Glass product, primary-color glass shell and manufacturing method of primary-color glass shell

Abstract

A method of making a housing for a consumer electronic device includes melting together precursor materials to form a glass article including a silicate glass having a multivalent colorant having a reduced form and an oxidized form. The multivalent colorant is a metal selected from the group consisting of cerium, titanium, cobalt, copper, nickel, vanadium, chromium, and combinations thereof. The molar ratio of the precursor may be different from the molar ratio of the glass article. The primary glass housing includes a glass article having a thickness of 200 [mu] m to 5 mm. The molar ratio of the glass article may be from 0.3 to 0.9. A total transmittance of at least one 10 nm wavelength band through the thickness may be 3% to 80% over a wavelength range of 380 nm to 750 nm.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119 to U.S. Provisional Application No. 63 / 536,103, filed on September 1, 2023, and claims priority under 35 U.S.C. §119 to U.S. Provisional Application No. 63 / 433,065, filed on December 16, 2022, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present disclosure relates generally to glass articles and natural glass enclosures and methods of making the same, and more particularly to glass articles and natural glass enclosures that include multivalent colorants. Background Art

[0004] Glass products are often used in display devices such as liquid crystal displays (LCDs), electrophoretic displays (EPDs), organic light emitting diode displays (OLEDs), plasma display panels (PDPs), etc. Glass products may form part of a housing or cover a display.

[0005] Aluminosilicate glass products exhibit excellent ion exchange and drop resistance. Various industries, including consumer electronics, require colored materials with strength and fracture toughness comparable to existing ion-exchange strengthened, non-colored glasses. However, the color of glass products can be limited by existing technology. Therefore, there is a need to develop methods for producing glass products with novel colors. Summary of the Invention

[0006] Described herein are glass articles comprising polyvalent colorants and pre-colored glass housings containing the glass articles. The glass articles can exhibit a high-brightness color (e.g., a CIE L* value greater than 50, or greater than 70 and less than 96.5). A predetermined color of the glass article and / or pre-colored glass can be achieved by controlling the amount of the reduced-form polyvalent colorant relative to the oxidized-form polyvalent colorant. Furthermore, by controlling the molar ratio of the reduced-form polyvalent colorant to the total amount of polyvalent colorant, colors previously unattainable from a given colorant package can be achieved.

[0007] 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., chemically strengthened) that can provide improved crack resistance, puncture resistance, impact resistance, and / or improved flexural strength. Furthermore, minimizing the combination of RO, CaO, MgO, and ZnO in the glass composition can result in a colored glass article having a desirable dielectric constant, for example, when the colored glass article is used as part of an electronic device housing. A dielectric constant of 5.6 to 6.4 at frequencies between 10 GHz and 60 GHz can enable wireless communication through the glass article.

[0008] Providing a natural glass housing with a colored glass article eliminates the need for an additional layer to add color to the housing, which can simplify assembly and provide a more consistent color. Thus, a natural glass housing including a glass article can provide an aesthetically pleasing appearance (e.g., color) while protecting the electronic device from damage and / or allowing wireless communication therethrough.

[0009] The method comprises forming a glass article from a precursor material comprising a polyvalent colorant, wherein the molar ratio of the precursor of the polyvalent colorant is different from the molar ratio of the polyvalent colorant in the resulting glass article. The molar ratio can be reduced by, for example, including a nitrate source, a sulfate source, a zinc source, or a combination thereof in the precursor material. The molar ratio can be increased by, for example, including a carbon source, an iron source, an antimony source, or a combination thereof in the precursor material. Adjusting the cooling rate of the melt formed by melting the precursor material can also be used to control the molar ratio of the polyvalent colorant. Controlling the molar ratio of the polyvalent colorant enables the glass article to reliably produce a predetermined color (e.g., CIE color coordinates). Controlling the molar ratio of the polyvalent colorant can increase the color gamut and / or resolution of the color obtained by a predetermined colorant package comprising the polyvalent colorant.

[0010] Some example aspects of the present disclosure are described below, and it should be understood that any features of the various aspects can be used alone or in combination with each other.

[0011] Aspect 1. A method for manufacturing a housing for a consumer electronic device, comprising:

[0012] melting the precursor materials together to form the glass article,

[0013] wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, the precursor material comprises the multivalent colorant, the multivalent colorant being a metal selected from the group consisting of cerium, titanium, cobalt, copper, nickel, vanadium, chromium, and combinations thereof, and a precursor molar ratio of the reduced form of the multivalent colorant in the precursor material to the sum of the oxidized and reduced forms of the multivalent colorant in the precursor material is different from a molar ratio of the oxidized form of the multivalent colorant in the glass article to the sum of the oxidized and reduced forms of the multivalent colorant in the glass article.

[0014] Aspect 2. The method of aspect 1, wherein the absolute value of the difference between the precursor molar ratio of the precursor material and the molar ratio of the glass article is from about 0.1 to about 0.5.

[0015] Aspect 3. The method of any one of aspects 1 to 2, wherein the precursor molar ratio of the precursor material is greater than the molar ratio of the glass article.

[0016] Aspect 4. The method according to any one of aspects 1 to 3, wherein the precursor material further comprises 0.02 wt % or more of a sulfate source, a zinc source, or a combination thereof.

[0017] Aspect 5. The method according to aspect 4, wherein the precursor material comprises 0.1 wt% to 0.3 wt% of the sulfate source.

[0018] Aspect 6. The method according to any one of aspects 4 to 5, wherein the precursor material comprises 0.25 wt% to about 1 wt% of the zinc source.

[0019] Aspect 7. The method according to any one of aspects 1 to 6, wherein the precursor material further comprises 0.05 wt% or more of a nitrate source.

[0020] Aspect 8. The method according to aspect 7, wherein the precursor material comprises 0.1 wt% to 3 wt% of the nitrate source.

[0021] Aspect 9. The method of any one of aspects 1 to 2, wherein the molar ratio of the glass article is greater than the precursor molar ratio of the precursor material.

[0022] Aspect 10. The method of aspect 9, wherein the precursor material comprises about 0.01 wt % or more of an antimony source, an iron source, or a combination thereof.

[0023] Aspect 11. The method of aspect 10, wherein the precursor material comprises 300 ppm to about 1,300 ppm of the iron source.

[0024] Aspect 12. The method of any one of aspects 1 to 2 or 10 to 11, wherein the precursor material comprises 0.01 wt% to about 0.5 wt% of an antimony source.

[0025] Aspect 13. The method of any one of aspects 1 to 2 or 10 to 12, wherein the precursor material comprises 0.004 wt% to about 0.05 wt% of a carbon source.

[0026] Aspect 14. A method according to any one of aspects 1 to 13, wherein melting the precursor material includes heating the precursor material to a first temperature of about 1500°C or higher to form a melt, and cooling the melt from the first temperature to about 1400°C at a predetermined rate, and then forming the glass article from the melt.

[0027] Aspect 15. The method of aspect 14, wherein the predetermined rate is about 0.5°C / min or higher.

[0028] Aspect 16. The method according to any one of aspects 14 to 15, wherein the predetermined rate is about 0.5°C / min to about 2°C / min.

[0029] Aspect 17. The method according to any one of aspects 14 to 16, further comprising exposing the melt to an atmosphere comprising an oxygen partial pressure of about 25 kilopascals or greater.

[0030] Aspect 18. The method according to any one of aspects 14 to 17, wherein the precursor material comprises an iron source, a zinc source, or a combination thereof.

[0031] Aspect 19. The method of any one of aspects 1 to 18, wherein the multivalent colorant is chromium.

[0032] Aspect 20. The method of any one of aspects 1 to 19, further comprising placing the glass article on a reflector layer, the reflector layer being opaque and having a CIE L* value of 70 or greater.

[0033] Aspect 21. The method of any one of aspects 1 to 20, wherein the glass article has an absolute value of a CIE a* value of about 0.3 or greater, and the glass article has an absolute value of a CIE b* value of about 0.2 or greater.

[0034] Aspect 22. The method of any one of aspects 1 to 20, wherein the glass article has a CIE a* value of less than -3.

[0035] Aspect 23. The method of any one of aspects 1 to 20, wherein the glass article has a CIE b* value greater than 5.

[0036] Aspect 24. The method of any one of aspects 1 to 23, wherein the glass article has a CIE L* value of 70 or greater.

[0037] Aspect 25. The method of any one of aspects 1 to 24, wherein the molar ratio of the reduced form to the sum of the reduced form and the oxidized form in the glass article is from 0.5 to 0.9.

[0038] Aspect 26. A primary color glass housing for a consumer electronic device, the primary color glass housing comprising a glass article, the glass article comprising a thickness defined between a first major surface and a second major surface, the second major surface opposite the first major surface, the thickness being 200 μm to 5 mm, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, a molar ratio of the reduced form to the sum of the reduced form and the oxidized form of the multivalent colorant being 0.3 to 0.9, and a total transmittance through the thickness of at least one 10 nm band within the wavelength range of 380 nm to 750 nm being 3% to 80%.

[0039] Aspect 27. The natural glass envelope according to aspect 26, further comprising a reflector layer covering the second major surface, the reflector layer being opaque and having a CIE L* value of 70 or greater.

[0040] Aspect 28. The natural glass enclosure according to any one of aspects 26 to 27, wherein the absolute value of the CIE a* value of the glass article is about 0.3 or greater, and the absolute value of the CIE b* value of the glass article is about 0.2 or greater.

[0041] Aspect 29. The natural glass enclosure according to any one of aspects 26 to 28, wherein the glass article has a CIE a* value of less than -3.

[0042] Aspect 30. The natural glass enclosure of any one of aspects 26 to 29, wherein the glass article has a CIE b* value greater than 5.

[0043] Aspect 31. The natural glass enclosure of any one of aspects 26 to 30, wherein the glass article has a CIE L* value of 70 or greater.

[0044] Aspect 32. The natural glass enclosure of any one of aspects 26 to 31, wherein the molar ratio of the reduced form to the sum of the reduced form and the oxidized form is 0.5 to 0.9.

[0045] Aspect 33. The natural glass enclosure of any one of aspects 26 to 32, wherein the glass article further comprises 200 ppm or more of Fe2O3.

[0046] Aspect 34. The natural glass enclosure of aspect 33, wherein the glass article comprises 300 ppm to about 600 ppm of Fe2O3.

[0047] Aspect 35. The natural glass enclosure of any one of aspects 26 to 34, wherein the glass article comprises 0.25 wt% to about 1 wt% ZnO.

[0048] Aspect 36. The natural glass enclosure of any one of aspects 26 to 35, wherein the glass article comprises 0.01 wt% to about 0.5 wt% Sb2O3.

[0049] Aspect 37. The primary colored glass envelope of any one of aspects 26 to 36, wherein the multivalent colorant is a metal selected from the group consisting of cerium, titanium, cobalt, copper, nickel, vanadium, chromium, and combinations thereof.

[0050] Aspect 38. The natural color glass enclosure of aspect 37, wherein the multivalent colorant is chromium.

[0051] Aspect 39. The natural glass enclosure of any one of aspects 26 to 38, wherein the glass article comprises, in mol % of the glass article:

[0052] about 50 mol % to about 75 mol % SiO2;

[0053] about 7 mol% to about 20 mol% Al2O3;

[0054] from about 10 mol% to about 20 mol% of at least one alkali metal oxide, the alkali metal oxide comprising Li2O, Na2O, and K2O;

[0055] 0.001 mol % to about 1 mol % of said polyvalent colorant; and

[0056] At least one of B2O3 or P2O5.

