of the glass composition. Accordingly, CaO, SrO, and/or BaO may be included in the glass articles to lower the melting point of the glass composition, which may help improve colorant retention.
• the glass articles described herein may further comprise CaO.
• CaO lowers the viscosity of a glass composition, which enhances the formability, the strain point and the Young’s modulus, and may improve the ionexchangeability.
• the diffusivity of sodium and potassium ions in the glass composition decreases which, in turn, adversely impacts the ion-exchange performance (i.e., the ability to ionexchange) of the resultant glass.
• the concentration of CaO in the glass article may be 0 mol% or more, 0.25 mol% or more, 0.5 mol% or more, 0.75 mol% or more, 1 mol% or more, 7 mol% or less, 6.5 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.75 mol% or less, 1.5 mol% or less, 1.25 mol% or less, or 1 mol% or less.
• the concentration of CaO in the glass article may be from greater than 0 mol% to 7 mol%, from greater than 0 mol% to 6.5 mol%, from 0.25 mol% to 6 mol%, from 0.25 mol% to 5.5 mol%, from 0.25 mol% to 5 mol%, from 0.5 mol% to 4.5 mol%, from 0.5 mol% to 4 mol%, from 0.5 mol% to 3.5 mol%, from 0.75 mol% to 3 mol%, from 0.75 mol% to 2.5 mol%, from 0.75 mol% to 2 mol%, from 1 mol% to 1.75 mol%, from 1 mol% to 1.5 mol%, or any range or subrange therebetween.
• the concentration of SrO in the glass article may be greater than 0 mol%, 0.25 mol% or more, 0.5 mol% or more, 0.75 mol% or more, 1 mol% or more, 2 mol% or less, 1.75 mol% or less, 1.5 mol% or less, 1.25 mol% or less, or 1 mol% or less.
• the concentration of SrO in the glass article may be from greater than 0 mol% to 2 mol%, from 0.25 mol% to 1.75 mol%, from 0.5 mol% to 1.5 mol%, from 0.75 mol% to 1.25 mol%, from 0.75 mol% to 1 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of SrO.
• the concentration of BaO in the glass article may be greater than 0 mol%, 0.25 mol% or more, 0.5 mol% or more, 0.75 mol% or more, 1 mol% or more, 2 mol% or less, 1.75 mol% or less, 1.5 mol% or less, 1.25 mol% or less, or 1 mol% or less
• the concentration of BaO in the glass article may be from greater than 0 mol% to 2 mol%, from 0.25 mol% to 1.75 mol%, from 0.5 mol% to 1.5 mol%, from 0.75 mol% to 1.25 mol%, from 0.75 mol% to 1 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of BaO.
• the concentration of R'O in the glass article may be greater than 0 mol%, 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 8 mol% or less, 7.5 mol% or less, 7 mol% or less, 6.5 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, or 3.5 mol% or less.
• the concentration of R'O in the glass article may be from greater than 0 mol% to 8 mol%, from 0.5 mol% to 7.5 mol%, from 0.5 mol% to 7 mol%, from 1 mol% to 6.5 mol% from 1 mol% to 6 mol%, from 1.5 mol% to 5.5 mol%, from 1.5 mol% to 5 mol%, from 2 mol% to 4.5 mol%, from 2 mol% to 4 mol%, from 2.5 mol% to 3.5 mol%, or any range or subrange therebetween.
• a sum of R 2 O, CaO, MgO, and ZnO may be 35 mol% or less, for example, from 1 mol% to 30 mol%, from 2 mol% to 30 mol%, from 3 mol% to 25 mol%, from 4 mol% to 25 mol%, from 5 mol% to 20 mol%, 6 mol% to 20 mol%, from 7 mol% to 15 mol%, from 8 mol% to 10 mol%, or any range or subrange therebetween.
• a sum of Al 2 O 3 , MgO, and ZnO present in the glass article may be from 12 mol% to 22 mol%.
• Al 2 O 3 (mol%) + MgO (mol%) + ZnO (mol%) may be from 12 mol% to 22 mol%.
• combinations of Al 2 O 3 , MgO, and ZnO within this range may aid in avoiding the formation of undesired crystal phases in the resultant colored glass articles.
• a sum of Al 2 O 3 , MgO, and ZnO in the glass article may be from 13 mol% to 21.5 mol%.
• the sum of Al 2 O 3 , MgO, and ZnO in the glass article may be 12 mol% or more, 13 mol% or more, 14 mol% or more, 15 mol% or more, 16 mol% or more, 22 mol% or less, 21.5 mol% or less, 21 mol% or less, 20.5 mol% or less, or 20 mol% or less.
• the sum of Al 2 O 3 , MgO, and ZnO in the glass article may be from 12 mol% to 22 mol%, from 13 mol% to 21.5 mol%, from 14 mol% to 21 mol%, from 15 mol% to 20.5 mol%, from 16 mol% to 20 mol%, or any range or subrange therebetween.
• a sum of Al 2 O 3 , MgO, CaO, and ZnO present in the glass article may be from 12 mol% to 24 mol%.
• Al 2 O 3 (mol%) + MgO (mol%) + CaO (mol%) + ZnO (mol%) may be from 12 mol% to 24 mol%.
• combinations of Al 2 O 3 , MgO, CaO, and ZnO within this range may aid in avoiding the formation of undesired crystal phases in the glass article.
• a relatively high concentration of high field strength modifiers may also improve the mechanical properties, for example fracture toughness, elastic modulus, and drop test performance, of the resultant colored glass article.
• a sum of Al 2 O 3 , MgO, CaO, and ZnO in the glass article may be from 12 mol% to 24 mol%.
• the sum of Al 2 O 3 , MgO, CaO, and ZnO in the glass article may be 12 mol% or more, 13 mol% or more, 14 mol% or more, 15 mol% or more, 16 mol% or more, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21.5 mol% or less, 21 mol% or less, 20.5 mol% or less, or 20 mol% or less
• the sum of Al 2 O 3 , MgO, CaO, and ZnO in the glass article may be from 12 mol% to 24 mol%, from 13 mol% to 23 mol%, from 13 mol% to 22 mol%, from 14 mol% to 21.5 mol%, from 14 mol% to 21 mol%, from 15 mol% to 20.5 mol%, from 16 mol% to 20 mol%, or any range or subrange therebetween.
• the glass article may optionally include Cl, which may enable growth of particular crystal phases containing colorant.
• the colorant package included in the glass comprises Au
• the inclusion of Cl may enable the growth of certain Au crystals.
• the concentration of Cl in the glass article may be greater than 0 mol%, 0.1 mol% or more, 0.5 mol% or less, or 0.25 mol% or less.
• the concentration of Cl in the glass article may be from greater than 0 mol% to 0.5 mol%, from 0.1 mol% to 0.25 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of Cl.
• the colorant package comprises Ag
• the glass article can include less than 100 ppm of halides, including Cl.
• the glass articles described herein may further comprise ZrO 2 .
• ZrCF may act as a multivalent species that serves as redox couples to supply oxygen to certain colorants, for example Au, during relatively low-temperature heat treatment, which helps improve retention of the colorant.
• ZrO 2 may also act as an additional colorant, producing colored glass articles that may be, for example, red in color.
• the glass article may comprise ZrCC in an amount of 0.01 mol% or more, 0.1 mol% or more, 0.2 mol% or more 0.25 mol% or more, 0.5 mol% or more, 0.75 mol% or more, 1 mol% or more, 2 mol% or less, 1.75 mol% or less, 1.5 mol% or less, 1 mol% or less, or 0.5 mol% or less.
• the glass article may comprise ZrO 2 in an amount from 0.01 mol% to 2 mol%, from 0.1 mol% to 1.75 mol%, from 0.2 mol% to 1.5 mol%, from 0.25 mol% to 1.25 mol%, from 0.5 mol% to 1 mol%, from 0.75 mol% to 1 mol%, or any range or subrange therebetween.
• the glass compositions and the resultant colored glass articles described herein may further comprise Fe 2 O 3 , which may help improve colorant retention.
• Fe 2 O 3 is a multivalent species that serves as redox couples to supply oxygen to certain colorants, for example Au, during relatively low-temperature heat treatment, which helps improve retention of the colorant.
• Fe2O 3 may also act as a colorant, producing colored glass articles that may, for example, be pink or red in color.
• the glass article may comprise Fe 2 O 3 in an amount of greater than 0 mol%, 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 1 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, or 0.1 mol% or less.
• the glass article may comprise Fe 2 O 3 in an amount from greater than 0 mol% to 1 mol%, from 0.01 mol% to 0.75 mol%, from 0.05 mol% to 0.5 mol%, from 0.1 mol% to 0.25 mol%, or any range or subrange therebetween.
• the glass article may comprise Fe 2 O 3 in an amount of 200 parts-per-million (ppm) or more, 250 ppm or more, 300 ppm or more, 350 ppm or more, 400 ppm or less, 1,000 ppm or less, 600 ppm or less, 550 ppm or less, 500 ppm or less, or 450 ppm or less.
• the glass article can comprise Fe 2 O 3 in an amount from about 200 ppm to about 1,000 ppm, from about 300 ppm to about 600 ppm, from about 350 ppm to about 550 ppm, from about 400 ppm to about 500 ppm, or any range or subrange therebetween.
• the glass article may be substantially free or free of Fe 2 O 3 .
• the glass compositions and the resultant colored glass articles described herein may further comprise SnO 2 , Sb2O 3 , and/or Bi2O 3 .
• SnO 2 , Sb2O 3 , and Bi2O 3 may help lower the melting point of the glass composition. Accordingly, SnO 2 , Sb2O 3 , and/or Bi2O 3 may be included in the glass articles to lower the melting point and improve colorant retention.
• the colorant package includes Ag
• SnO 2 also aids in the reduction of Ag in the glass leading to the formation of silver particles in the glass.
• the colorant package includes Au
• additions of SnO 2 may also aid in the reduction of Au in the glass, leading to the formation of gold particles.
• the SnO 2 and/or Sb2O 3 may also function as a fining agent.
• the glass article may comprise SnO 2 in an amount of greater than 0 mol%, 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.25 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, or 0.1 mol% or less.
• the glass article may comprise SnO 2 in an amount from greater than 0 mol% to 1 mol%, from 0.01 mol% to 0.75 mol%, from 0.05 mol% to 0.5 mol%, from 0.1 mol% to 0.25 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of SnO 2 .
• the concentration of Sb2O 3 in the glass article may be greater than 0 mol%, 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, or 0.1 mol% or less, aspects, the concentration of Sb2O 3 in the glass article may be from greater than 0 mol% to 1 mol%, from 0.01 mol% to 0.75 mol%, from 0.05 mol% to 0.5 mol%, from 0. 1 mol% to 0.25 mol%, or any range or subrange therebetween. In aspects, the glass article may be substantially free or free of Sb2O 3 .
• the glass article can comprise Sb 2 O 3 in an amount from 0.01 wt% to about 0.5 wt%, from 0.02 wt% to about 0.4 wt%, from 0.05 wt% to about 0.3 wt%, from 0.1 wt% to about 0.2 wt%, or any range or subrange therebetween.
• the concentration of Bi2O 3 in the glass article may be greater than 0 mol%, 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, or 0.1 mol% or less.
• the concentration of B i 2 O 3 in the glass article may be from greater than 0 mol% to 1 mol%, from 0.01 mol% to 0.75 mol%, from 0.05 mol% to 0.5 mol%, from 0.1 mol% to 0.25 mol%, or any range or subrange therebetween.
• the glass article may be substantially free or free of Bi2O 3 .
• the concentration of SO 3 in the glass article may be 0.1 mol% or less, 0.01 mol% or less, or 0.001 mol% or less. In aspects, the glass article may be substantially free or free of SO 3 .
• the glass articles described herein may further comprise a reduced concentration or be substantially free or free of P 2 O 5 .
• the P 2 O 5 may enhance the ion exchange characteristics of the resultant colored glass article.
• an increased concentration (i.e., greater than 1 mol%) of P 2 O 5 may reduce the retention of one or more colorants in the colorant package.
• P 2 O 5 may be more volatile than other glass network formers, for example SiO 2 , which may contribute to reduced retention of colorants in the colorant package.
• the concentration of P 2 O 5 in the glass article may comprise be greater than 0 mol%, 0.1 mol% or more, 0.25 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or 0.25 mol% or less. In aspects, the concentration ofP 2 O 5 in the glass article may comprise be from greater than 0 mol% to 1 mol%, from 0.1 mol% to 0.75 mol%, from 0.25 mol% to 0.5 mol%, or any range or subrange therebetween. In aspects, the glass article may be substantially free or free of P 2 O 5 .
• the glass articles can comprise at least one colorant in a colorant package that functions to impart a desired color to the glass article.
• the colorant package may comprise at least one of Au, Ag, Cr 2 O 3 , transition metal oxides (e.g., CuO, NiO, Co 3 O 4 , TiO 2 , Cr 2 O 3 ), rare earth metal oxides (e.g., CeCO 2 ), and/or combinations thereof.
• the glass articles may be from 1x1 O’ 6 mol% to 10 mol% of colorant (i.e., the sum of all colorants in the colorant package).
• the concentration of the colorant package in the glass article may be 1 x 10" 6 mol% or more, 0.0005 mol% or more, 0.001 mol% or more, 0.01 mol% or more, 0.1 mol% or more, 10 mol% or less, 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7 mol% or less, 6.5 mol% or less, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less 1.5 mol% or less 1 mol% or less, 0.5 mol% or less.
• the concentration of the colorant package in the glass article may be from 1 x 1 O’ 6 mol% to 10 mol%, from 1 x 1 O’ 6 mol% to 9 mol%, from 1 x 10 -6 mol% to 8 mol%, from 0.0005 mol% to 7 mol%, from 0.0005 mol% to 6 mol%, from 0.0005 mol% to 5 mol%, from 0.001 mol% to 4 mol%, from 0.001 mol% to 3 mol%, from 0.001 mol% to 2 mol%, from 0.01 mol% to 1.5 mol%, from 0.01 mol% to 1 mol%, from 0.1 mol% to about 0.5 mol%, or any range or subrange therebetween.
• the concentration of the colorant package in the glass article may be from 1 x 10 -6 mol% to 1 mol%, from 0.0005 mol% to about 0.5 mol%, from 0.001 mol% to 0.25 mol%, from 0.01 mol% to 0.1 mol%, or any range or subrange therebetween.
• the colorant package in the glass articles may include colorants that comprise or consist of transition metal oxides, rare earth oxides, or combinations thereof, to achieve a desired color.
• transition metal oxides and/or rare earth oxides may be included in the glass compositions as the sole colorant or in combination with other colorants.
• colorants based on transition metal oxides and/or rare earth oxides may include NiO, Co 3 O 4 , Cr2O 3 , CuO, CeO 2 , TiO 2 and/or combinations thereof.
• colorants based on transition metal oxides and/or rare earth oxides may further include oxides of V, Mn, Fe, Cu, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er.
• the glass article may comprise a concentration of NiO + Co 3 O 4 + Cr 2 O 3 + CuO + CeO 2 + TiO 2 of greater than 0 mol%, 0.001 mol% or more, 0.01 mol% or more, 0.02 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 0.9 mol% or more, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or 0.25 mol% or less.
• the glass article may comprise a concentration of NiO + CO 3 O 4 + Cr 2 O 3 + CuO + CeO 2 + TiO 2 can range from grater that 0 mol% to 5 mol%, from 0.001 mol% to 4 mol%, from 0.01 mol% to 3 mol%, from 0.02 mol% to 2.5 mol%, from 0.1 mol% to 2 mol%, from 0.5 mol% to 1.5 mol%, from 0.7 mol% to 1 mol%, or any range or subrange therebetween.
• the glass composition and resultant glass article may comprise 0 mol% of one or more of NiO, Co 3 O 4 , Cr2O 3 , CuO, CeO 2 , and/or TiO 2 .
• the glass article may comprise a concentration of NiO + Co 3 O 4 + Cr 2 O 3 + CuO from 0.001 mol to 3 mol%.
• the glass article may comprise a concentration of NiO + Co 3 O 4 + Cr 2 O 3 + CuO of greater than 0 mol%, 0.001 mol% or more, 0.01 mol% or more, 0.02 mol% or more, 0.1 mol% or more, 0.2 mol%, 0.5 mol%, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.5 mol% or less, or 0.4 mol% or less.
• the glass article may comprise a concentration of NiO + CO 3 O 4 + Cr 2 O 3 + CuO from greater than 0 mol% to 3 mol%, from 0.001 mol% to 2.5 mol%, from 0.01 mol% to 2 mol%, from 0.02 mol% to 1.5 mol%, from 0.1 mol% to 1 mol%, from 0.2 mol% to 0.5 mol%, from 0.2 mol% to 0.4 mol%, or any range or subrange therebetween.
• the glass composition and resultant glass article may comprise 0 mol% of one or more of NiO, Co 3 O 4 , Cr 2 O 3 , and/or CuO.
• the glass article may comprise a concentration of TiO 2 of greater than 0 mol%, 0.01 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or 0.4 mol% or less.
• the glass article may comprise a concentration of TiCC from greater than 0 mol% to 2 mol%, from 0.01 mol% to 1.5 mol%, from 0.1 mol% to 1 mol%, from 0.2 mol% to 0.75 mol%, from 0.3 mol% to 0.5 mol%, from 0.3 mol% to 0.4 mol%, or any range or subrange therebetween.
• the glass article may comprise a concentration of CeO 2 of 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or 0.4 mol% or less.
• the glass article may comprise a concentration of CeCO 2 from 0. 1 mol% to 2 mol%, from 0.2 mol% to 1.5 mol%, from 0.2 mol% to 1 mol%, from 0.3 mol% to 0.75 mol%, from 0.3 mol% to 0.5 mol, from 0.3 mol% to 0.4 mol%, or any range or subrange therebetween.
• the glass article may comprise a concentration of NiO of greater than 0 mol%, 0.01 mol% or more, 0.015 mol% or more, 0.02 mol% or more, 0.05 mol% or less, 0.04 mol% or less, 0.035 mol% or less, 0.03 mol% or less, 0.025 mol% or less, 0.02 mol% or less, or 0.015 mol% or less.
• the glass article may comprise a concentration of NiO can be from greater than 0 mol% to 0.05 mol%, from 0.01 mol% to 0.04 mol%, from 0.01 mol% to 0.035 mol%, from 0.015 mol% to 0.03 mol%, from 0.02 mol% to 0.025 mol%, or any range or subrange therebetween.
• the glass article may comprise a concentration of CuO of greater than 0 mol%, 0.1 mol% or more, 0.15 mol% or more, 0.5 mol% or less, 0.4 mol% or less, 0.35 mol% or less, 0.3 mol% or less, 0.25 mol% or less, 0.2 mol% or less, or 0.15 mol% or less.
• the glass article may comprise a concentration of CuO from greater than 0 mol% to 0.5 mol%, from 0.1 mol% to 0.4 mol% from 0.1 mol% to 0.35 mol%, from 0.15 mol% to 0.3 mol%, from 0.15 mol% to 0.25 mol%, from 0.15 mol% to 0.2 mol%, or any range or subrange therebetween.
• the glass article may comprise a concentration of Co 3 O 4 of greater than 0 mol%, 0.0001 mol% or more, 0.0002 mol% or more, 0.0005 mol% or more, 0.001 mol% or more, 0.01 mol% or less, 0.0095 mol% or less, 0.009 mol% or less, 0.0085 mol% or less, 0.008 mol% or less, 0.0075 mol% or less, 0.007 mol% or less, 0.0065 mol% or less, 0.006 mol% or less, 0.0055 mol% or less, 0.005 mol% or less, 0.0045 mol% or less, 0.004 mol% or less, 0.0035 mol% or less, 0.003 mol% or less, 0.0025 mol% or less, or 0.002 mol% or less.
• the glass article may comprise a concentration of Co 3 O 4 from greater than 0 mol% to 0.01 mol% or less, from 0.0001 mol% to 0.009 mol% or less, from 0.0001 mol% to 0.008 mol%, from 0.0001 mol% to 0.007 mol%, from 0.0002 mol% to 0.006 mol%, from 0.0002 mol% to 0.005 mol%, from 0.0005 mol% to 0.004 mol%, from 0.0005 mol% to 0.003 mol%, from 0.01 mol% to 0.02 mol%, or any range or subrange therebetween.
• the glass article may comprise at least one of: 0.001 mol% or more of NiO + CO 3 O 4 + Cr2O 3 + CuO (e.g., from 0.001 mol% to 3 mol or any of the ranges of NiO + Co 3 O 4 + Cr 2 O 3 + CuO described herein); 0.1 mol% or more of CeO 2 (e.g., from 0.1 mol% to 1.5 mol% or any of the ranges of CeO 2 described herein); and/or 0.1 mol% or more of TiCE (e.g., from 0.1 mol% to 2 mol% or any of the ranges of TiCE described herein).
• NiO + CO 3 O 4 + Cr2O 3 + CuO e.g., from 0.001 mol% to 3 mol or any of the ranges of NiO + Co 3 O 4 + Cr 2 O 3 + CuO described herein
• CeO 2 e.g., from 0.1 mol% to 1.5 mol% or any of the ranges of CeO 2 described
• the colorant package in the glass compositions and the resultant colored glass articles may comprise or consist of Au as a colorant to achieve a desired color.
• Au may be included in the glass compositions as the sole colorant or in combination with other colorants.
• the glass compositions and the resultant colored glass articles may be formulated to improve the retention of Au, thereby expanding the color gamut achievable in the resultant colored glass articles.
• the glass article may comprise a concentration of Au of 0.0005 mol% or more, 0.001 mol% or more, 0.002 mol% or more, 0.005 mol% or more, 0.01 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, 0.1 mol% or less, or 0.05 mol% or less.
• the glass article may comprise a concentration of Au from 0.0005 mol% to 1 mol%, from 0.001 mol% to 0.75 mol%, from 0.002 mol% to 0.5 mol%, from 0.005 mol% to 0.25 mol%, from 0.01 mol% to 0.1 mol%, from 0.01 mol% to 0.05 mol%, or any range or subrange therebetween.
• the glass article may comprise a concentration of Au of 1 ppm or more, 5 ppm or more, 10 ppm or more, 15 ppm or more, 100 ppm or more, 500 ppm or more, 1,000 ppm or more, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 10,000 ppm or less, 2,000 ppm or less, 1,000 ppm or less, 500 ppm or less, 100 ppm or less, 50 ppm or less, or 20 ppm or less.
• the glass article may comprise a concentration of Au from 1 ppm to 10,000 ppm, from 1 ppm to 2,000 ppm, from 5 ppm to 1,000 ppm, from 5 ppm to 500 ppm, from 10 ppm to 100 ppm, from 15 ppm to 50 ppm, or any range or subrange therebetween.
• a different color gamut may be achieved by including secondary colorants in addition to Au.
• the glass composition and resultant colored glass article may comprise greater than or equal to 0 mol% and less than or equal to 1 mol% of a cation “M”, wherein “M” is at least one of F, Cl, Br, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Te, W, Ir, Pt, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er.
• M is at least one of F, Cl, Br, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Te, W, Ir, Pt, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er.
• the colorant package used in the glass compositions and the resultant colored glass articles described herein may comprise or consist of Cr 2 O 3 as a colorant to achieve a desired color.
• Cr 2 O 3 may be included in the glass compositions as the sole colorant or in combination with other colorants.
• other transition metal oxides may be included in the glass composition to modify the color imparted to the glass, including, for example and without limitation, CuO, NiO, and/or Co 3 O 4 .
• the glass compositions and the resultant colored glass articles may be formulated to improve the solubility of Cr 2 O 3 , thereby expanding the color gamut achievable in the resultant colored glass articles.
• the glass article may comprise Cr 2 O 3 of greater than 0 mol% or more, 0.001 mol% or more, 0.005 mol% or less, 0.01 mol% or more, 0.05 mol% or more, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.5 mol% or less, or 0.1 mol% or less.
• the glass article may comprise Cr 2 O 3 from greater than 0 mol% to 2 mol%, from 0.001 mol% to 1.5 mol%, from 0.005 mol% to 1 mol%, from 0.01 mol% to 0.05 mol%, from 0.05 mol% to 0.1 mol%, or any range or subrange therebetween.
• the glass article may comprise Cr 2 O 3 from 100 ppm to 10,000 ppm, from 100 ppm to 5,000 ppm, from 300 ppm to 2,000 ppm, from 500 ppm to 1,000 ppm, or any range or subrange therebetween.
• the glass compositions and the resultant colored glass articles are per-alkali (i.e., R 2 O (mol%) + R'O (mol%) - Al 2 O 3 (mol%) is 0.5 mol% or more) to increase the solubility of Cr 2 O 3 and avoid Cr-spinel crystal formation.
• R 2 O + R'O - Al 2 O 3 in the glass article may be limited (e.g., less than or equal to 6 mol%) to prevent a reduction in fracture toughness.
• R 2 O + R'O - Al 2 O 3 in the glass article may be from 0.5 mol% to 6 mol% or from 1 mol% to 5.5 mol%.
• R 2 O + R'O - Al 2 O 3 in the glass article may be 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, or 2.5 mol% or less.
• R 2 O + R'O - Al 2 O 3 in the glass article may be from 0.5 mol% to 6 mol%, from 0.5 mol% to 5.5 mol%, from 1 mol% to 5 mol%, from 1 mol% to 4.5 mol%, from 1.5 mol% to 4 mol%, from 1.5 mol% to 3.5 mol%, from 2 mol% to 3 mol%, from 2 mol% to 2.5 mol%, or any range or subrange therebetween.
• the glass compositions and the resultant colored glass articles may satisfy at least one of the following conditions and achieve the desired color: (1) less than or equal to 17.5 mol% Al 2 O 3 and/or R 2 O + R'O - Al 2 O 3 greater than or equal to 0.5 mol%; (2) Al 2 O 3 + MgO + ZnO less than or equal to 22 mol%; and (3) MgO + ZnO less than or equal to 4.5 mol%.
• the colorant comprises Cr 2 O 3
• different color gamuts may be achieved by including other colorants in addition to Cr 2 O 3 .
• the glass composition and resultant colored glass article may comprise NiO, Co 3 O 4 , CuO, or combinations thereof in addition to Cr 2 O 3 .
• the glass article may comprise from greater than 0 mol% to 4 mol% NiO as a colorant in addition to Cr2O 3 .