[0057] Aspect 40. The natural glass enclosure of any one of aspects 26 to 38, wherein the glass article comprises, in mol % of the glass article:

[0058] 60 mol% to 65 mol% SiO2;

[0059] 12 mol% to 17 mol% Al2O3;

[0060] 3 mol% to 6 mol% B2O3;

[0061] 10 mol% to 16 mol% of at least one alkali metal oxide, the alkali metal oxide comprising Li2O, Na2O, and K2O;

[0062] 3 mol% to 5 mol% CaO;

[0063] 0 mol% to 1 mol% ZrO2;

[0064] 0 mol% to 0.25 mol% SnO2; and

[0065] 0.005 mol% to about 0.2 mol% of said multivalent colorant.

[0066] Aspect 41. The natural glass enclosure of any one of aspects 26 to 40, wherein the glass article comprises at least one crystalline phase.

[0067] Aspect 42. The natural glass enclosure according to aspect 41, wherein the crystallinity of the glass article is 10 wt% or less.

[0068] Aspect 43. The natural glass envelope according to any one of aspects 26 to 42, further comprising a first compressive stress region extending from the first compressive stress region to a first compression depth.

[0069] Aspect 44. The natural glass envelope of aspect 43, wherein the maximum compressive stress of the first compressive stress region is about 400 MPa or greater.

[0070] Aspect 45. The natural glass enclosure of any one of aspects 26 to 44, wherein the glass article has a dielectric constant of about 5.6 to about 6.4 at a frequency of 10 GHz to 60 GHz.

[0071] Aspect 46. The natural glass enclosure according to any one of aspects 26 to 45, wherein the glass article exhibits a 0.60 MPa m 1 / 2 or higher fracture toughness and a Young's modulus of about 50 GPa to about 100 GPa.

[0072] Aspect 47. The primary color glass housing according to any one of aspects 26 to 46, further comprising:

[0073] A circuit comprising an antenna that transmits a signal in the range of 26 GHz to 40 GHz;

[0074] the primary glass housing at least partially surrounding the circuit; and

[0075] a structure formed as an integral part of the glass article, wherein the structure includes a perimeter delimiting a second thickness of the structure, the second thickness differing from a thickness of the glass article by at least 150 μm,

[0076] The antenna is positioned and oriented so that the signal is transmitted through the structure of the glass sheet of the panel of the housing.

[0077] Throughout this disclosure, the accompanying drawings are used to emphasize certain aspects. Therefore, unless otherwise explicitly indicated, the relative sizes of the various regions, parts, and substrates shown in the accompanying drawings should not be considered to be proportional to their actual relative sizes. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] The above and other features and advantages of various aspects of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which:

[0079] Figure 1 is a schematic plan view of an example consumer electronic device according to aspects of the present disclosure;

[0080] Figure 2 yes Figure 1 a schematic perspective view of an example consumer electronic device;

[0081] Figure 3 is a conceptual diagram of a rear view of a communication device, more particularly, a cellular phone, according to one aspect of the present disclosure;

[0082] Figure 4 So along Figure 3 A slightly exploded cross-sectional view taken along line 4-4 shows Figure 3 A simplified conceptual diagram of the device;

[0083] Figure 4A show Figure 4 Amplification Figure 4A ;

[0084] Figure 4B show Figure 4 Amplification Figure 4B ;

[0085] Figure 5 is a cross-sectional view of a natural glass housing including a glass article according to aspects of the present disclosure; and

[0086] Figure 6A flow chart illustrating a method for manufacturing a glass product and / or a natural glass housing according to various aspects of the present disclosure is provided;

[0087] Figure 7 A step in a method of manufacturing a glass article and / or a natural glass casing comprising ion exchange is illustrated;

[0088] Figure 8-9 Plotting the results of X-ray photoelectron spectroscopy of chromium-containing raw materials;

[0089] Figure 10-15 schematically represents a cross-section of a glass article as discussed in the Examples and in accordance with aspects of the present disclosure; and

[0090] Figure 16 The transmission of glass articles having various amounts of iron according to aspects of the present disclosure is shown as a function of wavelength. DETAILED DESCRIPTION

[0091] Various aspects will now be described more fully hereinafter with reference to the accompanying drawings, in which example aspects are shown. Wherever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts.

[0092] Figure 3-5 A view of a natural glass housing 322 or 500 including a glass article 511 is shown, which may be incorporated into a consumer electronic product (eg, a display device), such as a Figure 1-4 Unless otherwise indicated, discussion of features of various aspects of a foldable device may apply equally to corresponding features of any aspect of the disclosure. For example, identical part numbers throughout the disclosure may indicate that features identified in some aspects are identical to one another, and discussion of features identified in one aspect may apply equally to features identified in any other aspect of the disclosure unless otherwise indicated.

[0093] Aspects of the present disclosure may include consumer electronic products. The consumer electronic product may include a front surface, a rear surface, and side surfaces. The consumer electronic product may also include an electrical component at least partially located within a housing. The electrical component may include a controller, a memory, and a display. The display may be located at or adjacent to the front surface of the housing. The display may include a liquid crystal display (LCD), an electrophoretic display (EPD), an organic light emitting diode (OLED) display, or a plasma display panel (PDP). The consumer electronic product may include a cover plate positioned above the display. In various aspects, at least a portion of the housing or the cover plate includes a foldable device discussed throughout this disclosure. The consumer electronic product may include a portable electronic device, such as a smartphone, a tablet computer, a wearable device, or a laptop computer.

[0094] The foldable devices disclosed herein can be incorporated into another article, such as an article with a display (or display article) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches), etc.), a building article, a transportation article (e.g., a car, train, airplane, marine vessel, etc.), an electrical article, or any article that may benefit from some transparency, scratch resistance, wear resistance, or a combination thereof. An exemplary article having any of the foldable devices disclosed herein is shown in FIG. Figure 1-2 Specifically, Figure 1-2 A consumer electronic device 100 is shown, which includes a housing 102 having a front surface 104, a rear surface 106, and side surfaces 108. Although not shown, the consumer electronic device may include electrical components at least partially within the housing or completely within the housing. For example, the electrical components may include at least a controller, a memory, and a display. Figure 1-2 , display 110 can be located at or adjacent to the front surface of housing 102. The consumer electronic device can include a cover plate 112 at or above the front surface of housing 102, such that the cover plate is above display 110. In various aspects, at least a portion of housing 102 can include the glass and / or natural glass housing disclosed herein.

[0095] See Figure 3-4 , a communication device 310 (i.e., an electronic device having wireless signal communication capabilities; such as a broadband communication device, a cellular phone, a smart phone, a control panel, a console, a dashboard, a tablet computer, a handheld computer, an electronic tool) includes a circuit 312 (see Figure 4 ). Figure 1-2 The consumer electronic device 100 shown in FIG is an example of a communication device 310. In various aspects, the circuit 312 includes an antenna 314. The circuit 312 may also include other components, such as a camera 316 ( Figure 3 ), printed circuit board, processor, memory, display 110 ( Figure 3 ), batteries, connector ports and other components.

[0096] In various aspects, antenna 314 may comprise a patterned metal wire or metal layer, or other such device (e.g., a transceiver, a receiver, a transmitter, an antenna array, a communication module) configured to transmit and / or receive communication signals at or within a frequency range. The surface area of an antenna is defined as the area within a perimeter 338 surrounding the antenna. In other aspects, the surface area of an antenna may be 25 cm 2 or smaller, 15cm 2 or smaller, 10cm 2 or smaller, 100μm 2 or larger, 1mm 2or larger, 25mm 2 or larger, or 100mm 2 or greater. In other aspects, the antenna 314 can be configured for wireless communication (e.g., transmitting, receiving, operating, and / or otherwise communicating) and transmit signals at a frequency of 100 MHz or greater, 1 GHz or greater, 10 GHz or greater, 24 GHz or greater, 24.25 GHz or greater, GHz or greater, 26 GHz or greater, 28 GHz or greater, 100 GHz or less, 60 GHz or less, 50 GHz or less, 47 GHz or less, or 40 GHz or less. For example, the antenna can operate at frequencies in the range of 26 GHz to 40 GHz or 60 GHz to 80 GHz. Communications at frequencies greater than 26 GHz can particularly benefit from the present disclosure because these signals can be more difficult to transmit through solid materials and can therefore be significantly improved by using a housing 102 incorporating the structure 326 described herein. Accordingly, the antenna 314 can be positioned and / or oriented so that signals are transmitted through the structure 326 (e.g., directly facing the structure 326, which can cover at least a portion of the antenna 314). In other aspects, the minimum distance between the antenna 314 and the 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. Alternatively, the antenna 314 and the portion of the glass article defining the structure 326 can be in direct contact or separated only by the thickness of the coating 328.

[0097] In various aspects, such as Figure 3-4 As shown in FIG, the communication device 310 includes a housing 102 that encloses some or all of the circuitry 312. The housing 102 may include a frame 320, such as metal (e.g., aluminum, steel) sidewalls, a primary glass housing 322 (e.g., a back), and a display 110 (e.g., see FIG). Figure 1-2 Housing 102 may also include alternative structures, such as a panel integral with the frame, forming the back surface and having side walls within which circuitry 312 and other components may be located, and / or housing 102 may be integral with a keyboard, touch panel, or other features, in addition to or in lieu of a display.

[0098] In various aspects, such as Figure 3-4 As shown in , the primary glass housing 322 may include (e.g., comprise, consist essentially of, by weight or volume) a glass article 350. The glass article 350 may be flat, may have curved edges, may be arched, or may be in other forms. Figure 4As shown in FIG, the primary glass housing 322 may include one or more layers 328 on the surface of the glass article 350 (e.g., the first major surface 332, the second major surface 330 of the glass article 350), such as a scratch-resistant coating, an anti-reflective coating, or other coating, and may also include decorative ink and / or other layers on its surface. For example, the coating 328 on the second major surface 330 of the glass article may include the following reference Figure 5 Any aspects of the reflector 501 discussed and / or identical to the reflector described. It is envisioned that, although not shown, the natural glass housing could consist solely of a sheet of glass, in which case no layers, coatings, etc. would be required for the corresponding device.

[0099] In various aspects, such as Figure 4 As shown in , the glass article 350 includes a structure 326. The structure 326 can be an integral part of the glass article 350, such that the glass of the glass article 350 extends continuously throughout the glass article 350, including defining the structure 326. For example, the structure 326 can be a groove, a groove, a bump, a platform or other feature formed in or on the glass article 350. The glass article 350 can have more than one such structure 326. Such a structure can be formed in many conceivable ways, such as 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 into a mold, welding additional glass to the glass article 350. Thus, the glass forming the structure 326 can have the same composition as the glass of the glass article 350 outside of the structure 326. The glass of the structure 326 can also share a common microstructure with the glass of the glass article 350 outside of the structure 326, such as having the same crystal type and distribution (for example, when the glass is a glass ceramic) and / or the same colorant type and distribution. In various aspects, as Figure 4 As shown in FIG, structure 326 forms a recess relative to a major surface (e.g., second major surface 330) of glass article 350. As used herein, a "major surface" of a sheet of glass article 350 is the side of the sheet having the largest surface area (e.g., the front and back surfaces). A major surface may be surrounded by an edge of the sheet extending between the major surfaces. For more complex bodies, a major surface may have an area on its surface defined by an edge perimeter, wherein the major surface has a surface area that is substantially greater than other surfaces (e.g., the sidewalls) of the body, for example, at least 50% greater.

[0100] In various aspects, such as Figure 4 As shown in FIG, glass article 350 includes a thickness 337, which is defined as the average distance between second major surface 330 and first major surface 332, excluding any portion of glass article 350 that includes structure 326 described above, opposite first major surface 332. In other aspects, thickness 337 may be defined as follows with reference to Figure 5 In other aspects, thickness 337 can be substantially uniform across second major surface 330 , and / or more than 50% of the glass article can include a local thickness within 10% of thickness 337 .