• the concentration of NiO in the glass article may be greater than 0 mol%, 0.01 mol% or more, 0.05 mol% or more, 4 mol% or less, 3 mol% or less, 2 mol% or less 1 mol% or less, 0.5 mol% or less, 0.25 mol% or less, 0.1 mol% or less.
• the concentration of NiO in the glass article may be from greater than 0 mol% to 4 mol%, from greater than 0 mol% to 3 mol%, from 0.01 mol% to 2 mol%, from 0.01 mol% to 1 mol%, from 0.01 mol%, from 0.5 mol%, from 0.05 mol% to 0.25 mol%, from 0.05 mol% to 0.1 mol%, or any range or subrange therebetween.
• the glass article may comprise from greater than 0 mol% to 2 mol% Co 3 O 4 as a colorant in addition to Cr 2 O 3 .
• the concentration of Co 3 O 4 in the glass article may be greater than 0 mol%, 0.001 mol% or more, 0.005 mol% or more, 0.01 mol% or more, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.1 mol% or less, or 0.05 mol% or less.
• the concentration of Co 3 O 4 in the glass article may be from greater than 0 mol% to 2 mol%, from 0.001 mol% to 1.5 mol%, from 0.001 mol% to 1 mol%, from 0.005 mol% to 0.5 mol%, from 0.005 mol% to 0.1 mol%, from 0.01 mol% to 0.05 mol%, or any range or subrange therebetween.
• the glass article may comprise from greater than 0 mol% to 5 mol% CuO as a colorant in addition to Cr 2 O 3 .
• the concentration of CuO in the glass article may be greater than 0 mol%, 0.05 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 5 mol% or less, 4 mol% or less, 3 mol% or less, or 2 mol% or less.
• the concentration of CuO in the glass article may be from greater than 0 mol% to 5 mol%, from 0.05 mol% to 4 mol%, from 0.1 mol% to 3 mol%, from 0.5 to 2 mol%, from 1 mol% to 2 mol%, or any range or subrange therebetween.
• the colorant package used in the glass compositions and the resultant colored glass articles may comprise or consist of Ag as a colorant to achieve a desired color.
• the glass compositions and the resultant colored glass articles may be formulated to improve the retention of Ag, thereby expanding the color gamut achievable in the resultant colored glass articles.
• Ag may be included in the glass compositions as the sole colorant or in combination with other colorants.
• the color is created by the presence of anisotropic silver particles in the colored glass article that are formed from the reduction of silver ions in the glass composition.
• the glass article may comprise a concentration of Ag from 0.01 mol% to 5 mol%.
• the glass article may comprise a concentration of Ag of 0.01 mol% or more, 0.05 mol% or more, 0. 1 mol% or more, 5 mol% or less, 2.5 mol% or less, 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less.
• the concentration of Ag in the glass article may be from 0.01 mol% to 5 mol%, from 0.01 mol% to 2.5 mol%, from 0.05 mol% to 1 mol%, from 0.05 mol% to 0.75 mol%, from 0.1 mol% to 0.5 mol%, from 0.1 mol% to 0.25 mol%, or any range or subrange therebetween.
• halide-free colored glass articles that comprise silver in as-formed condition (i.e., colored glass articles that have not been subjected to mechanical stretching) produce only yellow, orange, and red colors upon a suitable heat treatment applied to the glass article in as-formed condition.
• These colors are generated by the formation of isotropic (i.e., nominally spherical) silver particles in the conventional, halide-free colored glass article.
• isotropic silver particles support a single localized surface plasmon resonance. Isotropic silver particles are the most energetically favorable to form because they have the lowest surface area to volume ratio and, as a result, they are the most common geometry observed in colored glass articles that comprise silver.
• anisotropic silver particles refer to silver particles having an aspect ratio greater than 1 , where the aspect ratio is the ratio of a longest dimension of the particle to a shortest dimension of the particle (e.g., a ratio of the length of the particle to the width of the particle is greater than 1). This is in contrast to an isotropic silver particle in which the aspect ratio is 1.
• the broader color gamut produced in glasses having anisotropic silver particles is because anisotropic silver particles support two distinct plasmonic modes: a higher energy transverse mode, and a lower energy longitudinal mode.
• anisotropic metallic silver particles in glass can be either induced by elongating spherical particles of silver through shear forces (e.g., by stretching the colored glass article via re-draw) using mechanical stretching processes.
• the mechanical stretching process results in a glass article having silver particles that are generally aligned in parallel with one another along the stretching direction (i.e., the glass is polarized).
• a conventional alternative to mechanical stretching processes for creating anisotropic metallic particles in a glass article is the incorporation of halides (e.g., F, Cl, and Br) in the glass composition.
• halides e.g., F, Cl, and Br
• anisotropic silver particles are formed by templating the particles on elongated and/or pyramidal-shaped halide crystals.
• the inclusion of halides in the glass composition may be undesirable.
• the colored glass articles comprising Ag as a colorant described herein may generate a broad range of colors, for example yellow, orange, red, green, pink, purple, brown, and black without the inclusion of halides in the glass composition or the use of mechanical stretching processes.
• anisotropic silver particles may form in the colored glass articles of the present disclosure due to a mechanism similar to the template growth caused by the inclusion of halides in the glass composition.
• anisotropic silver crystals may form on nano-sized crystals of spodumene, lithium silicate, and/or beta quartz during heat treatment of the glass article in its as-formed condition. Additionally and/or alternatively, it is believed that anisotropic silver particles may precipitate at the interfaces between phase-separated regions of the colored glass article and/or regions that are only partially crystalized. Further, these crystals and/or phase-separated regions may form a nucleation site for the growth of anisotropic silver particles.
• the glass article including silver as a colorant may comprise less than 100 parts per million (ppm) of halides.
• the glass compositions and the resultant colored glass articles comprising Ag as a colorant may comprise less than 100 ppm halides, for example less than 50 ppm halides, less than 25 ppm halides, less than 10 ppm halides, or even 0 ppm halides.
• colored glass articles comprising Ag produced using mechanical stretching processes generally include anisotropic silver particles similar to those of the colored glass article of the present application.
• these mechanical stretching processes also result in the anisotropic silver particles being ordered and aligned (e.g., the longer dimensions of each anisotropic silver particles are facing in the same direction, for example in the direction of mechanical stretching).
• the colored glass articles produced using mechanical stretching processes are polarized due to the alignment of the anisotropic silver particles in the glass as a result of mechanical stretching.
• the colored glass articles comprising Ag as a colorant which are not subjected to mechanical stretching processes, are non-polarized.
• the anisotropic silver particles of the colored glass article are not aligned (e.g., the longer dimensions of two or more anisotropic silver particles are facing in different directions) and, instead, the anisotropic silver particles are randomly aligned in the glass.
• length refers to the longest dimension of the anisotropic silver particle.
• the “width” refers to the dimension of the anisotropic particle that is perpendicular to the length.
• a calibration is set by measuring the scale bar on the electron micrograph, converting each pixel to the appropriate unit length. The image is then converted into a grayscale image. A software measuring tool is then used to measure the number of pixels from one end to the other of each particle as well as the number of pixels across the greatest width of the particle.
• an automated script is run to measure the length and aspect ratios of multiple particles automatically.
• a length of the anisotropic silver particles can be 10 nm or more, 12 nm or more, 14 nm or more, 16 nm or more, 18 nm or more, 22 nm or more, 34 nm or more, 36 nm or more, 38 nm or more, 40 nm or less, 38 nm or less, 36 nm or less, 34 nm or less, 32 nm or less, 30 nm or less, 28 nm or less, 26 nm or less, 24 nm or less, 22 nm or less, or 20 nm or less.
• the length of the anisotropic silver particles can range from 10 nm to 40 nm, from 12 nm to 36 nm, from 14 nm to 34 nm, from 14 nm to 32 nm, from 14 nm to 28 nm, from 14 nm to 26 nm, from 16 nm to 22 nm, from 16 nm to 20 nm, or any range or subrange therebetween.
• a width of the anisotropic silver particles can be 6 nm or more, 8 nm or more, 10 nm or more, 12 nm or more, 14 nm or more, 20 nm or less, 18 nm or less, 16 nm or less, 14 nm or less, 12 nm or less, or 10 nm or less.
• the width of the anisotropic silver particles can be from 6 nm to 20 nm, from 8 nm to 18 nm, from 8 nm to 16 nm, from 10 nm to 14 nm, or any range or subrange therebetween.
• “aspect ratio” is defined as the ratio of the length to the width of an anisotropic silver particle.
• an aspect ratio of the anisotropic silver particle can be greater than 1 , 1.5 or more, 2 or more, 2.5 or more, 3 or less, 2.5 or less, 2 or less, or 1.5 or less. In aspects, the aspect ratio of the anisotropic silver particle can range from greater than 1 to 3, from 1.5 to 2.5, from 2 to 2.5, or any range or subrange therebetween.
• the glass articles that include Ag as a colorant may further comprise one or more rare-earth oxides, for example CeCO 2 , Nd 2 O 3 , and/or Er2O 3 .
• Rare-earth oxides may be added to provide additional visible light absorbance to the glass (in addition to that imparted by the silver) to further alter the color of the glass.
• Rare- earth oxides may also be added to increase the Young’s modulus and/or the annealing point of the glass.
• the glass articles that include Ag as a colorant may further comprise a concentration of CeCO 2 of greater than 0 mol%, 0.05 mol% or more, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, or 0.5 mol% or less.
• the glass articles that include Ag as a colorant may further comprise a concentration of CeCO 2 from greater than 0 mol% to 4 mol%, from greater than 0 mol% to 3 mol%, from 0.05 mol% to 1 mol%, from 0.05 mol% to 0.5 mol%, or any range or subrange therebetween.
• the glass article may be substantially free and/or free of CeO 2 .
• the glass articles that include Ag as a colorant may comprise a concentration of Nd 2 O 3 that is greater than 0 mol%, 0. 1 mol% or more, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, or 0.5 mol% or less.
• the glass articles that include Ag as a colorant may comprise a concentration of Nd 2 O 3 from greater than 0 mol% to 4 mol%, from greater than 0 mol% to 3 mol%, from 0.1 mol% to 1 mol%, from 0.1 mol% to 0.5 mol%, or any range or subrange therebetween.
• the glass articles that include Ag as a colorant may comprise a concentration of E ⁇ Ch that is greater than 0 mol%, 0.1 mol% or more, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, or 0.5 mol% or less.
• the glass articles that include Ag as a colorant may comprise a concentration of Er 2 O 3 from greater than 0 mol% to 4 mol%, from greater than 0 mol% to 3 mol%, from 0.1 mol% to 1 mol%, from 0.1 mol% to 0.5 mol%, or any range or subrange therebetween.
• the glass articles described herein may further include tramp materials, for example, TiO 2 , MnO, MoO 3 , WO 3 , Y2O 3 , CdO, AS2O 3 , sulfurbased compounds (e.g., sulfates), halogens, or combinations thereof.
• the glass article may be substantially free or free of tramp materials, for example TiO 2 , MnO, MoO 3 , WO 3 , Y2O 3 , CdO, AS2O 3 , sulfur-based compounds (e.g., sulfates), halogens, or combinations thereof.
• decreasing the melting point of the glass article may help improve colorant retention because the glass compositions may be melted at relatively lower temperatures and colorant evaporation may be reduced.
• the glass articles described herein may optionally include MgO and/or ZnO, which help lower the melting point of the glass articles.
• B2O 3 , Li 2 O, and Na 2 O also decrease the melting point of the glass articles.
• other components may be added to the glass article to lower the melting point thereof, for example SnO 2 , Sb2O 3 , and Bi2O 3 .
• the glass article may have a melting point of 1300°C or more, 1325°C or more, 1350°C or more, 1375 °C or more, 1400°C or more, 1550°C or less, 1525 °C or less, 1500°C or less, 1475°C or less, or 1450°C or less.
• the melting point of the glass article can be from 1300°C to 1550°C, from 1325°C to 1525°C, from 1350°C to 1500°C, from 1375°C to 1475°C, from 1400°C to 1450°C, or any range or subrange therebetween.
• a liquidus temperature of the glass article may be 1000°C or more, 1050°C or more, 1100°C or more, 1400°C or less, 1350°C or less, or 1300°C or less. In aspects, a liquidus temperature of the glass article may be from 1000°C to 1400°C, from 1050°C to 1350°C, from 1100°C to 1300, or any range or subrange therebetween.
• the viscosity of the glass article may be adjusted to prevent devitrification of the glass composition and formation of colorant particles, for example Au particles, during melting and forming. Formation of colorant particles during melting and forming may limit the color gamut that may be achieved by heat treatment.
• colorant particles for example Au particles
• the glass articles described herein may satisfy the relationship 5.72*Al 2 O 3 (mol%) - 21.4*ZnO (mol%) - 2.5*P 2 O 5 (mol%) - 35*Li 2 O (mol%) - 16.6*B 2 O 3 (mol%) - 20.5*MgO (mol%) - 23.3*Na 2 O (mol%) - 27.9*SrO (mol%) - 18.5*K 2 O (mol%) - 26.3*CaO (mol%) is greater than -609 mol%.
• the glass articles described herein may satisfy the relationship 5.72*Al 2 O 3 (mol%) - 2I.4*ZnO (mol%) - 2.5*P 2 O 5 (mol%) - 35*Li 2 O (mol%) - 16.6*B 2 O 3 (mol%) - 20.5*MgO (mol%) - 23.3*Na 2 O (mol%) - 27.9*SrO (mol%) - 18.5*K 2 O (mol%) - 26.3*CaO (mol%) is greater than -609 mol%, greater than or equal to -575 mol%, greater than or equal to -550 mol%, or even greater than or equal to -525 mol%.
• the glass compositions and the resultant glass articles described herein may satisfy the relationship 5.72*Al 2 O 3 (mol%) - 21.4*ZnO (mol%) - 2.5*P 2 O 5 (mol%) - 35*Li 2 O (mol%) - 16.6*B 2 O 3 (mol%) - 20.5*MgO (mol%) - 23.3*Na 2 O (mol%) - 27.9*SrO (mol%) - 18.5*K 2 O (mol%) - 26.3*CaO (mol%) is less than or equal to -400 mol%, less than or equal to -425 mol%, or even less than or equal to -450 mol%.
• the glass articles described herein may satisfy the relationship 5.72*Al 2 O 3 (mol%) - 21.4*ZnO (mol%) - 2.5*P 2 O 5 (mol%) - 35*Li 2 O (mol%) - 16.6*B 2 O 3 (mol%) - 20.5*MgO (mol%) - 23.3*Na 2 O (mol%) - 27.9*SrO (mol%) - 18.5*K 2 O (mol%) - 26.3*CaO (mol%) is from -609 mol% to -400 mol%, from -575 mol% to -425 mol%, from -550 mol% to -450 mol%, from -525 mol% to - 450 mol%, or any range or subrange therebetween.
• the colorant package comprises Au
• relatively smaller concentrations of R 2 O - Al 2 O 3 e.g., less than or equal to 1.5 mol%) may result in a blue or purple glass article.
• Relatively higher concentrations of R 2 O - Al 2 O 3 e.g., greater than 1.5 mol%) may result in an orange or red glass article.
• R 2 O - Al 2 O 3 may be from -5 mol% to 1.5 mol% and b* may be from -25 to 10 (exclusive of b* greater than -0.5 and less than 0.5).
• R 2 O - Al 2 O 3 may be from -3 mol% to 1.5 mol% and b* may be from -15 to 7 (exclusive of b* greater than -0.5 and less than 0.5).
• R 2 O - Al 2 O 3 may be from -5 mol% to 1.5 mol%, from -1 mol% to 1.5 mol%, from 0 mol% to 1.5 mol%, or any range or subrange therebetween; and b* may be from -25 to 10 (exclusive of b* greater than -0.5 and less than 0.5), from -15 to 7, from -10 to 5 (exclusive of b* greater than -0.5 and less than 0.5), from -10 to 5 (exclusive of b* greater than -0.5 and less than 0.5), or any range or subrange therebetween.
• R 2 O - Al 2 O 3 may be from 1.5 mol% to 7 mol% and b* may be from 0.5 to 25. In aspects, R 2 O - Al 2 O 3 may be from 1.5 mol% to 5 mol% and b* may be from 0.5 to 15. In aspects, R 2 O - Al 2 O 3 may be from 1.5 mol% to 7 mol%, from 1.5 mol% to 5 mol%, from 1.5 mol% to 3 mol%, or any range or subrange therebetween; and b* may be from 0.5 to 25, from 2.5 to 15, from 5 to 10, or any range or subrange therebetween.
• the glass article may comprise from 60 mol% to 70 mol% SiO 2 ; from 11 mol% to 17 mol% Al 2 O 3 ; from 2 mol% to 8 mol% B2O 3 ; from 9 mol% to 14 mol% Li 2 O; from 2 mol% to 6 mol% Na 2 O; and from 1 x 10 -6 mol% to 0.01 mol% Au.
• the glass article can further comprise from 0.1 mol% to 2 mol% MgO; from 0.1 mol% to 2 mol% ZnO; and.
• MgO + ZnO is from 0. 1 mol% to 4.5 mol%.
• the glass article can further comprise from 0.1 mol% to 0.5 mol% K 2 O; and from 1 x 10 -6 mol% to 0.05 mol% Au.
• R 2 O - Al 2 O 3 is from 0 mol% to 3 mol%.
• the glass article may comprise from 40 mol% to 70 mol% SiO 2 ; from 8 mol% to 20 mol% Al 2 O 3 ; from 1 mol% to 10 mol% B2O 3 ; from 1 mol% to 20 mol% Li 2 O; from 1 mol% to 15 mol% Na 2 O; from 0 mol% to 6 mol% MgO; from 0 mol% to 5 mol% ZnO; and from 1 x 10 -6 mol% to 1 mol% Au, wherein: MgO + ZnO is from 0.1 mol% and to 6 mol%.
• the glass article may further comprise from 0 mol% to 8 mol% MgO and from 0.0005 mol% to 1 mol% Au.
• the glass article may comprise from 50 mol% to 80 mol% SiO 2 ; from 7 mol% to 25 mol% Al 2 O 3 ; from 1 mol% to 15 mol% B2O 3 ; from 5 mol% to 20 mol% Li 2 O; from 0.5 mol% to 15 mol% Na 2 O; from greater than 0 mol% to 1 mol% K 2 O; and from 1 x 1 O’ 6 mol% to 1 mol% Au, wherein: R 2 O - Al 2 O 3 is from -5 mol% to 7 mol%.
• the glass article can comprise from 50 mol% to 70 mol% SiO 2 ; from 10 mol% to 17.5 mol% Al 2 O 3 ; from 3 mol% to 10 mol% B2O 3 ; from 8.8 mol% to 14 mol% Li 2 O; from 1.5 mol% to 8 mol% Na 2 O; and from 0 mol% to 2 mol% Cr 2 CO 3 , wherein: R 2 O + R'O - Al 2 O 3 is from 0.5 mol% to 6 mol%, and Al 2 O 3 + MgO + ZnO is from 12 mol% to 22 mol%.
• the glass article may comprise from 50 mol% to 70 mol% SiO 2 ; from 10 mol% to 20 mol% Al 2 O 3 ; from 4 mol% to 10 mol% B2O 3 ; from 7 mol% to 17 mol% Li 2 O; from 1 mol% to 9 mol% Na 2 O; from 0.01 mol% to 1 mol% SnO2; and from 0.01 mol% to 5 mol% Ag, wherein R 2 O - Al 2 O 3 is from 0.2 mol% to 5.00 mol%.
• the glass article may comprise from 50 mol% to 70 mol% SiO 2 ; from 10 mol% to 20 mol% Al 2 O 3 ; from 1 mol% to 10 mol% B2O 3 ; from 7 mol% to 14 mol% Li 2 O; from 0.01 mol% to 8 mol% Na 2 O; from 0.01 mol% to 1 mol% K 2 O; from 0 mol% to 7 mol% CaO; and from 0 mol% to 8 mol% MgO, wherein Li 2 O + K 2 O + Na 2 O + CaO + MgO + ZnO is 25 mol% or more and at least one of: CuO + NiO + Co 3 O 4 + Cr 2 O 3 is 0.001 mol% or more, CeO 2 is 0.1 mol% or more, and/or TiO 2 is 0.1 mol% or more.
• fracture toughness represents the ability of a glass composition to resist fracture. Fracture toughness is measured on a non-strengthened glass article, such as measuring the Kic value prior to ion exchange (IOX) treatment of the glass article, thereby representing a feature of a glass substrate prior to IOX.
• IOX ion exchange
• the fracture toughness of an ion exchanged article means the fracture toughness of a non-ion exchanged article with the same composition and microstructure (when present) as the center (i.e., a point located at least 0.5t from every surface of the article or substrate where t is the thickness of the article or substrate) of the ion exchanged article (which corresponds to the portion of the ion exchanged article least affected by the ion exchange process and, hence, a composition and microstructure comparable to a non-ion exchanged glass).
• Fracture toughness is measured by the chevron notched short bar method.
• the chevron notched short bar (CNSB) method is disclosed in Reddy, K.P.R.
• the glass article may have an increased fracture toughness such that the colored glass articles are more resistant to damage.
• the glass article may have a Kic fracture toughness as measured by a CNSB method, prior to ion exchange, of 0.7 MPa-m 1/2 or more, 0.8 MPa-m 1/2 or more, 0.9 MPa-m 1/2 or more, or 1.0 MPa-m 1/2 or more.
• the glass article 350 and/or 511 formed from the glass compositions described herein may have an increased fracture toughness such that the colored glass articles are more resistant to damage.
• the glass article 350 and/or 511 may have a Kic fracture toughness as measured by the DCB method, prior to ion exchange, of 0.6 MPa-m 1/2 or more, 0.7 MPa-m 1/2 or more, 0.8 MPa-m 1/2 or more, 0.9 MPa-m 1/2 or more, 1.0 MPa-m 1/2 or more.
• the dielectric constant of the glass article is measured using a split post dielectric resonator (SPDR) at a frequency of 10 GHz.
• SPDR split post dielectric resonator
• the dielectric constant was measured on samples of the glass article having a length of 3 inches (76.2 mm), a width of 3 inches (76.2 mm), and a thickness of less than 0.9 mm.
• the glass article 350 and/or 511 comprises a dielectric constant Dk at 10 GHz of 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6 or less, 5.6 or more, 5.7 or more, 5.8 or more, 5.9 or more, or 6.0 or more.
• the glass article 350 and/or 511 comprises a dielectric constant Dk at 10 GHz in a range from 5.6 to 6.4, from 5.7 to 6.3, from 5.8 to 6.2, from 5.9 to 6.1, from 5.9 to 6, or any range or subrange therebetween.
• the dielectric constant at frequencies from 10 GHz to 60 GHz can be within one or more of the above- mentioned ranges.
• the dielectric constant of the glass article measured at 10 GHz approximates the dielectric constant at frequencies from 10 GHz to 60 GHz.
• a dielectric constant reported for a colored glass article at a frequency of 10 GHz approximates the dielectric constant of the colored glass article at frequencies in a range from 10 GHz to 60 GHz, inclusive of endpoints.
• the natively colored glass housing can further comprise a coating disposed on the first major surface of the glass article, for example.
• the coating can be an anti-reflective coating, an anti-glare coating, an easy-to-clean coating, a low-friction coating, an oleophobic coating, a diamond-like coating, a scratch-resistant, coating, an abrasion-resistant coating, a polymeric hard coating, or a combination thereof.
• a scratch-resistant coating may comprise an oxynitride, for example, aluminum oxynitride or silicon oxynitride with a thickness of about 500 micrometers or more.
• the abrasion-resistant layer may comprise the same material as the scratch-resistant layer.
• a low friction coating may comprise a highly fluorinated silane coupling agent, for example, an alkyl fluorosilane with oxymethyl groups pendant on the silicon atom.
• an easy-to-clean coating may comprise the same material as the low friction coating.
• the easy-to-clean coating may comprise a protonatable group, for example an amine, for example, an alkyl aminosilane with oxymethyl groups pendant on the silicon atom.
• the oleophobic coating may comprise the same material as the easy-to-clean coating.
• a diamond-like coating comprises carbon and may be created by applying a high voltage potential in the presence of a hydrocarbon plasma.
• a polymeric hard coating can comprise one or more of an ethylene-acid copolymer, a polyurethane-based polymer, an acrylate resin, and a mercapto-ester resin.
• ethylene-acid copolymers include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-acrylic -methacrylic acid terpolymers (e.g., Nucrel, manufactured by DuPont), ionomers of ethylene acid copolymers (e.g., Surlyn, manufactured by DuPont), and ethylene-acrylic acid copolymer amine dispersions (e.g., Aquacer, manufactured by BYK).
• Example aspects of polyurethane-based polymers include aqueous-modified polyurethane dispersions (e.g., Eleglas®, manufactured by Axalta).
• Example aspects of acrylate resins that can be UV curable include acrylate resins (e.g., Uvekol® resin, manufactured by Allinex), cyanoacrylate adhesives (e.g., Permabond® UV620, manufactured by Krayden), and UV radical acrylic resins (e.g., Ultrabond windshield repair resin, for example, Ultrabond (45CPS)).
• Example aspects of mercapto-ester resins include mercapto-ester triallyl isocyanurates (e.g., Norland optical adhesive NOA 61).
• the polymeric hard coating can comprise ethylene-acrylic acid copolymers and ethylene -methacrylic acid copolymers, which may be ionomerized to form ionomer resins through neutralization of the carboxylic acid residue with typically alkali-metal ions, for example, sodium and potassium, and also zinc.
• ethylene-acrylic acid and ethylene-methacrylic acid ionomers may be dispersed in water and coated onto the substrate to form an ionomer coating.
• acid copolymers may be neutralized with ammonia which, after coating and drying liberates the ammonia to reform the acid copolymer as the coating.
• the foldable apparatus can comprise low energy fracture.
• the polymeric hard coating can comprise an optically transparent hard-coat layer.
• Suitable materials for an optically transparent polymeric hard-coat layer include but are not limited to a cured acrylate resin material, an inorganic-organic hybrid polymeric material, an aliphatic or aromatic hexafimctional urethane acrylate, a siloxane-based hybrid material, and a nanocomposite material, for example, an epoxy and urethane material with nanosilicate.