[0101] In various aspects, such as Figure 3-4 As shown in FIG, structure 326 includes a perimeter 340 on a major surface (e.g., second major surface 330) of glass article 350, wherein perimeter 340 delimits a second thickness 327 of structure 326 that is different from thickness 337, e.g., by 50 μm or more, 100 μm or more, 150 μm or more, 200 μm or more, 300 μm or more, or 500 μm or more (e.g., at corner 336, e.g., at corner 337). Figure 4B ). For example, second thickness 327 of structure 326 can be 600 μm or less, 500 μm or less, or 400 μm or less, while thickness 337 of glass article 350 can be 600 μm or greater, 700 μm or greater, 800 μm or greater (or any of the ranges described herein for thickness 517). Alternatively, although not shown, second thickness 327 can be 50 μm or greater, 100 μm or greater, 150 μm or greater, 200 μm or greater, 300 μm or greater, or 500 μm or greater than thickness 337. Figure 3-4 As shown in , the perimeter 340 forms a closed loop on a major surface (e.g., the second major surface 330), wherein the shape of the perimeter 340 can be linear, curved, or arcuate, and can include any shape (e.g., square, block, pyramid-shaped with multiple rows of rectangles of decreasing length stacked on top of each other (ziggurat-shaped), triangle, ellipse, or even more complex geometric shapes). For example, the perimeter 340 of the structure 326 can be shaped as the outline of a logo and / or registered trademark, or other recognizable design or shape. As used herein, the surface area of a structure is defined as the surface area within the perimeter of the structure projected onto the first major surface of the glass article. In various aspects, the surface area of the structure 326 can be 100 cm 2 or smaller, 50cm 2 or smaller, 25cm 2 or smaller, 25μm 2 or larger, 100μm 2 or larger, 1mm 2 or larger, 25mm 2 or larger, or 4cm 2 In various aspects, the glass article may include a housing for a communication device, and the glass article may have more than one such structure, such as Figure 3, where structure 326 overlies antenna 314, while another structure 342 forms part of a camera or sensor encasement, such as camera 316. In other aspects, structures 326 and / or 342 can cover at least a portion and / or all of the surface area corresponding to antenna 314 and / or camera 316.

[0102] Structures 326 and / or 342 are formed in the middle or inner portion of the glass article 350 and are spaced from the outer edge 344 of the glass article 350 (see FIG. Figure 3 ) can help alleviate structural weaknesses or stress concentrations in the glass article 350 that may be associated with forming structures 326 and / or 342. When forming structure 326, edges or corners 334 and / or 336 are formed (see Figures 4A-4B ) or having a perimeter 340 of the structure 326 that reduces stress concentrations at the edges or corners 334 and / or 336 can also help strengthen the glass article 350. Such geometry can include rounded or blunted vertices or corners 334 and / or 336 of the structure 326, which can be achieved by etching or localized melting / heating (e.g., with a laser). For example, the glass article 350 can smoothly transition between the thickness 337 at the corners 334 and / or 336 and the second thickness 327 over a distance "D" (see Figure 4A ), when measured in a direction perpendicular to the direction of thickness 337, the distance is about 5 μm to 700 μm, about 10 μm to about 500 μm, about 20 μm to about 500 μm, about 100 μm to about 500 μm, or any range or sub-range therebetween.

[0103] Throughout this disclosure, CIE color coordinates are referenced to the CIELAB 1976 color space established by the International Commission on Illumination (CIE). Unless otherwise indicated, CIE color coordinates are measured as transmittance through a glass article using an F02 illuminant and an observation angle of 10°. The CIELAB 1976 color space represents color as three values: L*: lightness from black (0) to white (100), a*: lightness from green (-) to red (+), and b*: lightness from blue (-) to yellow (+).

[0104] Figure 5A primary glass housing 500 is depicted that includes a glass article 511 and a reflector 501. In various aspects, the reflector 501 comprises an opaque material. As used herein, opaque means that the average transmittance through a 1.0 mm thick block of material in the wavelength range of 400 nm to 700 nm is 10% or less. The average transmittance in the wavelength range of 400 nm to 700 nm is calculated by measuring the transmittance at integer wavelengths of about 400 nm to about 700 nm and averaging the measured values. In various aspects, the reflector comprises a CIE L* value of about 70 or greater. An exemplary material for the reflector is aluminum. In various aspects, as Figure 5 As shown in FIG, glass article 511 can be disposed on and / or in contact with surface 503 of reflector 501, which can contact glass article 511. Providing a reflector can increase the perceived brightness of the glass article.

[0105] Unless otherwise indicated, transmittance data in the visible spectrum (total transmittance and diffuse transmittance) were measured using a Lambda 950 UV / Vis / NIR spectrophotometer manufactured by PerkinElmer (Waltham, Massachusetts USA). The Lambda 950 instrument was equipped with a 150 mm integrating sphere. An open beam baseline and Data is collected with reference to a reflective disk. For total transmittance (total Tx), the sample is fixed at the entrance point of the integrating sphere. As used herein with respect to the visible spectrum, the term "average transmittance" refers to the average value of transmittance measurements taken within a given wavelength range, with equal weighting for each integer wavelength. Unless otherwise indicated, as described herein, "average transmittance" with respect to the visible spectrum is reported within a wavelength range of 380nm to 750nm (inclusive). Unless otherwise indicated, average transmittance refers to the average transmittance of an article having a thickness of 0.4mm to 5mm (inclusive). Unless otherwise indicated, when average transmittance is indicated, this means that each thickness within the thickness range of 0.4mm to 5mm has a specified average transmittance. For example, a colored glass product having an average transmittance of 10% to 92% in the wavelength range of 380nm to 750nm means that each thickness in the range of 0.4mm to 5mm (e.g., 0.6mm, 0.9mm, 2mm, etc.) has an average transmittance in the range of 10% to 92% for the wavelength range of 380nm to 750nm.

[0106] As used herein, if a first layer and / or component is described as being “disposed above” 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. In addition, as used herein, “disposed above” does not refer to a relative position with respect to gravity. For example, a first layer and / or component may be considered to be “disposed above” a second layer and / or component when the first layer and / or component is disposed below, above, or to one side of the second layer and / or component. As used herein, a first layer and / or component is described as being “bonded to” a second layer and / or component meaning that the layers and / or components are bonded to each other by direct contact and / or bonding between the two layers and / or components or via an adhesive layer. As used herein, a first layer and / or component is described as “contacting” a second layer and / or component or “in contact with a second layer and / or component” means direct contact and includes situations where the layers and / or components are bonded to each other.

[0107] like Figure 5 , glass article 511 includes a first major surface 513 and a second major surface 515 opposite first major surface 513. In various aspects, as shown, first major surface 513 and / or second major surface 515 can comprise flat surfaces, although other shapes and designs are possible in other aspects. Thickness 517 of glass article 511 is defined as the average distance between first major surface 513 and second major surface 515. In various aspects, the thickness 517 can be about 30 μm (micrometers) or greater, about 50 μm or greater, about 80 μm or greater, about 100 μm or greater, about 150 μm or greater, about 200 μm or greater, about 400 μm or greater, about 500 μm or greater, about 600 μm or greater, about 5 mm (millimeter) or less, about 3 mm or less, about 2 mm or less, about 1 mm or less, about 800 μm or less, about 700 μm or less, about 600 μm or less, about 550 μm or less, about 500 μm or less, or about 300 μm or less. In various aspects, the thickness 517 can be in the range of about 30 μm to about 5 mm, about 50 μm to about 5 mm, about 80 μm to about 5 mm, about 100 μm to about 5 mm, about 200 μm to about 5 mm, about 400 μm to about 3 mm, about 500 μm to about 2 mm, about 600 μm to about 1 mm, or any range or sub-range therebetween.

[0108] Glass articles 511 and / or 350 include a glass-based material. In various aspects, the glass-based material can include a pencil hardness of 8H or greater, such as 9H or greater. As used herein, pencil hardness is measured using ASTM D 3363-20 with a standard lead graded pencil. Throughout this disclosure, elastic modulus (e.g., Young's modulus) and / or Poisson's ratio are measured using ISO 527-1:2019. In various aspects, glass articles 511 and / or 350 can include an elastic modulus within a range of about 40 GPa to about 140 GPa, about 50 GPa to about 100 GPa, about 60 GPa to about 80 GPa, or any range or sub-range therebetween.

[0109] As used herein, "glass-based" includes both glass and glass-ceramics, wherein the glass-ceramics have one or more crystalline phases and an amorphous residual glass phase. Glass-based materials may include amorphous materials (e.g., glass) and optionally one or more crystalline materials (e.g., ceramics). Amorphous materials and glass-based materials may be strengthened. As used herein, the term "strengthening" may refer to a material that has been chemically strengthened, such as by ion exchange of larger ions with smaller ions in the surface of a glass article, as discussed below. However, other strengthening methods, such as thermal tempering, or the mismatch of thermal expansion coefficients between parts of a glass article to produce a compressive stress zone and a central tension zone, may also be utilized to form a strengthened glass article. Exemplary glass-based materials that may or may not contain lithium oxide include soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali-containing aluminoborosilicate glass, alkali-containing phosphosilicate glass, and alkali-containing aluminophosphosilicate glass. In various aspects, the glass-based material may include alkali-containing glass or alkali-free glass, either of which may or may not contain lithium oxide. In various aspects, the glass material can be alkali-free and / or include a low content of alkali metals (e.g., about 10 mol% or less of RO, wherein RO includes LiO, NaO, KO, or the more extensive list provided below). In one or more aspects, the glass-based material can include, by mole percentage (mol%), SiO in a range of about 40 mol% to about 80 mol%, AlO in a range of about 5 mol% to about 30 mol%, BO in a range of 0 mol% to about 10 mol%, ZrO in a range of 0 mol% to about 5 mol%, PO in a range of 0 mol% to about 15 mol%, TiO in a range of 0 mol% to about 2 mol%, RO in a range of 0 mol% to about 20 mol%, and RO in a range of 0 mol% to about 15 mol%. As used herein, RO can refer to alkali metal oxides, including LiO, NaO, and KO. As used herein, RO may refer to MgO, CaO, SrO, BaO, and ZnO. In other aspects, the glass-based material may include (in mol%) about 50 mol% to about 75 mol% SiO2, about 7 mol% to about 20 mol% Al2O3, about 10 mol% to about 20 mol% of at least one alkali metal oxide (RO), 0.001 mol% to about 1 mol% of a multivalent colorant, and at least one of B2O3 or PO5.In other aspects, the glass-based material may include (in mol%) 60 to 65 mol% SiO2, 12 to 17 mol% Al2O3, 3 to 6 mol% B2O3, 10 to 16 mol% of at least one alkali metal oxide (RO), 3 to 5 mol% CaO, 0 to 1 mol% ZrO2, 0 to 0.25 mol% SnO2, and 0.005 to about 0.2 mol% of a multivalent colorant. In various aspects, the glass-based material may also optionally include each of the following in the range of 0 to about 2 mol%: Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, As2O3, Sb2O3, SnO2, Fe2O3, MnO, MnO2, MnO3, Mn2O3, Mn3O4, Mn2O7. In various aspects, the glass-based material may include iron oxide, titanium dioxide, antimony oxide, cobalt oxide, cerium oxide, and / or chromium oxide. In various aspects, the glass-based material may include a multivalent colorant selected from the group consisting of chromium, cobalt, cerium, titanium, copper, nickel, vanadium, or combinations thereof. In other aspects, the glass-based material may include 200 ppm (parts per million) to about 5,000 ppm chromium.

[0110] Unless otherwise indicated, the composition is described in mole percent (mol%). The terms "0 mol%" and "free of" when used to describe the concentration and / or absence of a particular constituent component in a glass composition mean that the constituent component is not present in the glass composition. The term "substantially free of" when used to describe the concentration and / or absence of a particular constituent component in a glass composition and a colored glass product obtained therefrom means that the constituent component is not intentionally added to the glass composition and the colored glass product obtained therefrom. However, unless otherwise specified herein, the glass composition and the colored glass product obtained therefrom may contain trace amounts of the constituent components as contaminants or tramps, in an amount less than 200 ppm. It should be noted that the definition of "substantially free of" does not include gold (Au), which can be intentionally added to the glass composition in relatively small amounts, such as, but not limited to, an amount of less than 200 ppm (or an equivalent amount in mol%), to obtain a desired color in the resulting colored glass product.

[0111] "Glass ceramics" include materials produced by controlled crystallization of glass. In various aspects, the glass ceramics have a crystallinity of about 1% to about 99%. Examples of suitable glass ceramics may include Li2O-Al2O3-SiO2 system (i.e., LAS system) glass ceramics, MgO-Al2O3-SiO2 system (i.e., MAS system) glass ceramics, ZnO×Al2O3×nSiO2 (i.e., ZAS system) and / or glass ceramics comprising a main crystalline phase comprising β-quartz solid solution, β-spodumene, cordierite, petalite and / or lithium disilicate. The glass ceramic material can be strengthened using a chemical strengthening method. In one or more aspects, the MAS system glass ceramic material can be strengthened in a Li2SO4 molten salt, thereby being able to undergo 2Li + With Mg 2+ In various aspects, the glass article 511 and / or 350 can be a glass-ceramic comprising one or more crystalline phases. In other aspects, the total amount of the one or more crystalline phases, based on the weight percent (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.

[0112] As used herein, a polyvalent colorant comprises at least two oxidation states, wherein the oxidation state of the colorant is non-zero valent and two or more of the at least two oxidation states exhibit color as measured by absorbance at 400 nm to 750 nm or CIE a* and / or b* values. For example, chromium is a polyvalent colorant because chromium can be Cr 3+ and Cr 6+ There are Cr 3+ Related to green and Cr 6+ Can be associated with yellow. Similarly, cerium is also a polyvalent colorant because cerium can Ce 4 + and Ce 3+ exists in the form of Ce 4+ Related to yellow and Ce 3+ Related to red. Similarly, titanium is also a polyvalent colorant because it can 2+ and Ti 4+ Form exists, where Ti 2+ Associated with purple and Ti 4+ Related to white or can be colorless. Similarly, copper is also a polyvalent colorant because copper can Cu 1+ and Cu 2+ exists in the form of Cu 1+ Related to green and Cu2+ Associated with blue. Similarly, nickel is also a polyvalent colorant because nickel can Ni 2+ and Ni 3+ Form exists, where Ni 2+ Associated with yellow and Ni 3+ Associated with purple. Similarly, vanadium is also a polyvalent colorant because vanadium can V 4+ and V 5+ The form exists, where V 4+ Associated with green and V 5+ Associated with the color blue. However, the "multivalent colorants" of the present disclosure do not include iron. Although the colorant package of the glass of the present disclosure may include iron, the colorant package will also include a multivalent colorant.

[0113] The glass articles described herein can be described as aluminoborosilicate glass compositions and colored glass articles, and include SiO2, Al2O3, and B2O3. In addition, the glass articles described herein include one or more colorants from a colorant package to provide the resulting colored glass article with a desired color. The glass articles described herein also include alkali metal oxides (e.g., Li2O and Na2O) to enable ion exchangeability of the colored glass article. In various aspects, the glass articles described herein may also include other components to improve the retention of the colorant and produce a colored glass article with a desired color. In various aspects, the difference between R2O and Al2O3 (i.e., R2O (mol%) - Al2O3 (mol%)) in the glass articles described herein can be adjusted to produce a desired observed color (e.g., pink, purple, red, orange, or blue). In various aspects, the viscosity of the glass composition can be adjusted to prevent devitrification of the glass composition.

[0114] SiO is the main glass former in the glass products described herein and can be used to stabilize the network structure of colored glass products. The concentration of SiO in the glass products should be high enough (e.g., 40 mol% or higher) to enhance the chemical durability of the glass composition, particularly the resistance of the glass composition to degradation when exposed to acidic solutions, alkaline solutions, and in water. The amount of SiO can be limited (e.g., 80 mol% or lower) to control the melting point of the glass composition, because the melting point of pure SiO or high-SiO glass is undesirably high. Therefore, limiting the concentration of SiO can help improve the meltability and formability of the resulting colored glass products. In various aspects, the glass products can include 40 mol% to 80 mol% SiO or 50 mol% to 80 mol% SiO. In various aspects, the glass products can include about 45 mol% to about 67 mol% SiO or 53 mol% to 67 mol% SiO. In various aspects, the concentration of SiO2 in the glass article can 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, 60 mol% or less, or 59 mol% or less. In various aspects, the concentration of SiO2 in the glass article can be 40 mol% to 70 mol%, 45 mol% to 70 mol%, 50 mol% to about 68 mol%, about 52 mol% to about 68 mol%, about 53 mol% to about 67 mol%, about 54 mol% to about 67 mol%, about 55 mol% to about 66 mol%, about 56 mol% to about 65 mol%, about 57 mol% to about 65 mol%, about 58 mol% to about 65 mol%, about 60 mol% to about 65 mol%, about 60 mol% to about 64 mol%, about 60 mol% to about 63 mol%, about 60 mol% to about 62 mol%, or any range or sub-range therebetween.

[0115] Like SiO2, Al2O3 can also stabilize the glass network and additionally provide the glass article with improved mechanical properties and chemical durability. The amount of Al2O3 can also be tailored to control the viscosity of the glass composition. Inclusion of Al2O3 can provide the resulting glass article with a desired fracture toughness (e.g., greater than or equal to 0.7 MPa·m 1 / 2). However, if the amount of Al2O3 is too high (e.g., 25 mol% or more), the viscosity of the glass melt may increase, thereby reducing the formability of the glass article. In various aspects, if the amount of Al2O3 is too high, the solubility of one or more colorants of the colorant package in the glass melt may decrease, causing undesirable crystalline phases to form in the glass. For example, but not limited to, when the colorant package includes Cr2O3, the solubility of Cr2O3 in the glass melt may decrease as the Al2O3 concentration (e.g., a concentration greater than or equal to 17.5 mol%) increases, causing undesirable crystalline phases to precipitate. Without wishing to be bound by theory, it is hypothesized that similar behavior may occur in the presence of colorants other than Cr2O3. Therefore, in various aspects, the glass com article may include 7 mol% to 25 mol% Al2O3, 7 mol% to 20 mol% Al2O3, or 8 mol% to 20 mol% Al2O3. In various aspects, the glass article can include 10 mol% to 20 mol% Al2O3, 10 mol% to about 17.5 mol% Al2O3, or 12 mol% to about 17.25 mol% Al2O3. In various aspects, the glass article can include 11 mol% to 19 mol% Al2O3, or 14 mol% to 17 mol% Al2O3. In various aspects, the concentration of Al2O3 in the glass article can 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. In various aspects, the concentration of Al2O3 in the glass article can be 7 mol% to 25 mol%, 7 mol% to 23 mol%, 8 mol% to 20 mol%, 9 mol% to 19 mol%, 10 mol% to 18 mol%, 11 mol% to 17.5 mol%, 12 mol% to 17.25 mol%, 13 mol% to 17 mol%, 14 mol% to 16.75 mol%, 14.5 mol% to 16 mol%, or any range or sub-range therebetween.

[0116] B2O3 lowers the melting point of the glass composition, thereby improving the retention of certain colorants in the glass, such as but not limited to Au. B2O3 may also improve the damage resistance of the resulting colored glass product. In addition, the addition of B2O3 can reduce the formation of non-bridging oxygen, the presence of which may reduce fracture toughness. The concentration of B2O3 should be high enough (e.g., 1 mol% or higher) to lower the melting point of the glass composition, improve formability and increase the fracture toughness of the colored glass product. However, if B2O3 is too high (e.g., 15 mol% or higher), the annealing point and strain point may be reduced, thereby increasing stress relaxation of the colored glass product and reducing its overall strength. In various aspects, the glass product may include 1 mol% to 15 mol% B2O3, 1 mol% to 10 mol% B2O3, 3 mol% to 10 mol% B2O3, or 3.5 mol% to 9 mol% B2O3. In various aspects, the glass article can include 2 mol% to 12 mol% B2O3 or 2 mol% to 8 mol% B2O3. In various aspects, the concentration of B2O3 in the glass article can 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. In various aspects, the concentration of B2O3 in the glass article can be 1 mol% to 15 mol%, 2 mol% to 12 mol%, 3 mol% to 10 mol%, 3.5 mol% to 9 mol%, 4 mol% to 8 mol%, 4.5 mol% to 7.5 mol%, 5 mol% to 7 mol%, 5.5 mol% to 6.5 mol%, or any range or sub-range therebetween.

[0117] As described above, the glass article may contain alkali metal oxides (eg, Li2O, Na2O, and K2O) to enable ion exchangeability of the glass article.

[0118] Li2O contributes to the ion exchangeability of the glass product and also lowers the softening point of the glass composition, thereby increasing the formability of the glass product. Adding Li2O will promote the Na + and K +Cations are exchanged into the glass to strengthen the glass and also promote the generation of relatively high surface compressive stress and relatively deep compression depth, thereby improving the mechanical characteristics of the resulting colored glass product. In addition, Li2O lowers the melting point of the glass composition, thereby improving the retention of colorants in the glass, such as but not limited to Au. The concentration of Li2O in the glass product should be high enough (e.g., 1 mol% or higher) to lower the melting point of the glass composition and achieve the desired maximum central tension (e.g., 40 MPa or higher) after ion exchange. However, if the amount of Li2O is too high (e.g., greater than 20 mol%), the liquidus temperature may increase, thereby reducing the manufacturability of the colored glass product. In various aspects, the glass product may include 1 mol% to 20 mol% Li2O or 1 mol% to 20 mol% Li2O. In various aspects, the glass product may include 3 mol% to 18 mol% Li2O, 7 mol% to 18 mol% Li2O, 8.8 mol% to 14 mol% Li2O, or 9 mol% to 13.5 mol% Li2O. In various aspects, the concentration of Li2O in the glass article can 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. In various aspects, the concentration of Li2O in the glass article can be 1 mol% to 20 mol%, 3 mol% to 18 mol%, 5 mol% to 17 mol%, 7 mol% to 16 mol%, 7.5 mol% to 15 mol%, 8 mol% to 14 mol%, 8.5 mol% to 13.5 mol%, 8.8 mol% to 13 mol%, 9 mol% to 12.5 mol%, 9.2 mol% to 12.5 mol%, 9.4 mol% to 12 mol%, 9.6 mol% to 12 mol%, 9.8 mol% to 11.5 mol%, 10 mol% to 11 mol%, or any range or sub-range therebetween.