• inorganic-organic hybrid polymeric material means a polymeric material comprising monomers with inorganic and organic components.
• An inorganic-organic hybrid polymer is obtained by a polymerization reaction between monomers having an inorganic group and an organic group.
• An inorganic-organic hybrid polymer is not a nanocomposite material comprising separate inorganic and organic constituents or phases, for example, inorganic particulates dispersed within an organic matrix.
• suitable materials for an optically transparent polymeric (OTP) hard-coat layer include, but are not limited to, a polyimide, a polyethylene terephthalate (PET), a polycarbonate (PC), a poly methyl methacrylate (PMMA), organic polymer materials, inorganic-organic hybrid polymeric materials, and aliphatic or aromatic hexafunctional urethane acrylates.
• an OTP hard-coat layer may consist essentially of an organic polymer material, an inorganic-organic hybrid polymeric material, or aliphatic or aromatic hexafunctional urethane acrylate.
• an OTP hard-coat layer may consist of a polyimide, an organic polymer material, an inorganic-organic hybrid polymeric material, or aliphatic or aromatic hexafunctional urethane acrylate.
• an OTP hard-coat layer may include a nanocomposite material.
• an OTP hard-coat layer may include a nano-silicate and at least one of epoxy or urethane materials. Suitable compositions for such an OTP hard-coat layer are described in U.S. Pat. Pub. No.
• organic polymer material means a polymeric material comprising monomers with only organic components.
• an OTP hard-coat layer may comprise an organic polymer material manufactured by Gunze Limited and having a hardness of 9H, for example Gunze’s “Highly Durable Transparent Film.”
• inorganic -organic hybrid polymeric material means a polymeric material comprising monomers with inorganic and organic components. An inorganic-organic hybrid polymer is obtained by a polymerization reaction between monomers having an inorganic group and an organic group.
• An inorganic-organic hybrid polymer is not a nanocomposite material comprising separate inorganic and organic constituents or phases, for example, inorganic particulates dispersed within an organic matrix.
• the inorganic-organic hybrid polymeric material may include polymerized monomers comprising an inorganic silicon-based group, for example, a silsesquioxane polymer.
• a silsesquioxane polymer may be, for example, an alkyl-silsesquioxane, an aryl- silsesquioxane, or an aryl alkyl-silsesquioxane having the following chemical structure: (RSiOi.s)n, where R is an organic group for example, but not limited to, methyl or phenyl.
• an OTP hard-coat layer may comprise a silsesquioxane polymer combined with an organic matrix, for example, SILPLUS manufactured by Nippon Steel Chemical Co., Ltd.
• an OTP hard-coat layer may comprise 90 wt% to 95 wt% aromatic hexafunctional urethane acrylate, e.g., PU662NT (Aromatic hexafunctional urethane acrylate) manufactured by Miwon Specialty Chemical Co.) and 10 wt% to 5 wt% photo-initiator (e.g., Darocur 1173 manufactured by Ciba Specialty Chemicals Corporation) with a hardness of 8H or more.
• aromatic hexafunctional urethane acrylate e.g., PU662NT (Aromatic hexafunctional urethane acrylate) manufactured by Miwon Specialty Chemical Co.
• 10 wt% to 5 wt% photo-initiator e.g., Darocur 1173 manufactured by Ciba Specialty Chemicals Corporation
• an OTP hard-coat layer composed of an aliphatic or aromatic hexafunctional urethane acrylate may be formed as a stand-alone layer by spin-coating the layer on a polyethylene terephthalate (PET) substrate, curing the urethane acrylate, and removing the urethane acrylate layer from the PET substrate.
• PET polyethylene terephthalate
• the glass article 350 and/or 511 can comprise one or more compressive stress regions.
• a compressive stress region may be created by chemically strengthening. Chemically strengthening may comprise an ion exchange process, where ions in a surface layer are replaced by-or exchanged with- larger ions having the same valence or oxidation state. Without wishing to be bound by theory, chemically strengthening the glass article can enable good impact resistance, good puncture resistance, and/or higher flexural strength.
• a compressive stress region may extend into a portion of glass article for a depth called the depth of compression (DOC).
• DOC depth of compression means the depth at which the stress in the chemically strengthened glass articles described herein changes from compressive stress to tensile stress.
• Depth of compression can be measured by a surface stress meter or a scattered light polariscope (SCALP, wherein values reported herein were made using SCALP-5 made by Glasstress Co., Estonia) depending on the ion exchange treatment and the thickness of the glass article being measured.
• a surface stress meter for example, the FSM-6000 (Orihara Industrial Co., Ltd. (Japan)
• compressive stress is measured by surface stress meter (FSM) using commercially available instruments, for example the FSM-6000, manufactured by Orihara.
• SOC stress optical coefficient
• ASTM standard C770-16 entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.
• SCALP is used to measure the depth of compression and central tension (CT).
• CT central tension
• the exchange depth of sodium may indicate the depth of compression while the exchange depth of potassium ions may indicate a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile).
• the refracted near-field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample”, which is incorporated herein by reference in its entirety) method also may be used to derive a graphical representation of the stress profile.
• the maximum central tension value provided by SCALP is utilized in the RNF method.
• depth of layer means the depth that the ions have exchanged into the glass article (e.g., sodium, potassium). Throughout the disclosure, DOL is measured in accordance with ASTM C-1422. Without wishing to be bound by theory, a DOL is usually greater than or equal to the corresponding DOC.
• the maximum CT can be approximated by a product of a maximum compressive stress and a depth of compression divided by the difference between the thickness of the glass article and twice the depth of compression, wherein the compressive stress and depth of compression are measured by FSM.
• the glass article 350 and/or 511 can comprise a first compressive stress region extending to a first depth of compression from the first major surface 332 and/or 513.
• the glass article 350 and/or 511 can comprise a second compressive stress region extending to a second depth of compression from the second major surface 330 and/or 515.
• the first depth of compression and/or the second depth of compression as a percentage of the thickness 337and/or 517 can be about 5% or more, about 10% or more, about 12% or more, about 15% or more, about 30% or less, about 25% or less, about 22% or less, about 20% or less, about 17% or less, or about 15% or less.
• the first depth of compression and/or the second depth of compression as a percentage of the thickness 337and/or 517 can be in a range from about 5% to about 30%, from about 10% to about 25%, from about 10% to about 22%, from about 12% to about 20%, from about 12% to about 17%, from about 15% to about 17%, or any range or subrange therebetween.
• the first depth of compression and/or the second depth of compression can be about 10 pm or more, about 20 pm or more, about 30 pm or more, about 40 pm or more, about 50 pm or more, about 60 pm or more, about 500 pm or less, about 200 pm or less, about 150 pm or less, about 100 pm or less, about 90 pm or less, or about 80 pm or less.
• the first depth of compression and/or the second depth of compression can be in a range from about 10 pm to about 500 pm, from about 20 pm to about 200 pm, from about 30 pm to about 150 pm, from about 40 pm to about 100 pm, from about 50 pm to about 90 pm, from about 60 pm to about 80 pm, or any range or subrange therebetween.
• the glass article 350 and/or 511 can comprise a first depth of layer of one or more alkali-metal ions associated with the first compressive stress region, and/or the glass article 350 and/or 511 can comprise a second depth of layer of one or more alkali-metal ions associated with the second compressive stress region and the second depth of compression.
• the one or more alkali-metal ions of a depth of layer of one or more alkali-metal ions can include sodium, potassium, rubidium, cesium, and/or francium.
• the one or more alkali ions of the first depth of layer of the one or more alkali ions and/or the second depth of layer of the one or more alkali ions comprises potassium.
• the first depth of layer and/or the second depth of layer, as a percentage of the thickness 517 can be about 1% or more, about 5% or more, about 10% or more, about 12% or more, about 15% or more, about 25% or less, about 20% or less, about 17% or less, about 15% or less, or about 10% or less.
• the first depth of layer and/or the second depth of layer, as a percentage of the thickness 517 can be in a range from about 1% to about 25%, from about 5% to about 20%, from about 10% to about 17%, from about 12% to about 15%, or any range or subrange therebetween.
• the first depth of layer of the one or more alkali-metal ions and/or the second depth of layer of the one or more alkali-metal ions can be about 1 pm or more, about 10 pm or more, about 15 pm or more, about 20 pm or more, about 25 pm or more, about 30 pm or more, about 200 pm or less, about 150 pm or less, about 100 pm or less, about 60 pm or less, about 45 pm or less, about 30 pm or less, or about 20 pm or less.
• the first depth of layer of the one or more alkali-metal ions and/or the second depth of layer of the one or more alkali-metal ions can be in a range from about 1 pm to about 200 pm, from about 1 pm to about 150 pm, from about 10 pm to about 100 pm, from about 15 pm to about 600 pm, from about 20 pm to about 45 pm, from about 20 pm to about 30 pm, or any range or subrange therebetween.
• the first compressive stress region can comprise a maximum first compressive stress
• the second compressive stress region can comprise a maximum second compressive stress.
• the maximum first compressive stress and/or the maximum second compressive stress can be about 100 MegaPascals (MPa) or more, about 300 MPa or more, 400 MPa or more, about 500 MPa or more, about 600 MPa or more, about 700 MPa or more, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less.
• the maximum first compressive stress and/or the maximum second compressive stress can be in a range from about 100 MPa to about 1,500 MPa, from about 300 MPa to about 1,200 MPa, from about 400 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, from about 600 MPa to about 900 MPa, from about 700 MPa to about 800 MPa, or any range or subrange therebetween.
• the glass article 350 and/or 511 can comprise a tensile stress region.
• the tensile stress region can be positioned between the first compressive stress region and the second compressive stress region.
• the tensile stress region can comprise a maximum tensile stress.
• the maximum tensile stress can be about 10 MPa or more, about 30 MPa or more, about 50 MPa or more, about 60 MPa or more, about 80 MPa or more, about 250 MPa or less, about 200 MPa or less, about 100 MPa or less, about 80 MPa or less, or about 60 MPa or less.
• the maximum tensile stress can be in a range from about 10 MPa to about 250 MPa, from about 30 MPa to about 200 MPa, from about 50 MPa to about 100 MPa, from about 60 MPa to about 80 MPa, or any range or subrange therebetween.
• the glass article 350 and/or 511 comprises an average transmittance over the wavelength range from 400 nm to 750 nm of 10% or more, about 15% or more, 20% or more, about 25% or more, about 30% or more, 40% or more, 60% or more, 70% or more, 75% or more, 80% or more, 82% or more, 85% or more, 87% or more, 92% or less, 91% or less, 90% or less, 89% or less, 88% or less, 87% or less 86% or less, 85% or less, 80% or less, 75% or less, or 70% or less.
• the glass article 350 and/or 511 comprises an average transmittance over the wavelength range from 400 nm to 750 nm from 10% to 92%, from 15% to 92%, from 20% to 91%, from 20% to 91%, from 25% to 91%, from 30% to 90%, from 40% to 90%, from 60% to 89%, from 70% to 88%, from 75% to 87%, from 80% to 86%, from 82% to 85%, or any range or subrange therebetween.
• the color exhibited by glass article 350 and/or 511 can correspond to at least one 10 nm band with lower transmittance than the average transmittance over the visible spectrum (e.g., from 400 nm to 700 nm).
• the glass article 350 and/or 511 can exhibit a total transmittance of at least one 10 nm band within the wavelength range of 380 nm to 750 nm that is 3% or more, 5% or more, 8% or more, 10% or more, 20% or more, 40% or more 50% or more, 60% or more, 70% or more, 80% or less, 78% or less, 75% or less, 72% or less, 70% or less, 68% or less, or 65% or less.
• the glass article 350 and/or 511 can exhibit a total transmittance of at least one 10 nm band within the wavelength range of 380 nm to 750 nm in range from 3% to 80% , from 5% to 78%, from 8% to 75%, from 10% to 72%, from 20% to 70%, from 40% to 68%, from 50% to 65%, or any range or subrange therebetween.
• the glass article 350 and/or 511 can comprise a CIE L* value of 50 or more, 70 or more, 75 or more, 85 or more, 90 or more, 96.5 or less, 96 or less, 95 or less, 94 or less, 93 or less, or 92 or less.
• the glass article 350 and/or 511 e.g., as-formed
• Providing a CIE L* value from 50 to 96.5 can provide an aesthetically pleasing, bright color of the glass article.
• photodarkening e.g., change in CIE L* value
• CIE L* values e.g., 70 or more, 90 or more
• “as-formed” means that the glass article has not been subjected to the extended (e.g., 10 hours or more) exposure to ultraviolet light (e.g., UV-C light) discussed below.
• glasses having CIELAB color coordinates within the range of CIE L* values from 50 to 96.5 are transparent to wavelengths of visible light (i.e., wavelengths of light from 380 nm to 750 nm, inclusive of endpoints) rather than opaque while still provided a noticeable color. Glass articles with a CIE L* value greater than 96.5 may appear as colorless.