[0119] Na2O improves the diffusion rate of alkali metal ions in the glass and thus shortens the ion exchange time, and helps achieve the required surface compressive stress (e.g., 300 MPa or higher). Adding Na2O also promotes K +Cations are exchanged into the glass to strengthen the resulting colored glass product and improve its mechanical properties. Na2O also improves the formability of the colored glass product. Additionally, Na2O lowers the melting point of the glass composition, thereby improving the retention of certain colorants in the glass, such as, but not limited to, Au. However, if too much Na2O is added to the glass composition, the melting point may be too low. In various aspects, the concentration of Li2O present in the glass product may be higher than the concentration of Na2O present in the glass product. In various aspects, the glass product may include greater than 0 mol%, 0.01 mol% to 15 mol%, 0.5 mol% to 15 mol% Na2O, or 1 mol% to 15 mol% Na2O. In various aspects, the glass product may include 1 mol% to 12 mol% Na2O, or 2 mol% to 10 mol% Na2O. In various aspects, the glass product may include 0.01 mol% to 4 mol% Na2O. In various aspects, the glass article may include 1.5 mol% to 8 mol% Na2 O or 2 mol% to 7.5 mol% Na2 O. In various aspects, the concentration of Na2O 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. In various aspects, the concentration of NaO in the glass article can be greater than 0 mol% to 15 mol%, 0.01 mol% to 12 mol%, 0.5 mol% to 12 mol%, 1 mol% to 10 mol%, 1.5 mol% to 9 mol%, 2 mol% to 8.5 mol%, 2.5 mol% to 8 mol%, 3 mol% to 7.5 mol%, 3.5 mol% to 7 mol%, 4 mol% to 6.5 mol%, 4.5 mol% to 6 mol%, or any range or sub-range therebetween.In various aspects, the concentration of NaO in the glass article can be 0.5 mol% to 10 mol%, 1 mol% to 9 mol%, 1 mol% to 8 mol%, 1 mol% to 7 mol%, 1 mol% to 6.5 mol%, 1 mol% to 6 mol%, 1 mol% to 5.5 mol%, 1 mol% to 5 mol%, 1.5 mol% to 4.5 mol%, 2 mol% to 4 mol%, or any range or sub-range therebetween.

[0120] When included, KO promotes ion exchange and can increase compression depth, and lowers the melting point to improve the formability of colored glass products. However, adding too much KO can cause surface compressive stress and a lower melting point. Therefore, in various aspects, the amount of KO added to the glass composition can be limited. In various aspects, the glass article can optionally include greater than 0 mol% to 3 mol% KO, greater than 0 mol% to 1 mol% KO, 0.01 mol% to 1 mol% KO, or 0.1 mol% to 1 mol% KO. In various aspects, the glass article can optionally include 0.1 mol% to 0.5 mol% KO. In various aspects, the concentration of KO in the glass article can 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. In various aspects, the concentration of KO in the glass article can be greater than 0 mol% to 3 mol%, 0.01 mol% to 2.5 mol%, 0.1 mol% to 2 mol%, 0.2 mol% to 1.5 mol%, 0.25 mol% to 1 mol%, 0.3 mol% to 0.75 mol%, 0.4 mol% to 0.5 mol%, or any range or sub-range therebetween.

[0121] As used herein, R2O is the sum (in mol%) of Li2O, Na2O, and KO present in the glass article (i.e., R2O = Li2O (mol%) + Na2O (mol%) + KO (mol%). Like B2O3, alkali metal oxides contribute to lowering the softening point and molding temperature of the glass composition, thereby counteracting increases in the softening point and molding temperature of the glass composition caused by, for example, a higher amount of SiO2 in the glass composition. The softening point and molding temperature can be further lowered by including a combination of alkali metal oxides (e.g., two or more alkali metal oxides) in the glass composition, a phenomenon known as the "mixed alkali effect." However, it has been found that if the amount of alkali metal oxides is too high, the average thermal expansion coefficient of the glass composition increases to above 100×10 -7 / °C, which may be undesirable. In various aspects, the concentration of RO in the glass article can be 1 mol% to 35 mol%, 6 mol% to 25 mol%, or 8 mol% to 23 mol%. In various aspects, the concentration of RO 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. In various aspects, the concentration of RO in the glass article can be in the range of 2 mol% to 35 mol%, 4 mol% to 30 mol%, 6 mol% to 25 mol%, 8 mol% to 23 mol%, 8 mol% to 22 mol%, 10 mol% to 21 mol%, 10.3 mol% to 20 mol%, 11 mol% to 19 mol%, 12 mol% to 18 mol%, 13 mol% to 17 mol%, 14 mol% to 16 mol%, or any range or sub-range therebetween.

[0122] In various aspects, the difference between R2O and Al2O3 in the glass article (i.e., R2O (mol%) - Al2O3 (mol%)) can be adjusted to produce a desired observable color (e.g., pink, purple, red, orange, or blue). As discussed herein, the analytical value of R2O-Al2O3 in the glass article and the added colorant package can be correlated to the color of the colored glass article observable after optional heat treatment. In various aspects, the R2O-Al2O3 in the glass article can be -5 mol% to 7 mol% or -3 mol% to 2 mol%. In various aspects, the R2O-Al2O3 in the glass article can be -3 mol% to 6 mol% or -1 mol% to 5 mol%. In various aspects, the R2O-Al2O3 in the glass article can be -5 mol% to 1.5 mol% or -3 mol% to 1.5 mol%. In various aspects, the R2O-Al2O3 in the glass article can be 1.5 mol% to 7 mol% or 1.5 mol% to 5 mol%. In various aspects, the RO-Al2O3 in the glass article can 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. In various aspects, the R2O-Al2O3 in the glass article can be -5 mol% to 7 mol%, -4 mol% to 6.5 mol%, -3 mol% to 6 mol%, -2.5 mol% to 5.5 mol%, -2 mol% to 5 mol%, -1.5 mol% to 4.5 mol%, 0.2 mol% to 4 mol%, 0.5 mol% to 3.5 mol%, 1 mol% to 3 mol%, 1.5 mol% to 2.5 mol%, or any range or sub-range therebetween.

[0123] In various aspects, the glass articles described herein further comprise MgO and / or ZnO, for example, to improve the retention of colorants, such as Au, in the glass by lowering the melting point of the glass composition. Lowering the melting point of the glass composition can help improve the retention of colorants because the glass composition can be melted at relatively low temperatures, and the evaporation of the colorant (e.g., gold) in the glass can be reduced. Without wishing to be bound by theory, it is also believed that partially replacing Li2O and / or Na2O with MgO and / or ZnO can also help improve the retention of the colorant. Specifically, the Li2O and / or Na2O included in the bulk glass composition are in the form of lithium carbonate and sodium carbonate, respectively. After the glass composition is melted, carbonate gas is released from the glass composition. The colorant (e.g., Au) escapes from the glass composition within the carbonate gas. Therefore, the improvement in colorant retention may be caused by the reduction in the amount of carbonate. Additionally, it is believed that MgO and / or ZnO can improve the solubility of some colorants (e.g., Cr2O3) in the glass, thereby avoiding the formation of undesirable crystalline phases (e.g., Cr-spinel crystals) and expanding the color gamut achievable by the resulting colored glass article. As used herein, "color gamut" refers to the range of colors (pallet) achievable by the colored glass article within the CIELAB color space. For example, in aspects where the colorant comprises Cr2O3, the sum of MgO and ZnO present in the glass article (i.e., MgO (mol%) + ZnO (mol%)) can be from greater than 0 mol% to 6 mol%, or 4.5 mol% or less. Without wishing to be bound by theory, it is hypothesized that similar behavior can occur in the presence of colorants other than Au and Cr2O3. In various aspects, the sum of MgO and ZnO (in mol %) in the glass article (i.e., MgO (mol %) + ZnO (mol %)) can 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. In various aspects, the sum of MgO and ZnO in the glass can be greater than 0 mol% to 8 mol%, 0.1 mol% to 7 mol%, 0.1 mol% to 6 mol%, 0.5 mol% to 6 mol%, 1 mol% to 5.5 mol%, 1.5 mol% to 5 mol%, 2 mol% to 4.5 mol%, 2.5 mol% to 4.25 mol%, 3 mol% to 4 mol%, or any range or sub-range therebetween.

[0124] In addition to improving colorant retention, MgO also reduces the viscosity of the glass composition, thereby enhancing formability, strain point, and Young's modulus, and can improve ion exchangeability. However, when too much MgO is added to the glass composition, the diffusivity of sodium and potassium ions in the glass composition is reduced, which in turn can adversely affect the ion exchange properties (i.e., the ability to exchange ions) of the resulting colored glass article. In various aspects, the glass article can include greater than 0 mol% to 8 mol% MgO or 0 mol% to 4.5 mol% MgO. In various aspects, the glass article can include 0.5 mol% to 7 mol% MgO. In various aspects, the concentration of MgO in the glass article can 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. In various aspects, the concentration of MgO in the glass article can be greater than or equal to 0 mol% to 8 mol%, 0.5 mol% to 7 mol%, 0.5 mol% to 6 mol%, 1 mol% to 5.5 mol%, 1 mol% to 5 mol%, 1.5 mol% to 4.5 mol%, 1.5 mol% to 4 mol%, 2 mol% to 3.5 mol%, 2.5 mol% to 3 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free or free of MgO.

[0125] In addition to improving colorant retention, ZnO also reduces the viscosity of the glass composition, thereby enhancing formability, strain point, and Young's modulus, and can improve ion exchangeability. However, when too much ZnO is added to the glass composition, the diffusivity of sodium and potassium ions in the glass composition is reduced, which in turn can adversely affect the ion exchange properties (i.e., the ability to exchange ions) of the resulting colored glass article. In various aspects, the glass article can include greater than 0 mol% to 5 mol% ZnO, greater than 0 mol% to 4.5 mol% ZnO, 0.1 mol% to 4 mol% ZnO, 0.25 mol% to 1.25 mol% ZnO, or 0.5 mol% to 1 mol% ZnO. In various aspects, the concentration of ZnO in the glass article can 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. In various aspects, the concentration of ZnO in the glass composition can be greater than 0 mol% to 5 mol%, 0.1 mol% to 4.5 mol%, 0.25 mol% to 4 mol%, 0.5 mol% to 3.5 mol%, 0.75 mol% to 3 mol%, 1 mol% to 2.5 mol%, 1.5 mol% to 2 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free or free of ZnO.

[0126] Like ZnO and the alkaline earth metal oxide MgO, other alkaline earth metal oxides, such as CaO, SrO, and BaO, also lower the melting point of the glass composition. Therefore, including CaO, SrO, and / or BaO in a glass article can lower the melting point of the glass composition, thereby helping to improve colorant retention.

[0127] In various aspects, the glass articles described herein may further include CaO. CaO reduces the viscosity of the glass composition, thereby enhancing formability, strain point, and Young's modulus, and can improve ion exchangeability. However, when too much CaO is added to the glass composition, the diffusivity of sodium and potassium ions in the glass composition decreases, which in turn can adversely affect the ion exchange properties (i.e., ion exchange capacity) of the resulting glass. In various aspects, the concentration of CaO in the glass article can 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. In various aspects, the concentration of CaO in the glass article can be greater than 0 mol% to 7 mol%, greater than 0 mol% to 6.5 mol%, 0.25 mol% to 6 mol%, 0.25 mol% to 5.5 mol%, 0.25 mol% to 5 mol%, 0.5 mol% to 4.5 mol%, 0.5 mol% to 4 mol%, 0.5 mol% to 3.5 mol%, 0.75 mol% to 3 mol%, 0.75 mol% to 2.5 mol%, 0.75 mol% to 2 mol%, 1 mol% to 1.75 mol%, 1 mol% to 1.5 mol%, or any range or sub-range therebetween.

[0128] In various aspects, the concentration of SrO in the glass article is 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. In various aspects, the concentration of SrO in the glass article can be greater than 0 mol% to 2 mol%, 0.25 mol% to 1.75 mol%, 0.5 mol% to 1.5 mol%, 0.75 mol% to 1.25 mol%, 0.75 mol% to 1 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free of or free of SrO.

[0129] In various aspects, the concentration of BaO in the glass article can 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. In various aspects, the concentration of BaO in the glass article can be greater than 0 mol% to 2 mol%, 0.25 mol% to 1.75 mol%, 0.5 mol% to 1.5 mol%, 0.75 mol% to 1.25 mol%, 0.75 mol% to 1 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free of or free of BaO.

[0130] As used herein, R ′ O is the sum of MgO, ZnO, CaO, BaO and SrO (in mol%) (i.e., R ′ O=MgO(mol%)+ZnO(mol%)+CaO(mol%)+BaO(mol%)+SrO(mol%)). In various aspects, R ′ The concentration of O can 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. In various aspects, the glass article has R ′ The concentration of O can be greater than 0 mol% to 8 mol%, 0.5 mol% to 7.5 mol%, 0.5 mol% to 7 mol%, 1 mol% to 6.5 mol%, 1 mol% to 6 mol%, 1.5 mol% to 5.5 mol%, 1.5 mol% to 5 mol%, 2 mol% to 4.5 mol%, 2 mol% to 4 mol%, 2.5 mol% to 3.5 mol%, or any range or sub-range therebetween.

[0131] In various aspects, the sum of RO, CaO, MgO and ZnO (RO (mol%) + CaO (mol%) + MgO (mol%) + ZnO (mol%)) can be 35 mol% or less, for example, 1 mol% to 30 mol%, 2 mol% to 30 mol%, 3 mol% to 25 mol%, 4 mol% to 25 mol%, 5 mol% to 20 mol%, 6 mol% to 20 mol%, 7 mol% to 15 mol%, 8 mol% to 10 mol%, or any range or sub-range therebetween.

[0132] In various aspects, the sum of Al2O3, MgO, and ZnO present in the glass article (i.e., Al2O3 (mol%) + MgO (mol%) + ZnO (mol%)) can be between 12 mol% and 22 mol%. Without wishing to be bound by theory, it is believed that combinations of Al2O3, MgO, and ZnO within this range can help avoid the formation of undesirable crystalline phases in the resulting colored glass article. For example, but not limited to, when the colorant in the glass article includes Cr2O3, combinations of Al2O3, MgO, and ZnO within this range can avoid the formation of Cr-spinel crystals by increasing the solubility of the Cr2O3 colorant and thereby expanding the achievable color gamut in the resulting colored glass article. In various aspects, the sum of Al2O3, MgO, and ZnO in the glass article can be between 13 mol% and 21.5 mol%. In various aspects, the sum of Al2O3, MgO, and ZnO in the glass article can 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. In various aspects, the sum of Al2O3, MgO, and ZnO in the glass article can 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 sub-range therebetween.

[0133] In various aspects, the sum of Al2O3, MgO, CaO, and ZnO present in the glass article (i.e., Al2O3 (mol%) + MgO (mol%) + CaO (mol%) + ZnO (mol%)) can be 12 mol% to 24 mol%. Without wishing to be bound by theory, it is believed that combinations of Al2O3, MgO, CaO, and ZnO within this range can help avoid the formation of undesirable crystalline phases in the glass article. Additionally, relatively high concentrations of high field strength modifiers, such as Mg, Ca, and Zn cations, can also improve the mechanical properties of the resulting colored glass article, such as fracture toughness, elastic modulus, and drop test performance. In various aspects, the sum of Al2O3, MgO, CaO, and ZnO in the glass article can be 12 mol% to 24 mol%. In various aspects, the sum of Al2O3, MgO, CaO, and ZnO in the glass article can 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. In various aspects, the sum of Al2O3, MgO, CaO, and ZnO in the glass article can be 12 mol% to 24 mol%, 13 mol% to 23 mol%, 13 mol% to 22 mol%, 14 mol% to 21.5 mol%, 14 mol% to 21 mol%, 15 mol% to 20.5 mol%, 16 mol% to 20 mol%, or any range or sub-range therebetween.

[0134] In various aspects, the glass article may optionally include Cl, which can enable the growth of specific crystalline phases containing the colorant. For example, when the colorant package included in the glass includes Au, the inclusion of Cl can enable the growth of certain Au crystals. In various aspects, the concentration of Cl in the glass article can be greater than 0 mol%, 0.1 mol% or greater, 0.5 mol% or less, or 0.25 mol% or less. In various aspects, the concentration of Cl in the glass article can be greater than 0 mol% to 0.5 mol%, 0.1 mol% to 0.25 mol%, or any range or subrange therebetween. In various aspects, the glass article can be substantially free of or free of Cl. In aspects where the colorant package includes Ag, the glass article can contain less than 100 ppm of halides, including Cl.

[0135] In various aspects, the glass articles described herein may further include ZrO . Without wishing to be bound by theory, it is believed that ZrO may act as a multivalent species that functions as a redox couple to supply oxygen to certain colorants (e.g., Au) during relatively low temperature heat treatment, thereby helping to improve colorant retention. ZrO may also act as an additional colorant, resulting in a colored glass article, which may, for example, be red. In various aspects, the glass article may include ZrO 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. In various aspects, the glass article can include ZrO2 in an amount of 0.01 mol% to 2 mol%, 0.1 mol% to 1.75 mol%, 0.2 mol% to 1.5 mol%, 0.25 mol% to 1.25 mol%, 0.5 mol% to 1 mol%, 0.75 mol% to 1 mol%, or any range or sub-range therebetween.

[0136] In various aspects, the glass compositions described herein and the colored glass articles resulting therefrom may further include Fe2O3, which may help improve colorant retention and / or color standout. Fe2O3 is a multivalent species that acts as a redox couple to supply oxygen to certain colorants (e.g., Au) during relatively low temperature heat treatment, thereby helping to improve colorant retention. Fe2O3 may also act as a colorant, resulting in a colored glass article that may be, for example, pink or red. In various aspects, the glass article may include Fe2O3 in an amount 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. In various aspects, the glass article may include Fe2O3 in an amount ranging 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 sub-range therebetween. In various aspects, the glass article may include Fe2O3 in an amount ranging from 200 ppm (parts per million) or more, from 250 ppm or more, from 300 ppm or more, from 350 ppm or more, from 400 ppm or less, from 1,000 ppm or less, from 600 ppm or less, from 550 ppm or less, from 500 ppm or less, or from 450 ppm or less. In various aspects, the glass article may include Fe2O3 in an amount ranging 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 sub-range therebetween. In various aspects, the glass article can be substantially free or free of Fe2O3.

[0137] In various aspects, the glass compositions described herein and the colored glass products obtained therefrom may also include SnO2, Sb2O3, and / or Bi2O3. Similar to MgO and ZnO, SnO2, Sb2O3, and Bi2O3 can help lower the melting point of the glass composition. Therefore, the inclusion of SnO2, Sb2O3, and / or Bi2O3 in the glass product can lower the melting point and improve the retention of the colorant. In aspects where the colorant package includes Ag, SnO2 can also help reduce the Ag in the glass, thereby forming silver particles in the glass. Without wishing to be bound by theory, in aspects where the colorant package includes Au, it is believed that the addition of SnO2 can also help reduce the Au in the glass, thereby forming gold particles. In aspects where SnO2 and / or Sb2O3 are included, SnO2 and / or Sb2O3 can also serve as a fining agent.

[0138] In various aspects, the glass article may include SnO2 in an amount 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. In various aspects, the glass article may include SnO2 in an amount greater than 0 mol% to 1 mol%, 0.01 mol% to 0.75 mol%, 0.05 mol% to 0.5 mol%, 0.1 mol% to 0.25 mol%, or any range or subrange therebetween. In various aspects, the glass article may be substantially free or free of SnO2.

[0139] In various aspects, the concentration of Sb2O3 in the glass article can 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. In various aspects, the concentration of Sb2O3 in the glass article can be greater than 0 mol% to 1 mol%, 0.01 mol% to 0.75 mol%, 0.05 mol% to 0.5 mol%, 0.1 mol% to 0.25 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free of or free of Sb2O3. In various aspects, the glass article can include Sb2O3 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 sub-range therebetween.

[0140] In various aspects, the concentration of Bi2O3 in the glass article can 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. In various aspects, the concentration of Bi2O3 in the glass article can be greater than 0 mol% to 1 mol%, 0.01 mol% to 0.75 mol%, 0.05 mol% to 0.5 mol%, 0.1 mol% to 0.25 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free of or free of Bi2O3.

[0141] In various aspects, the concentration of SO3 in the glass article can be 0.1 mol% or less, 0.01 mol% or less, or 0.001 mol% or less. In various aspects, the glass article can be substantially free of or free of SO3.

[0142] In various aspects, the glass articles described herein may also include a reduced concentration of PO, or be substantially free of or free of PO. In various aspects that include PO, PO can enhance the ion exchange characteristics of the resulting colored glass article. However, increased concentrations of PO (i.e., greater than 1 mol%) can reduce the retention of one or more colorants in the colorant package. Without wishing to be bound by theory, it is believed that PO may have a higher volatility than other glass network formers, such as SiO, which may result in reduced retention of the colorant in the colorant package. In various aspects, the concentration of PO in the glass article may include 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 various aspects, the concentration of P2O5 in the glass article can include greater than 0 mol% to 1 mol%, 0.1 mol% to 0.75 mol%, 0.25 mol% to 0.5 mol%, or any range or sub-range therebetween. In various aspects, the glass article can be substantially free of or free of P2O5.

[0143] In various aspects, the glass article may include at least one colorant from a colorant package to impart a desired color to the glass article. In various aspects, the colorant package may include at least one of the following: Au, Ag, Cr2O3, transition metal oxides (e.g., CuO, NiO, Co3O4, TiO2, Cr2O3, V2O5), rare earth metal oxides (e.g., CeO2), and / or combinations thereof. In various aspects, the glass article may be 1×10 -6 mol % to 10 mol % of colorant (i.e., the sum of all colorants in the colorant package). In various aspects, the concentration of the colorant package in the glass article can be 1×10 -6% or less, 0.5 mol% or less, 1 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.5 mol% or less, 1 mol% or less, 0.6 mol% or less, 1 mol% or less, 0.7 mol% or less, 0.8 mol% or less, 0.9 mol% or less, 1 mol% or less, 1 mol% or less, 2 mol% or less, 0.1 mol% or less, 0.2 mol% or less, 0.3 mol% or less, 0.4 mol% or less, 0.6 mol% or less, 0.7 mol% or less, 0.8 mol% or less, 0.9 ...5 mol% or less, 0.6 mol% or less, 0.7 mol% or less, 0.8 mol% or less, 0.9 mol% or less, 0.1 mol% or less, 0.2 mol% or less, 0.5 -6 mol% to 10mol%, 1×10 -6 mol% to 9mol%, 1×10 -6 % to 8 mol%, 0.0005 mol% to 7 mol%, 0.0005 mol% to 6 mol%, 0.0005 mol% to 5 mol%, 0.001 mol% to 4 mol%, 0.001 mol% to 3 mol%, 0.001 mol% to 2 mol%, 0.01 mol% to 1.5 mol%, 0.01 mol% to 1 mol%, 0.1 mol% to about 0.5 mol%, or any range or sub-range therebetween. In various aspects, the concentration of the colorant package in the glass article can be 1×10 -6 mol% to 1 mol%, 0.0005 mol% to about 0.5 mol%, 0.001 mol% to 0.25 mol%, 0.01 mol% to 0.1 mol%, or any range or sub-range therebetween.

[0144] In various aspects, the colorant package in the glass composition and the resulting colored glass article can include a colorant to achieve a desired color, the colorant comprising or consisting of a transition metal oxide, a rare earth metal oxide, or a combination thereof. In various aspects, the transition metal oxide and / or rare earth metal oxide can be included in the glass composition as the sole colorant or in combination with other colorants. In various aspects, the multivalent colorant can include Cr2O3, CeO2, Co3O4, CuO, TiO2, NiO, V2O5, or a combination thereof. In other aspects, the multivalent colorant can consist of Cr2O3, CeO2, or a combination thereof. In other aspects, the colorant can also include Co3O4. For example, in aspects utilizing Cr2O3 as the multivalent colorant, a transition metal oxide, such as Co3O4, can be included in the glass composition to modify the color imparted to the glass. As described herein, in various aspects, the glass composition and the resulting colored glass article can be formulated to increase the solubility of Cr2O3, thereby expanding the color gamut achievable by the resulting colored glass article. In various aspects, the transition metal oxide and / or rare earth metal oxide based colorants 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.