• the glass article 350 and/or 511 can comprise an absolute value of a CIE a* (i.e.,
• i.e.,
• the CIE a* value can be about -35 or more, -20 or more, -18 or more, -15 or more, -10 or more, -5 or more, -3 or more, -1 or more, 0.3 or more, 0.5 or more, 0.8 or more, 1 or more, 5 or more, 8 or more, 10 or more, 18 or more, 20 or more, 25 or more, 65 or less, 40 or less, 25 or less, 18 or less, 10 or less, 8 or less, 5 or less, 3 or less, 1 or less, -0.3 or more, -0.5 or more, -0.8 or more, -1 or less, -3 or less, -5 or less, -8 or less, -10 or less, -15 or less, -18 or less, -20 or less, or -25 or less.
• the CIE a* value (excluding values from -0.3 to 0.3) can range from about -35 to 65, from -20 to 40, from -18 to 25, from -15 to 20, from - 10 to 18, from -5 to 10, from -3 to 5, from -1 to 3, from -0.8 to I, or any range or subrange therebetween.
• the CIE a* value (excluding value from -0.3 to 0.3) can range from -35 to 60, -20 to 60, -10 to 25, from -5 to 25, or any range or subrange therebetween.
• the CIE a* value can range from -35 to -0.3, from -18 to -0.3, from -15 to -0.3, from -10 to -0.3, from -8 to -0.5, from -5 to -1, or any range or subrange therebetween.
• the CIE a* value can range from 0.3 to 65, from 0.3 to 25, from 0.3 to 18, from 0.3 to 10, from 0.5 to 8, from 1 to 5, or any range or subrange therebetween.
• the glass article 350 and/or 511 can comprise an absolute value of a CIE b* (i.e.,
• a CIE b* i.e.,
• the CIE b* value can be -90 or more, -85 or more, -75 or more, -50 or more, -35 or more, -20 or more, -5 or more, -1 or more, 0.2 or more, 0.3 or more, 0.5 or more, 1 or more, 3 or more, 5 or more, 8 or more, 10 or more, 20 or more, 50 or more, 70 or more, 120 or less, 90 or less, 82 or less, 75 or less, 50 or less, 35 or less, 20 or less, 8 or less, 5 or less, -0.2 or less, -0.3 or less, -0.5 or less, -1 or less, -5 or less, -10 or less, -20 or less, -35 or less, -50 or less, or -70 or less.
• the CIE b* value (excluding from -0.2 to 0.2) can range from -90 to 120, from -85 to 75, from -50 to 50, from -35 to 35, from -20 to 20, from -5 to 8, from -1 to 5, from 0.2 to 3, from 0.3 to 1, or any range or subrange therebetween.
• the CIE b* value can range from -20 to 5, from -10 to 5, from -5 to 5, from - 5 to 3, from -5 to I, from -5 to -0.2, from -3 to -0.3, from -1 to -0.5, or any range or subrange therebetween.
• the CIE b* value can range from 0.2 to 90, from 0.5 to 82, from 1 to 75, from 1 to 20, from 1 to 5, or any range or subrange therebetween.
• the CIE b* value can range from -90 to -0.2, from -85 to -0.5, from -20 to -1, from -10 to -1, from -1 to -5, or any range or subrange therebetween.
• UV light comprises optical wavelengths from 200 nm to 400 nm
• UV-C light comprises optical wavelengths from 200 nm to 280 nm.
• UV-C light can be used to disinfect (i.e., sanitize) articles.
• UV-C light can inactive the SARS-CoV-2 coronavirus as well as other disease-causing pathogens.
• the inventors have observed that extended or repeated exposure of a glass article to UV-C light can lead to photodarkening (i.e., decrease in CIE L* value) and/or other changes in the observed color.
• the glass article 350 and/or 511 can absorb a large portion (e.g., majority) of ultraviolet light in a first half of the thickness 337 or 517 of the glass article 350 and/or 511, which can reduce an amount of ultraviolet light incident on the other half of the glass article 350 and/or 511 and reduce (e.g., prevent) changes in the CIE coordinates associated with the other half of the glass article 350 and/or 511.
• a large portion e.g., majority
• ultraviolet light incident on the other half of the glass article 350 and/or 511 can reduce an amount of ultraviolet light incident on the other half of the glass article 350 and/or 511 and reduce (e.g., prevent) changes in the CIE coordinates associated with the other half of the glass article 350 and/or 511.
• the glass article 350 and/or 511 can comprise an average absorptivity for optical wavelengths from 360 nm to 400 nm of 0.1 mm 1 or more, 0.2 mm 1 or more, 0.3 mm' 1 or more, 0.5 mm' 1 or more, 0.8 mm' 1 or more, 1 mm' 1 or more, 2 mm' 1 or more, 3 mm' 1 or more, 5 mm' 1 or more, 8 mm' 1 or more, or 10 mm' 1 or more.
• the glass article 350 and/or 511 can comprise an average absorptivity for optical wavelengths from 200 nm to 280 nm (i.e., UV-C light) of 0.1 mm' 1 or more, 0.2 mm' 1 or more, 0.3 mm' 1 or more, 0.5 mm' 1 or more, 0.8 mm' 1 or more, 1 mm' 1 or more, 2 mm' 1 or more, 3 mm' 1 or more, 5 mm' 1 or more, 8 mm' 1 or more, or 10 mm' 1 or more.
• an average absorptivity for optical wavelengths from 200 nm to 280 nm i.e., UV-C light
• the glass article 511 can comprise a surface layer 541 extending from the first major surface 513 to a first depth 547.
• the first depth 547 can be about 90 pm or less, about 80 pm or less, about 70 pm or less, about 60 pm or less, about 50 pm or less, about 40 pm or less, about 30 pm or less, about 20 pm or less, about 10 pm or less, about 100 nm or more, about 500 nm or more, about 1 pm or more, about 5 pm or more, or about 10 pm or more.
• the first depth 547 can range from about 100 nm to about 90 pm, from about 500 nm to about 80 pm, from about 1 pm to about 70 pm, from about 1 pm to about 60 pm, from about 5 pm to about 50 pm, from about 50 pm to about 40 pm, from about 10 pm to about 30 pm, from about 10 pm to about 20 pm, or any range or subrange therebetween.
• the glass article 511 can further comprise a bulk region 531 including the second major surface 515.
• a composition of the surface layer 541 can be substantially the same and/or the same as the composition of the bulk region 531.
• a color or CIE color coordinates “on a thickness adjusted basis” is a linear correction for the color or CIE color coordinates based on a difference in thickness between the actual thickness that the color or CIE color coordinates was measured at and another thickness that is the color or CIE color coordinates are adjusted to correspond to.
• the correction “on a thickness adjusted basis” can be applied when the actual thickness is 400 pm or more. For example, if 100 pm is removed from a 1 mm thick glass article, the CIE color coordinates measured for the resulting 900 pm thick glass article can be modified “on a thickness adjusted basis” to a reference thickness of 1 mm using a linear correction for the CIE color coordinates to compensate for the 100 pm difference. Unless otherwise indicated, the reference thickness used for “on a thickness adjusted basis” is 2.4 mm.
• the CIE color coordinates of the layer can be determined by removing the layer, calculating the CIE color coordinates of the glass article without the layer, and determining the CIE color coordinates associated with the layer by comparing the CIE color coordinates of the original glass article and the glass article without the layer on a thickness adjusted basis (to the thickness of the original glass article).
• the CIE L* value corresponding to the surface layer 541 can be less than the CIE L* value of the glass article on a thickness adjusted basis by 0.1 or more. Consequently, the color associated with the surface layer is darker (i.e., lower CIE L* value) than the original glass article and the bulk region.
• the CIE L* value of the entire glass article can be substantially the same (e.g., less than 0.1, or less than 0.05) as the CIE L* value of the bulk region on a thickness adjusted basis.
• an instantaneous CIE coordinate refers to a CIE coordinate corresponding a specified depth (i.e., into the glass article) from the first major surface of the glass article.
• the instantaneous CIE coordinate is calculated from a series of measurements taken with material removed from the sample between measurement; then, the instantaneous CIE coordinate is calculated from the change in CIE values on a thickness adjusted basis.
• a profile of an instantaneous CIE coordinate can be determined from a series of calculations performed for different depths.
• an instantaneous CIE L* value can monotonically decrease as a depth from the first major surface increases.
• “monotonically decrease” means that the value decreases at least some of the time and either remains the same (i.e., constant) or decreases the rest of the time (i.e., the value never increases).
• the instantaneous CIE L* value can monotonically decrease for the glass article as-formed as well as after UV-C exposure (discussed below) (e.g., after 10 hours or more, after 25 hours or more, after 50 hours or more of UV-C radiation treatment).
• a maximum of an absolute value of a gradient (i.e., instantaneous slope) of the instantaneous CIE L* value can be calculated.
• a maximum of the absolute value of the gradient of the instantaneous CIE L* value can be about 0.01 or more per 100 pm of thickness, about 0.02 or more per 100 pm of thickness, about 0.05 or more per 100 pm of thickness, or about 0. 1 or more per 100 pm of thickness.
• a maximum of the absolute value of the gradient of the instantaneous CIE L* value can range from about 0.01 to about 10 per 100 pm of thickness, from about 0.02 to about 5 per 100 pm of thickness, from about 0.05 to about 2 per 100 pm of thickness, from about 0.1 to about 1 per 100 pm of thickness, or any range or subrange therebetween.
• the profile of the instantaneous CIE L* value can comprise at least a first region (e.g., extending from the first major surface and/or associated with the surface layer) and a second region (e.g., associated with a transition between the surface layer and a bulk region) abutting the first region.
• an absolute value of a first average slope of the first region can be less than an absolute value of a second average slope of the second region.
• the absolute value of the first average slope can be less than the absolute value of the second average slope by about 0.01 or more per 100 pm of thickness, about 0.02 or more per 100 pm of thickness, about 0.05 or more per 100 pm of thickness, or about 0.1 or more per 100 pm of thickness.
• the properties of the profile of the instantaneous CIE L* value discussed in this paragraph can apply to the as-formed glass article and/or to the glass article after UV-C exposure (discussed below) (e.g., after 10 hours or more, after 25 hours or more, after 50 hours of UV-C radiation treatment).
• UV-C radiation treatment of the glass article consists essentially of an optical wavelength of 254 nm with a fluence of 3 milliWatts per centimeter squared of the first major surface of the glass article (mW/cm 2 ).
• the inventors have discovered that the glass articles of the present disclosure will develop a maximum thickness of the glass article after extended (or repeated) UV-C exposure that can remain substantially constant after additional UV-C exposure.
• the glass article 511 after extended (or repeated) UV-C exposure can be a saturated glass article comprising a saturated surface layer 611 and a saturated bulk region 631.
• the composition of the saturated surface layer 611 and the composition of the saturated bulk region 631 can be substantially the same or identical.
• a color associated with the saturated bulk region 631 can be substantially the same and/or identical to the color of the bulk region 531 (see FIG. 5) and/or a color of the glass article 511.
• the saturated surface layer 611 can extend to a second depth 617 from the first major surface 513 that is greater than the first depth 547 (i.e., the saturated bulk region 631 includes the material corresponding to the surface layer 541, as shown in FIG. 6).
• the second depth 617 can be about 500 pm or less, about 450 pm or less, about 400 pm or less, about 350 pm or less, about 300 pm or less, about 250 pm or more, about 50 pm or more, about 100 pm or more, about 150 pm or more, about 200 pm or more, or about 250 pm or more.
• the second depth 617 can range from about 50 pm to about 600 pm, from about 100 pm to about 450 pm, from about 150 pm to about 400 pm, from about 200 pm to about 350 pm, from about 250 pm to about 300 pm, or any range or subrange therebetween.
• the saturated surface layer 611 can comprise correspond to a substantially uniform set of CIE color coordinated throughout the second depth 617.
• the glass article of the present disclosure can provide a saturated thickness that can remain substantially constant over additional UV-C exposure.
• the glass article of the present disclosure can provide a reduced saturated thickness compared to other glass articles.
• a transition between the saturated surface layer 611 and the saturated bulk region 631 is measured in a direction of the thickness 517.
• the glass articles of the present disclosure can provide a reduced thickness of a transition between a color corresponding to a well-defined saturated surface layer and the color corresponding to the saturated bulk region.
• the thickness of the transition can be about 400 pm or less, about 350 pm or less, about 300 pm or less, about 250 pm or less, about 200 pm or less, about 50 pm or more, about 100 pm or more, about 150 pm or more, about 200 pm or more, or about 250 pm or more.
• the thickness of the transition can range from about 50 pm to about 400 pm, from about 100 pm to about 350 pm, from about 150 pm to about 300 pm, from about 200 pm to about 250 pm, or any range or subrange therebetween.
• the saturated glass article with the saturated surface layer 611 can be achieved after being impinged by UV-C radiation (i.e., exposure to an optical wavelength of 265 nm with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface) for 10 hours or more, 25 hours or more, or 50 hours.
• the thickness of and color corresponding to the surface layer e.g., saturated surface layer
• the thickness of and color corresponding to the surface layer can be measured after impingement with UV-C radiation (i.e., exposure to an optical wavelength of 265 nm with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface) for 10 hours, 25 hours, and/or 50 hours.
• a CIE L* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) can be less than the CIE L* value of the glass article (as-formed) by about 2 or less, about 1.5 or less, about 1 or less, about 0.8 or less, about 0.7 or less, about 0.5 or less, about 0.3 or less, or about 0.25 or less.