[0145] In various aspects, the glass article may include 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 of Cr2O3. In various aspects, the glass article may include greater than 0 mol% to 2 mol%, 0.001 mol% to 1.5 mol%, 0.005 mol% to 1 mol%, 0.01 mol% to 0.05 mol%, 0.05 mol% to 0.1 mol%, or any range or sub-range therebetween. In various aspects, the glass article may include 100 ppm to 10,000 ppm, 100 ppm to 5,000 ppm, 300 ppm to 2,000 ppm, 500 ppm to 1,000 ppm, or any range or sub-range therebetween of Cr2O3.

[0146] In aspects where the colorant package includes Cr2O3 as the colorant, the glass composition and resulting colored glass article are per-alkali (i.e., R2O (mol%) + R ′O (mol%) - Al2O3 (mol%) is 0.5 mol% or more) to increase the solubility of Cr2O3 and avoid the formation of Cr-spinel crystals. However, when the glass composition has an excess of alkali metal after charge balancing Al2O3, the alkali metal can form non-bridging oxygen around SiO2, thereby degrading fracture toughness. Therefore, in various aspects, R2O+R ′ O-Al2O3 may be limited (eg, less than or equal to 6 mol%) to prevent a decrease in fracture toughness.

[0147] In various aspects, the glass article may include NiO + Co3O4 + Cr2O3 + CuO + CeO2 + TiO2 at a concentration 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. In various aspects, the glass articles may include a concentration of NiO + Co3O4 + Cr2O3 + CuO + CeO2 + TiO2 that may range from greater than 0 mol% to 5 mol%, 0.001 mol% to 4 mol%, 0.01 mol% to 3 mol%, 0.02 mol% to 2.5 mol%, 0.1 mol% to 2 mol%, 0.5 mol% to 1.5 mol%, 0.7 mol% to 1 mol%, or any range or sub-range therebetween. In various aspects, the glass compositions and resulting glass articles may include 0 mol% of one or more of: NiO, Co3O4, Cr2O3, CuO, CeO2, V2O5, and / or TiO2.

[0148] In various aspects, the glass article may include NiO + Co3O4 + Cr2O3 + CuO in a concentration of 0.001 mol% to 3 mol%. In various aspects, the glass article may include NiO + Co3O4 + Cr2O3 + CuO in a concentration 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. In various aspects, the glass articles may include NiO + Co3O4 + Cr2O3 + CuO at concentrations of greater than 0 mol% to 3 mol%, 0.001 mol% to 2.5 mol%, 0.01 mol% to 2 mol%, 0.02 mol% to 1.5 mol%, 0.1 mol% to 1 mol%, 0.2 mol% to 0.5 mol%, 0.2 mol% to 0.4 mol%, or any range or sub-range therebetween. In various aspects, the glass compositions and resulting glass articles may include 0 mol% of one or more of NiO, Co3O4, Cr2O3, and / or CuO.

[0149] In various aspects, the glass article may include TiO2 at a concentration 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. In various aspects, the glass article may include TiO2 at a concentration of greater than 0 mol% to 2 mol%, 0.01 mol% to 1.5 mol%, 0.1 mol% to 1 mol%, 0.2 mol% to 0.75 mol%, 0.3 mol% to 0.5 mol%, 0.3 mol% to 0.4 mol%, or any range or sub-range therebetween.

[0150] In various aspects, the glass article may include CeO2 at a concentration 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. In various aspects, the glass article may include CeO2 at a concentration of 0.1 mol% to 2 mol%, 0.2 mol% to 1.5 mol%, 0.2 mol% to 1 mol%, 0.3 mol% to 0.75 mol%, 0.3 mol% to 0.5 mol%, 0.3 mol% to 0.4 mol%, or any range or sub-range therebetween.

[0151] In various aspects, the glass article may include NiO at a concentration 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. In various aspects, the glass article may include NiO at a concentration of greater than 0 mol% to 0.05 mol%, 0.01 mol% to 0.04 mol%, 0.01 mol% to 0.035 mol%, 0.015 mol% to 0.03 mol%, 0.02 mol% to 0.025 mol%, or any range or sub-range therebetween.

[0152] In various aspects, the glass article may include CuO at a concentration 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. In various aspects, the glass article may include CuO at a concentration of greater than 0 mol% to 0.5 mol%, 0.1 mol% to 0.4 mol%, 0.1 mol% to 0.35 mol%, 0.15 mol% to 0.3 mol%, 0.15 mol% to 0.25 mol%, 0.15 mol% to 0.2 mol%, or any range or sub-range therebetween.

[0153] In various aspects, the glass article may include VO at a concentration 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. In various aspects, the glass article may include VO at a concentration of 0.1 mol% to 2 mol%, 0.2 mol% to 1.5 mol%, 0.2 mol% to 1 mol%, 0.3 mol% to 0.75 mol%, 0.3 mol% to 0.5 mol%, 0.3 mol% to 0.4 mol%, or any range or sub-range therebetween.

[0154] In various aspects, the glass article may include Nd2O in a concentration of 3： In various aspects, the glass article may include Nd2O3 in a concentration of greater than 0 mol%, 0.1 mol% or more, 4 mol% or less, 3 mol% or less, 1.5 mol% or less, or 0.5 mol% or less. In various aspects, the glass article may include Nd2O3 in a concentration of greater than 0 mol% to 4 mol%, 0 mol% to 3 mol%, 0.1 mol% to 1.5 mol%, 0.1 mol% to 0.5 mol%, or any range or sub-range therebetween. In various aspects, the glass article may include Er2O3 in one or more of the ranges discussed above in this paragraph with respect to the amount of Nd2O3.

[0155] In various aspects, the glass article may include Co3O4 at a concentration 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. In various aspects, the glass article may include Co3O4 at a concentration of greater than 0 mol% to 0.01 mol% or less, 0.0001 mol% to 0.009 mol% or less, 0.0001 mol% to 0.008 mol%, 0.0001 mol% to 0.007 mol%, 0.0002 mol% to 0.006 mol%, 0.0002 mol% to 0.005 mol%, 0.0005 mol% to 0.004 mol%, 0.0005 mol% to 0.003 mol%, 0.01 mol% to 0.02 mol%, or any range or sub-range therebetween.

[0156] In various aspects, the glass articles may include a significant amount of Cr2O3, the amount being greater than 0 mol%, 0.01 mol% or more, 0.015 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. In various aspects, the glass articles may include a significant amount of Cr2O3, the amount being greater than 0 mol% to 0.05 mol%, greater than 0 mol% to 0.04 mol%, 0.01 mol% to 0.035 mol%, 0.01 mol% to 0.03 mol%, 0.015 mol% to 0.025 mol%, 0.015 mol% to 0.02 mol%, or any range or sub-range therebetween.

[0157] In various aspects, the glass article may include at least one of: 0.001 mol% or more NiO + Co3O4 + Cr2O3 + CuO (e.g., 0.001 mol% to 3 mol%, or any range of NiO + Co3O4 + Cr2O3 + CuO described herein); 0.1 mol% or more CeO2 (e.g., 0.1 mol% to 1.5 mol% or any range of CeO2 described herein); and / or 0.1 mol% or more TiO2 (e.g., 0.1 mol% to 2 mol% or any range of TiO2 described herein).

[0158] In various aspects, the glass compositions and resulting colored glass articles described herein may further include impurity materials such as MnO, MoO3, WO3, Y2O3, CdO, As2O3, sulfur-containing compounds (e.g., sulfates), halogens, or combinations thereof. In various aspects, the glass compositions and resulting colored glass articles may be substantially free of or free of impurity materials such as MnO, MoO3, WO3, Y2O3, CdO, As2O3, sulfur-containing compounds (e.g., sulfates), halogens, or combinations thereof.

[0159] In various aspects, lowering the melting point of the glass article can help improve colorant retention because the glass composition can melt at a relatively low temperature and colorant evaporation can be reduced. Therefore, the glass articles described herein can optionally include MgO and / or ZnO, which can help lower the melting point of the glass article. B2O3, Li2O, and Na2O also lower the melting point of the glass article. As described herein, other components can be added to the glass article to lower its melting point, such as SnO2, Sb2O3, and Bi2O3. In various aspects, the glass article can have a melting point of 1300°C or higher, 1325°C or higher, 1350°C or higher, 1375°C or higher, 1400°C or higher, 1550°C or lower, 1525°C or lower, 1500°C or lower, 1475°C or lower, or 1450°C or lower. In various aspects, the glass article may have a melting point of 1300° C. to 1550° C., 1325° C. to 1525° C., 1350° C. to 1500° C., 1375° C. to 1475° C., 1400° C. to 1450° C., or any range or sub-range therebetween. In various aspects, the glass article may have a liquidus temperature of 1000° C. or greater, 1050° C. or greater, 1100° C. or greater, 1400° C. or less, 1350° C. or less, or 1300° C. or less. In various aspects, the glass article may have a liquidus temperature of 1000° C. to 1400° C., 1050° C. to 1350° C., 1100° C. to 1300° C., or any range or sub-range therebetween.

[0160] In various aspects, the viscosity of the glass articles can be adjusted to prevent devitrification of the glass composition and the formation of colorant particles (e.g., Au particles) during melting and forming. The formation of colorant particles during melting and forming can limit the color range that can be achieved through heat treatment. In various aspects, to achieve the desired viscosity and thereby prevent the formation of colorant particles prior to melting, the glass articles described herein can satisfy the following relationship: 5.72*Al2O3 (mol%) - 21.4*ZnO (mol%) - 2.5*P2O5 (mol%) - 35*Li2O (mol%) - 16.6*B2O3 (mol%) - 20.5*MgO (mol%) - 23.3*Na2O (mol%) - 27.9*SrO (mol%) - 18.5*KO (mol%) - 26.3*CaO (mol%) (greater than -609 mol%). In various aspects, the glass articles described herein may satisfy the following relationship: 5.72*Al2O3 (mol%) -21.4*ZnO (mol%) -2.5*P2O5 (mol%) -35*Li2O (mol%) -16.6*B2O3 (mol%) -20.5*MgO (mol%) -23.3*Na2O (mol%) -27.9*SrO (mol%) -18.5*K2O (mol%) -26.3*CaO (mol%) 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%. In various aspects, the glass compositions and resulting glass articles described herein can satisfy the following relationship: 5.72*Al2O3 (mol%) - 21.4*ZnO (mol%) - 2.5*P2O5 (mol%) - 35*Li2O (mol%) - 16.6*B2O3 (mol%) - 20.5*MgO (mol%) - 23.3*Na2O (mol%) - 27.9*SrO (mol%) - 18.5*KO (mol%) - 26.3*CaO (mol%) less than or equal to -400 mol%, less than or equal to -425 mol%, or even less than or equal to -450 mol%.In various aspects, the glass articles described herein may satisfy the following relationship: 5.72*Al2O3 (mol%) -21.4*ZnO (mol%) -2.5*P2O5 (mol%) -35*Li2O (mol%) -16.6*B2O3 (mol%) -20.5*MgO (mol%) -23.3*Na2O (mol%) -27.9*SrO (mol%) -18.5*KO (mol%) -26.3*CaO (mol%) is -609mol% to -400mol%, -575mol% to -425mol%, -550mol% to -450mol%, -525mol% to -450mol%, or any range or sub-range therebetween.