• a CIE L* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) can be less than the CIE L* value of the glass article (as-formed) by from about 0.01 to about 2, from about 0.05 to about 1.5, from about 0.1 to about I, from about 0.1 to about 0.8, from about 0.15 to about 0.7, from about 0.15 to about 0.5, from about 0.2 to about 0.3, from about 0.2 to about 0.25, or any range or subrange therebetween.
• the above- mentioned difference in CIE L* value can apply after 10 hours or more, 25 hours or more, or 50 hours of being impinged by UV-C radiation (i.e., exposure to an optical wavelength of 265 nm with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface).
• an absolute value of a difference between the CIE a* value of the glass article (as-formed) and the CIE a* value of the saturated glass article can be about 1 or less, about 0.5 or less, about 0.4 or less, about 0.3 or less, about 0.25 or less, about 0.2 or less, about 0.15 or less, or about 0.1 or less.
• the CIE a* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) can be less than the CIE a* value of glass article (as-formed) by about 1 or less, about 0.5 or less, about 0.4 or less, about 0.3 or less, about 0.25 or less, about 0.2 or less, about 0.15 or less, or about 0.1 or less.
• the CIE a* value of the saturated glass article can be less than the CIE a* value of glass article (as-formed) by from 0.01 to about I, from about 0.01 to about 0.5, from about 0.05 to about 0.4, from about 0.05 to about 0.3, from about 0.1 to about 0.25, from about 0.1 to about 0.2, from about 0.1 to about 0.15, or any range or subrange therebetween.
• the above-mentioned difference in CIE a* value can apply after 10 hours or more, 25 hours or more, or 50 hours of being impinged by UV-C radiation (i.e., exposure to an optical wavelength of 265 nm with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface).
• an absolute value of a difference between the CIE b* value of the glass article (as-formed) and the CIE b* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) can be about 0.2 or less, about 0.15 or less, about 0.12 or less, or about 0.1 or less.
• the CIE b* value of the glass article (as-formed) can be greater than the CIE b* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) by from 0 to 0.2, from 0.01 to 0.15, from 0.02 to 0.12, from 0.05 to 0.10, or any range or subrange therebetween.
• the CIE b* value of the glass article (as-formed) can be less than the CIE b* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation) by from 0 to 0.2, from 0.01 to 0.15, from 0.02 to 0.12, from 0.05 to 0.10, or any range or subrange therebetween.
• the CIE b* value of the glass article (as-formed) can be about 1 or more, and an absolute value of a difference between the CIE b* value of the glass article (as-formed) and the CIE b* value of the saturated glass article (e.g., after 10 hours or more of being impinged by UV-C radiation), as a percentage of the CIE b* value of the glass article (as-formed), can be about 33% or less, about 25% or less, about 20% or less, about 15% or less, or about 10% or less, for example, from 0% to about 33%, from about 1% to about 25%, from about 2% to about 20%, from about 5% to about 15%, from about 5% to about 10%, or any range or subrange therebetween.
• the above-mentioned difference in CIE b* value can apply after 10 hours or more, 25 hours or more, or 50 hours of being impinged by UV-C radiation (i.e., exposure to an optical wavelength of 265 nm with a fluence of 3 milliwatts per centimeter squared of a surface area of the first major surface).
• a first step 701 of methods of the disclosure methods can start with obtaining raw materials for the glass article and/or natively colored glass article, which can be obtained, for example, by purchase or otherwise obtaining the raw materials.
• the raw materials can be melted together and formed in a glass article by the end of step 701.
• precursor materials comprising a combination of constituent glass components and one or more colorants in a colorant package described herein may be melted together.
• the glass article can be provided by forming them with a variety of ribbon forming processes, for example, slot draw, down-draw, fusion down-draw, up-draw, press roll, redraw, or float.
• the glass article may be provided by purchase or otherwise obtaining a substrate or by forming the glass article.
• the initial glass article may be exposed to a heat treatment to produce color in the glass article, as described below in step 705.
• step 703 methods can proceed to step 703 comprising melting together the raw materials to form a glass article.
• Amounts the raw materials (mol% on an oxide basis) can be within one or more of the ranges discussed above for the composition of glass article.
• the raw materials can further comprise an additive that can impact the resulting color and/or UV-related properties of the glass article but will volatilize during the melting of the raw materials to form the glass article.
• additives include nitrates (e.g., KNO 3 , NaNO 3 ) and carbon (e.g., charcoal, carbon black).
• the raw materials can include a source of nitrate (e.g., KNO 3 , NaNO 3 ) with the amount of nitrate in the raw materials can be about 1.5 wt% or more, about 2 wt% or more, about 2.5 wt% or more, about 5 wt% or less, about 3 wt% or less, or about 2.9 wt% or less.
• a source of nitrate e.g., KNO 3 , NaNO 3
• the raw materials can include a source of nitrate (e.g., KNO 3 , NaNO 3 ) with the amount of nitrate in the raw materials can range from about 1.5 wt% to about 5 wt%, from about 2 wt% to about 3 wt%, from about 2.5 wt% to about 2.9 wt%, or any range or subrange therebetween.
• a source of nitrate e.g., KNO 3 , NaNO 3
• step 703 methods can proceed to step 705 comprising heating the glass article.
• heating the glass article can comprise placing the glass article 511 in an oven 801.
• different color coordinates within the color gamut may be achieved by altering the heat treatment cycle of the glass composition 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 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 described herein are heat treated in an isothermal oven to produce the resultant colored glass articles.
• methods may follow arrow 706 or 708 from step 703 omitting step 705, for example, if the glass article does not need to be heat treated to be colored or if the color was otherwise developed by the end of step 703.
• the precursor glass article may be exposed to a heat treatment to produce color in the glass.
• the heat treatment may induce the formation of colorant particles in the glass which, in turn, cause the glass to become colored.
• the glass may appear clear (i.e., colorless) prior to heat treatment.
• colorant particles may include, for example and without limitation, Au particles (e.g., when the colorant package in the glass comprises Au), randomly oriented, anisotropic silver particles (e.g., when the colorant package comprises Ag) and/or the like, thereby forming a colored glass article.
• the time and/or temperature of the heat treatment may be specifically selected to produce a colored glass article having a desired color.
• a desired color is a result of the morphology of the particles precipitated in the glass which, in turn, is dependent on the time and/or temperature of the heat treatment. Accordingly, it should be understood that a single glass composition can be used to form colored glass articles having different colors based on the time and/or temperature of the applied heat treatment in addition to the composition of the colorant package included in the glass. Specifically, different color coordinates within the color gamut may be achieved by altering the heat treatment cycle of the glass composition 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 exposed to the heated environment).
• 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 500°C or more, 550°C or more, 575°C or more, 600°C or more, 625°C or more, 650°C or more, 800°C or less, 775°C or less, 750°C or less, 725°C or less, or 700°C or less.
• the temperature of the heat treatment cycle can range from 500°C to 800°C, from 550°C to 750°, from 575°C to 725°C, from 600°C to 725°C, from 625°C to 700°C, from 650°C to 700°C, or any range or subrange therebetween.
• the duration of the heat treatment cycle can be 0.15 hours or more, 0.25 hours or more, 0.5 hours or more, 1 hour or more, 2 hours or more, 24 hours or less, 16 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, or 3 hours or less. In aspects, the duration of the heat treatment cycle can range from 0.15 hours to 24 hours, from 0.25 hours to 16 hours, from 0.5 hours to 8 hours, from 1 hour to 6 hours, from 1 hour to 4 hours, from 2 hours to 4 hours, or any range or subrange therebetween.
• the heat treatment may comprise ramping up to a heat treatment temperature at a heating rate and cooling down from the heat treatment temperature at a cooling rate.
• the selected heating rate and cooling rate may affect the color coordinates of the resultant colored glass articles.
• the heating rate of the heat treatment may be 2°C/min or more, 3°C/min or more, 10°C/min or less, 7°C/min or less, or 5°C/min or less.
• the heating rate of the heat treatment can range from 2°C/min to 10°C/min, from 3°C/min to 7°C/min, from 3°C/min to 5°C/min, or any range or subrange therebetween.
• the cooling rate of the heat treatment may be l°C/min or more, 2°C/min or more, 10°C/min or less, 8°C/min or less, 6°C/min or less, or 4°C/min or less.
• the cooling rate of the heat treatment can range from l°C/min to 10°C/min, from l°C/min to 8°C/min, from 2°C/min to 6°C/min, from 2°C/min to 4°C/min, or any range or subrange therebetween.
• colored glass articles having an orange color may be formed by heat treating the precursor glass article at a heat treatment temperature from about 590°C to about 610°C for a heat treatment time from about 45 minutes to about 180 minutes.
• colored glass articles having a red color may be formed by heat treating the precursor glass article at a heat treatment temperature from about 600°C to about 615°C for a heat treatment time from about 180 minutes to about 300 minutes
• colored glass articles having a green color may be formed by heat treating the precursor glass article at a heat treatment temperature from about 620°C to about 640°C for a heat treatment time from about 20 minutes to about 40 minutes.
• colored glass articles having a brown color may be formed by heat treating the precursor glass article at a heat treatment temperature from about 640°C to about 660°C for a heat treatment time from about 30 minutes to about 90 minutes.
• colored glass articles having a purple color may be formed by heat treating the precursor glass article at a heat treatment temperature from about 625 °C to about 650°C for from about 30 minutes to about 90 minutes.
• step 707 can comprise contacting at least a portion of the glass article 511 with a molten salt solution 903 (e.g., contained in a bath 901).
• a molten salt solution 903 e.g., contained in a bath 901.
• the glass article 511 can be immersed in the molten salt solution 903 contained in the bath 901.
• step 707 can develop the first compressive stress region, the second compressive stress region, and/or the tensile stress region discussed above and the corresponding region can comprise a maximum stress and/or depth of compression within one or more of the corresponding ranges discussed above.
• the molten salt solution comprises sodium and/or potassium ions (e.g., from KNO 3 and/or NaNO 3 ).
• the temperature of the molten salt solution 903 can be about 300°C or more, about 360°C or more, about 400°C or more, about 500°C or less, about 460°C or less, or about 420°C or less.
• the temperature of the molten salt solution 903 can be in a range from about 300°C to about 500°C, from about 360°C to about 460°C, from about 400°C to about 420°C, or any range or subrange therebetween.
• the glass article 511 can be in contact with the molten salt solution 903 for about 30 minutes or more, about 45 minutes or more, about 1 hour or more, about 8 hours or less, about 4 hours or less, about 2 hours or less, or about 1.5 hours or less. In aspects, the glass article 511 can be in contact with the molten salt solution 903 for a time in a range from about 30 minutes to about 8 hours, from about 45 minutes to about 4 hours, from about 1 hour to about 2 hours, from about 1 hour to about 1.5 hours, or any range or subrange therebetween.
• step 709 comprising impinging the glass article with ultraviolet radiation.
• step 709 can comprise impinging the first major surface 513 of the glass article 511 with ultraviolet radiation 1003 emitted from a radiation source 1001 at a predetermined fluence for a predetermined period of time to develop the surface layer 541 extending from the first major surface 513 to a first depth 547.
• the ultraviolet radiation 1003 can comprise UV-C radiation (i.e., optical wavelengths from 200 nm to 280 nm), for example, primarily having an optical wavelength of about 254 nm.
• the radiation source 1001 can comprise a UV (e.g., UV-C) emitting bulb (e.g., Hg-lamp), a laser, a filtered light source, or combinations thereof.
• the predetermined fluence can be about 1 mW/cm 2 or more, about 2 mW/cm 2 or more, about 2.5 mW/cm 2 or more, about 3 mW/cm 2 or more, about 10 mW/cm 2 or less, about 7 mW/cm 2 or less, about 5 mW/cm 2 or less, about 4 mW/cm 2 or less, about 3.5 mW/cm 2 or less, or about 3 mW/cm 2 .
• the predetermined fluence can range from about 1 mW/cm 2 to about 10 mW/cm 2 , from about 1 mW/cm 2 to about 7 mW/cm 2 , from about 2 mW/cm 2 to about 5 mW/cm 2 , from about 2 mW/cm 2 to about 4 mW/cm 2 , from about 2.5 mW/cm 2 to about 3.5 mW/cm 2 , or any range or subrange therebetween.
• step 709 can disinfect (e.g., sanitize) the glass article 511 and/or provide the surface layer with a different color (e.g., CIE color coordinates) than the bulk region 531 of the glass article.
• the surface layer 541 developed in step 709 can correspond to the surface layer 541 of the glass article 511 shown in FIG. 5.
• the first depth 547 and/or properties of the CIE color coordinates of the surface layer 541 can be within one or more of the corresponding ranges discussed above with reference to the surface layer 541 and/or the first depth 547 shown in FIG. 5.
• the ultraviolet radiation 1003 can impinge the glass article 511 for about 1 minute or more, about 3 minutes or more, about 5 minutes or more, about 7 minutes or more, about 10 minutes or more, about 1 hour or less, about 40 minutes or less, about 20 minutes or less, or about 15 minutes or less.
• the ultraviolet radiation 1003 can impinge the glass article 511 for a period of time from about 1 minute to about 1 hour, from about 3 minutes to about 40 minutes, from about 5 minutes to about 20 minutes, from about 7 minutes to about 15 minutes, or any range or subrange therebetween.
• Providing the surface layer can reduce a color change of the glass article such that it may not be discernable to a user that intermittently exposes the glass article to UV-C light.
• the surface layer 541 developed in step 709 can correspond to the saturated surface layer 611 of the glass article 511 shown in FIG.6.
• the second depth 617 and/or properties of the CIE color coordinates of the surface layer 541 can be within one or more of the corresponding ranges discussed above with reference to the saturated surface layer 611 and/or the second depth 617 shown in FIG. 6.
• the ultraviolet radiation 1003 can impinge the glass article 511 for about 6 hours or more, about 10 hours or more, about 16 hour or more, about 168 hours or less, about 50 hours or less, about 36 hours or less, about 25 hours or less, or about 10 hours or less.
• the ultraviolet radiation 1003 can impinge the glass article 511 for a period of time ranging from about 6 hours to about 168 hours, from about 10 hours to about 50 hours, from about 10 hours to about 36 hours, from about 16 hours to about 25 hours, or any range or subrange therebetween.
• Providing a saturated surface layer can prevent the glass article from changing color as a result of subsequent (e.g., frequent or extended) UV- C exposure.
• step 711 comprising assembling the glass article 511 into a natively colored glass housing and/or an electronic device.
• step 711 can comprise disposing and/or attaching the glass article to the reflector (e.g., in a natively colored glass housing).
• methods can follow arrow 702 from step 701 to step 707, for example, if the glass article is colored by the end of step 701.
• methods can follow arrow 704 from step 701 to step 709, for example if the glass article is colored by the end of step 701 and the glass article already has a predetermined number of compressive stress regions at the end of step 701.
• methods can follow arrow 706 from step 703 to step 707, for example, if the glass article does not need to be heat treated to be colored or if the color was otherwise developed by the end of step 703.
• methods can follow arrow 708 from step 703 to step 709, for example, if the glass article does not need to be heat treated to be colored or if the color was otherwise developed by the end of step 703 and the glass article already has the predetermined number of compressive stress regions (e.g., 0) at the end of step 703.
• methods can follow arrow 710 from step 707 to step 711, for example, if the glass article already comprises a predetermined set of CIE color coordinates and/or is to have a minimal surface layer.
• methods can follow arrow 712 from step 707 to step 713, for example, if methods are complete at the end of step 707.
• methods can follow arrow 714 from step 709 to step 713, for example, if methods are complete at the end of step 709. Any of the above options may be combined to make a foldable apparatus in accordance with the embodiments of the disclosure.
• Examples AA-CC and Examples 1-15 were formed as glass articles with the composition stated in Table 1.
• Examples 1-13 comprised a thickness of 2.4 mm
• Examples 14-15 comprised a thickness of 3.6 mm.
• nitrates that are reported as a wt% of the raw materials, the other components correspond to the amounts in the glass article in mol% (or ppm if explicitly indicated in Table 1).
• Examples 1-15 comprise SiO 2 from about 58 mol% to about 64 mol%, Al 2 O 3 from about 14 mol% to about 25 mol%, B2O 3 from 0 to about 7 or from about 4.5 mol% to about 7 mol%, R 2 O from about 5 mol% to about 17 mol% (e.g., Li 2 O from 0 mol% to about 11 mol% or from about 4 mol% to about 11 mol%, Na 2 O from about 1 mol% to about 5 mol%, and/or K 2 O from 0 mol% to about 1 mol% or from about 0.2 mol% to about 0.9 mol%), MgO from 0 mol% to about 2 mol% or from about 0.02 mol% to about 0.13 mol%, CaO from about 0.01 mol% to about 4 mol% or from about 1 mol% to about 4 mol%, ZnO from 0 mol% to about 0.1 mol%, SnO 2
• Examples 3-4, 6-8, and 15 comprise nonzero amounts of TiO 2 .
• Examples 1, 3-4, 5-10, and 14-15 comprise non-zero amounts of Fe 2 O 3 (e.g., from 100 ppm to 1200 ppm).
• Examples 1-5, 7, 11, and 14-15 comprise Au, for example, from about 5 ppm to about 20 ppm.
• Examples 12-13 comprise Ag, for example, from about 900 ppm to about 1100 ppm.
• Examples 6 and 9 comprise non-zero amounts of CeO 2 ; and Example 8 comprises non-zero amounts of Co 3 O 4 , Cr 2 O 3 , and MnO 2 .
• Table 1 Composition (mol%) of Comparative Examples AA-CC and Examples 1-12
• Comparative Examples BB-CC exhibit a decrease in CIE L* values greater than 2 after 10 hours of UV-C exposure.
• Comparative Example AA exhibits a decrease in CIE b* value of more than 0.5 after 10 hours of UV-C exposure and a decrease of 0.8 after 50 hours of UV-C exposure.
• Comparative Example AA exhibits a ⁇ E of 0.65 after 10 hours of UV-C exposure and a ⁇ E of 0.85 after 50 hours of UV-C exposure.
• Comparative Examples BB-CC exhibit a ⁇ E of more than 2 after 10 hours of UV-C exposure.
• Table 3 Properties of Comparative Examples BB-CC and Examples 2, 4-5, 7, 10, and 12-15 [00278] As shown in Tables 2-3, Examples 1-15 exhibited as-formed CIE L* values of 50 or more, 70 or more, and 75 or more. Examples 1-9 and 11 exhibit as- formed CIE L* values of 90 or more. After 10 hours of UV-C exposure, the absolute value of the change in CIE L* value is less than 0.2 for Examples 1-3, 6, 8-9, 11, and 14, which is less than the change seen for Comparative Examples AA-CC.
• Examples 1-15 exhibited as-formed CIE a* values from about -3.1 to about 13.
• Examples 1-5, 7, 10, and 12-15 exhibited as- formed CIE a* values greater than 0 (e.g., from about 1 to about 13) while Examples 6 and 8-10 exhibited as-formed CIE a* values less than 0 (e.g., from about -3.1 to about -0.1).
• Examples 1-11 exhibited an absolute value of the change in CIE a* value of less than 0.1 after 10 hours of UV-C exposure, which is less than the change seen for Comparative Examples BB-CC.
• Examples 1-15 exhibited as-formed CIE b* values from about -2 to about 105.
• Examples 2-7 and 9-15 exhibit as-formed CIE b* values greater than 0 (e.g., from about 0.2 to about 105) with Examples 6 and 11-15 having as-formed CIE b* values greater than 5.
• Examples 1 and 8 exhibit as-formed CIE b* values less than 0 (e.g., from about -2 to about -0.1).
• Examples 1-9 and 11 exhibit an absolute value of the change in CIE b* value of 0.2 or less after 10 hours of UV-C exposure.
• Examples 2, 5, 7, 10, and 12-15 exhibit an absolute value of a percentage change in the CIE b* value of less than 10%, which is better than Comparative Example CC. Further, Examples 12-13 exhibit an absolute value of a percentage change in the CIE b* value of less than 1%. Of note, Example 6 demonstrated a maximum absolute value of a difference in any CIE coordinate after 10 hours, after 25 hours, and after 50 hours of 0.03.
• Example 3 Compared to Comparative Example AA, Example 3 has more CaO, more R 2 O, and less Al 2 O 3 . After 50 hours of UV-C exposure, Comparative Example AA exhibits photodarkening of 0.28 while Example 3 exhibits a photodarkening of 0.17. Likewise, Example 3 has a smaller change in CIE b* value after 50 hours of UV-C exposure relative to Comparative Example AA. Further, after 50 hours of UV- C exposure, Comparative Example has a ⁇ E of 0.85 while Example 3 has a ⁇ E of 0.50.
• Example 2 has more CaO and more ZrO 2 while Example 3 has more R 2 O and MgO.
• the photodarkening is 0.18 for Example 2 and 0.16 for Example 3; the absolute value of the change in CIE a* value is 0.03 for Example 2 and 0.07 for Example 3; the absolute value of the CIE b* value is 0.07 for Example 2 and 0.13 for Example 3.
• increasing the amount of ZrO 2 (and CaO) is associated with decreases in changes of CIE L* coordinates after UV-C exposure.
• Example 4 had 2.9 wt% nitrate while Example 5 had 1.4 wt% nitrate. Comparing Examples 4 and 5, Example 4 had more nitrate in the raw materials (by including more nitrate as an anion paired with an alkali metal).
• Table 3 after 10 hours of UV-C exposure, the absolute value of the change in CIE L* value is 0.2 for Example 4 and 0.36 for Example 5; the absolute value of the change in CIE a* value is 0.03 for Example 4 and 0.08 for Example 5; and the absolute value of the change in CIE b value is 0.14 for Example 4 and 0.32 for Example 5.
• increasing the amount of nitrate in the raw material is associated with decreases in changes of CIE L*, a*, and b* coordinates after UV-C exposure.
• Examples 1-13 demonstrate a range of colors with reduced photodarkening and/or increased stability of CIE L* coordinates. For example, Examples 1-3 are associated with a pink color, Example 6 is associated with a yellow color, Example 8 is associated with a white color, and Example 9 is associated with a green color.
• Table 4 presents the transmittance (T) properties for Examples 10 and 12-15.
• Examples 10 and 12-15 have an average transmittance over optical wavelengths from 360 nm to 400 nm from 0% to about 50 with Examples 12-13 having an average transmittance over optical wavelengths less than 2% (e.g., from about 0.5% to about 1.5%).
• Examples 10 and 12-15 have an average transmittance over optical wavelengths from 400 nm to 700 nm from about 35% to about 70%.
• the minimum transmittance for a sliding 10 nm window is observed at 450 nm or 520 nm for Examples 10 and 12-15 with the minimum transmittance from about 0.2% to about 56%.
• Examples 12-13 have a minimum transmittance less than 1% while Examples 10 and 14-15 have a minimum transmittance from about 30% to about 56%.
• FIGS. 11-12 show differences in CIE coordinates as a function of remaining thickness on a thickness adjusted basis for Examples 14 and 15, respectively. Examples 14-15 were exposed to UV-C radiation for 10 hours, as described above. Then, thickness was removed evenly from both major surfaces by polishing.
• FIGS. 11-12 show the actual thickness of the sample at each stage.
• the horizontal axis 1101 and 1201 corresponds to the thickness of the sample remaining
• the vertical axis 1103 and 1203 is the difference in CIE coordinate.
• Curves 1105 and 1205 correspond to the difference in CIE L* value
• curves 1107 and 1207 correspond to the difference in CIE a* value
• curves 1109 and 1209 correspond to the difference in CIE b* value.
• the above observations can be combined to provide glass articles and natively colored glass articles including the same that are resistant to color change from ultraviolet (e.g., UV-C) light exposure.
• the glass articles can exhibit a high brightness (e.g., CIE L* value greater than 50 or greater than 70 and less than 96.5) color that can be consistent through UV-C exposure.
• the glass article can comprise a surface layer where any photodarkening can be restricted to, for example, even after repeated and/or extended UV-C exposure.
• Providing the surface layer can reduce a color change of the glass article such that it may not be discernable to a user that intermittently exposes the glass article to UV-C light.
• Providing a saturated surface layer can prevent the glass article from changing color as a result of subsequent (e.g., frequent or extended) UV-C exposure.
• the glass-based material of the glass article can provide good dimensional stability, good impact resistance, good crack resistance, good puncture resistance, and/or good flexural strength.
• the glass article can include a compressive stress region (e.g., be chemically strengthened), which can provide improved crack resistance, puncture resistance, impact resistance, and/or improved flexural strength.
• Providing the glass article with ZrO 2 e.g., from 0.2 mol% to 0.5 mol%) can provide enhanced resistance to color change from UV-C exposure.
• forming the glass article with a precursor material comprising nitrates can provide enhanced resistance to color change from UV-C exposure.
• minimizing the combination of R 2 O, CaO, MgO, and ZnO in the glass composition may provide the resultant colored glass article with a desirable dielectric constant, such as when the colored glass article is used as a portion of a housing for an electronic device.
• Providing a dielectric constant for frequencies from 10 GHz to 60 GHz from 5.6 to 6.4 can allow wireless communication through the glass article.
• the glass articles and housings of the present disclosure can absorb a large portion (e.g., majority) of ultraviolet light in a first half of the thickness of the glass article, which can reduce an amount of ultraviolet light incident on the other half of the glass article and reduce (e.g., prevent) changes in the CIE coordinates associated with the other half of the glass article.
• Providing a natively colored glass housing with a colored glass article can eliminate the need for an additional layer to impart color to the housing, which can simplify assembly and provide a more consistent color. Consequently, the natively colored glass housing including the glass article can provide an aesthetically pleasing appearance (e.g., color) while simultaneously protecting an electronic device from damage and/or permitting wireless communication therethrough.
• the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, aspects include 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 aspect.
• 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 similar is intended to denote that two values are equal or approximately equal. In aspects, “substantially similar” may denote values within about 10% of each other, for example, within about 5% of each other, or within about 2% of each other.
• U.S. Patent Application No. 17/677,345 filed February 22, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/841,776 filed June 16, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/677,375 filed February 22, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/691,813 filed March 10, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/843,096 filed June 17, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/713,313 filed April 5, 2022 is hereby incorporated by reference herein in its entirety.
• U.S. Patent Application No. 17/843,001 filed June 17, 2022 is hereby incorporated by reference herein in its entirety.

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• 2023
  • 2023-12-07 WO PCT/US2023/082801 patent/WO2024129477A2/fr not_active Ceased
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