[0161] In various aspects, the glass article may include 50 mol% to 80 mol% SiO2; 7 mol% to 25 mol% Al2O3; 1 mol% to 15 mol% B2O3; 5 mol% to 20 mol% Li2O; 0.5 mol% to 15 mol% Na2O; greater than 0 mol% to 1 mol% K2O; and 1×10 -6 mol% to 1mol% Au, wherein: R2O-Al2O3 is -5mol% to 7mol%. In various aspects, the glass article may include 50mol% to 70mol% SiO2; 10mol% to 17.5mol% Al2O3; 3mol% to 10mol% B2O3; 8.8mol% to 14mol% Li2O; 1.5mol% to 8mol% Na2O; and 0mol% to 2mol% Cr2O3, wherein: R2O+R ′ O-Al2O3 is 0.5 mol% to 6 mol%, and Al2O3+MgO+ZnO is 12 mol% to 22 mol%.

[0162] In various aspects, the glass article may include 50 mol% to 70 mol% SiO2; 10 mol% to 20 mol% Al2O3; 4 mol% to 10 mol% B2O3; 7 mol% to 17 mol% Li2O; 1 mol% to 9 mol% Na2O; 0.01 mol% to 1 mol% SnO2; and 0.01 mol% to 5 mol% Ag, wherein R2O-Al2O3 is 0.2 mol% to 5.00 mol%. In various aspects, the glass article may include 50 mol% to 70 mol% SiO2; 10 mol% to 20 mol% Al2O3; 1 mol% to 10 mol% B2O3; 7 mol% to 14 mol% Li2O; 0.01 mol% to 8 mol% Na2O; 0.01 mol% to 1 mol% KO; 0 mol% to 7 mol% CaO; and 0 mol% to 8 mol% MgO, wherein Li2O+KO+Na2O+CaO+MgO+ZnO is 25 mol% or more, and at least one of the following: CuO+NiO+Co3O4+Cr2O3 is 0.001 mol% or more, CeO2 is 0.1 mol% or more, and / or TiO2 is 0.1 mol% or more.

[0163] Throughout this disclosure, fracture toughness (K IC ) represents the ability of a glass composition to resist fracture. Fracture toughness is measured on a non-strengthened glass article, for example, the K ICThe fracture toughness test method described herein is not applicable to glass that has undergone 10X treatment. Therefore, when referring to the fracture toughness of an ion-exchanged article, it means the fracture toughness of an union-exchanged article having the same composition and microstructure (if any) as the center (i.e., a point at least 0.5t from each surface of the article or substrate, where t is the thickness of the article or substrate) of the ion-exchanged article (corresponding to the portion of the ion-exchanged article that is least affected by the ion-exchange process and is therefore similar in composition and microstructure to glass that has not undergone ion exchange). Fracture toughness is measured by the chevron notched short bar method. The CNSB method is disclosed in Reddy, KPR et al., “Fracture Toughness Measurement of Glass and Ceramic Materials Using Chevron-Notched Specimens”, Journal of the American Ceramic Society (J.Am.Ceram.Soc.), 71[6], C-310-C-313 (1988), but Y* m Calculated using Equation 5 from Bubsey, RT et al., "Closed-Form Expressions for Crack-Mouth Displacement and Stress Intensity Factors for Chevron-Notched Short Bar and Short Rod Specimens Based on Experimental Compliance Measurements," NASA Technical Memorandum 83796, pp. 1-30 (October 1992). Unless otherwise noted, all fracture toughness values are measured using the V-notched short bar (CNSB) method.

[0164] In various aspects, glass articles formed from the glass compositions described herein can have increased fracture toughness, making the colored glass articles more resistant to damage. In various aspects, the glass articles can have a strength of 0.7 MPa·m 2 before ion exchange as measured by the CNSB method. 1 / 2 or higher, 0.8MPa·m 1 / 2 or higher, 0.9MPa·m 1 / 2 or higher, or 1.0 MPa·m1 / 2 or higher K IC Fracture toughness. In various aspects, the glass articles 350 and / or 511 formed from the glass compositions described herein can have increased fracture toughness, making the colored glass articles more resistant to damage. In various aspects, the glass articles 350 and / or 511 can have a fracture toughness of 0.6 MPa·m 2 before ion exchange, as measured by the DCB method. 1 / 2 or higher, 0.7MPa·m 1 / 2 or higher, 0.8MPa·m 1 / 2 or higher, 0.9MPa·m 1 / 2 or higher, 1.0MPa·m 1 / 2 or higher K IC Fracture toughness.

[0165] Throughout this disclosure, the dielectric constant of a glass article is measured using a split postdielectric resonator (SPDR) at a frequency of 10 GHz. The dielectric constant is measured on a sample 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. In various aspects, the dielectric constant Dk of the glass article 350 and / or 511 at 10 GHz is 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6 or less, 5.6 or greater, 5.7 or greater, 5.8 or greater, 5.9 or greater, or 6.0 or greater. In various aspects, the dielectric constant Dk of the glass article 350 and / or 511 at 10 GHz ranges from 5.6 to 6.4, 5.7 to 6.3, 5.8 to 6.2, 5.9 to 6.1, 5.9 to 6, or any range or sub-range therebetween. In various aspects, the dielectric constant at a frequency of 10 GHz to 60 GHz (e.g., 26 GHz to 40 GHz) can be within one or more of the above-mentioned ranges. Without wishing to be bound by theory, it is believed that the dielectric constant of the glass article measured at 10 GHz is close to the dielectric constant at a frequency of 10 GHz to 60 GHz. Therefore, the dielectric constant reported for the colored glass article at a frequency of 10 GHz is close to the dielectric constant of the colored glass article at a frequency within the range of 10 GHz to 60 GHz (inclusive).

[0166] In various aspects, although not shown, the primary glass housing may further include a coating disposed, for example, on the first major surface of the glass article. For example, the coating may 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 polymer hard coating, or a combination thereof. The scratch-resistant coating may include an oxynitride, such as aluminum oxynitride or silicon oxynitride, having a thickness of approximately 500 microns or greater. In these aspects, the abrasion-resistant layer may include the same material as the scratch-resistant layer. In various aspects, the low-friction coating may include a highly fluorinated silane coupling agent, such as an alkylfluorosilane with oxymethyl groups pendant on the silicon atoms. In these aspects, the easy-to-clean coating may include the same material as the low-friction coating. In other aspects, the easy-to-clean coating may include protonatable groups, such as amines, such as alkylaminosilanes with oxymethyl groups pendant on the silicon atoms. In these aspects, the oleophobic coating may include the same material as the easy-to-clean coating. In various aspects, the diamond-like coating may include carbon and may be produced by applying a high voltage potential in the presence of a hydrocarbon plasma.

[0167] In other aspects, the polymer hard coat may include one or more of ethylene-acid copolymers, polyurethane polymers, acrylate resins, and mercaptoester resins. Exemplary aspects of ethylene-acid copolymers include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-acrylic acid-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). Exemplary aspects of polyurethane polymers include water-based modified polyurethane dispersions (e.g., ). Exemplary aspects of UV-curable acrylate resins include acrylate resins (e.g., resins), cyanoacrylate adhesives (such as those manufactured by Krayden UV620) and UV radical acrylic resins (UV radical acrylic resins) (e.g., Ultrabond windshield repair resin, such as Ultrabond (45CPS)). Example aspects of mercapto ester resins include mercapto ester triallyl isocyanurate (e.g., Norland Optical Adhesive NOA61). In other aspects, the polymer hard coating may include ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers, which can be ionized by neutralizing the carboxylic acid residues, typically with alkali metal ions (e.g., sodium and potassium) and zinc, to form ionomer resins. Such ethylene-acrylic acid and ethylene-methacrylic acid ionomers can be dispersed in water and applied to a substrate to form an ionomer coating. Alternatively, such acid copolymers can be neutralized with ammonia, which, after application and drying, releases the ammonia and reforms the acid copolymer as a coating. By providing a coating comprising a polymer coating, a foldable device can achieve low energy fracture. In other aspects, the polymer hard coating may include an optically transparent hard coating. The materials suitable for optically transparent polymer hard coats include, but are not limited to, cured acrylate resin materials, inorganic-organic hybrid polymer materials, aliphatic or aromatic six-functional urethane acrylates, silicone hybrid materials, and nanocomposite materials, such as epoxy resins and urethane materials with nanosilicates. As used herein, "inorganic-organic hybrid polymer materials" refer to polymer materials comprising monomers containing inorganic and organic components. Inorganic-organic hybrid polymers are obtained by polymerization reactions between monomers having inorganic and organic groups. Inorganic-organic hybrid polymers are not nanocomposites comprising independent inorganic and organic components or phases, such as inorganic particles dispersed in an organic matrix. More specifically, the materials suitable for optically transparent polymer (OTP) hard coats include, but are not limited to, polyimides, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), organic polymer materials, inorganic-organic hybrid polymer materials, and aliphatic or aromatic six-functional urethane acrylates. In various aspects, the OTP hard coating can be essentially composed of an organic polymer material, an inorganic-organic hybrid polymer material, or an aliphatic or aromatic hexafunctional urethane acrylate. In various aspects, the OTP hard coating can be composed of a polyimide, an organic polymer material, an inorganic-organic hybrid polymer material, or an aliphatic or aromatic hexafunctional urethane acrylate. In various aspects, the OTP hard coating can include a nanocomposite material. In various aspects, the OTP hard coating can include a nanosilicate and at least one of an epoxy resin or a urethane material. Compositions suitable for such OTP hard coatings are described in U.S. Patent Publication No. 2015 / 0110990, which is incorporated herein by reference in its entirety. As used herein, "organic polymer material" means a polymer material comprising monomers containing only organic components.In various aspects, the OTP hard coating may include an organic polymer material manufactured by Gunze Co., Ltd. and having a hardness of 9H, such as Gunze's "High Durable Transparent Film". As used herein, "inorganic-organic hybrid polymer material" refers to a polymer material comprising monomers containing inorganic and organic components. Inorganic-organic hybrid polymers are obtained by polymerization reactions between monomers having inorganic groups and organic groups. Inorganic-organic hybrid polymers are not nanocomposites comprising independent inorganic and organic components or phases, such as inorganic particles dispersed in an organic matrix. In various aspects, the inorganic-organic hybrid polymer material may include polymerized monomers containing inorganic silicon-like groups, such as silsesquioxane polymers. The silsesquioxane polymer may be, for example, an alkyl silsesquioxane, an aryl silsesquioxane, or an arylalkyl silsesquioxane having the following chemical structure: (RSiO. 1.5 ) n , wherein R is an organic group such as, but not limited to, methyl or phenyl. In various aspects, the OTP hard coating may include a combination of a silsesquioxane polymer and an organic matrix, such as SILPLUS manufactured by Nippon Steel Chemical Co., Ltd. In various aspects, the OTP hard coating may include 90% to 95% by weight of an aromatic hexafunctional urethane acrylate, such as PU662NT (aromatic hexafunctional polyurethane acrylate) manufactured by Miwon Specialty Chemical; and 10% to 5% by weight of a photoinitiator (such as Darocur 1173 manufactured by Ciba Specialty Chemicals), having a hardness of 8H or greater. In various aspects, the OTP hard coating composed of an aliphatic or aromatic hexafunctional urethane acrylate can be formed as a freestanding 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.

[0168] In various aspects, the glass article 350 and / or 511 may include one or more compressive stress regions. In various aspects, the compressive stress region may be generated by chemical strengthening. Chemical strengthening may include ion exchange, wherein ions in the surface layer are replaced 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 provide good impact resistance, good puncture resistance, and / or high bending strength. The compressive stress region may extend into a portion of the glass article, reaching a depth referred to as the depth of compression (DOC). As used herein, depth of compression refers to the depth at which the stress in the chemically strengthened glass article described herein changes from compressive stress to tensile stress. Depending on the ion exchange treatment and the thickness of the glass article being measured, the depth of compression can be measured using a surface stress meter or a scattered light polarizer (SCALP, where the values reported here are obtained using a SCALP-5 manufactured by Glasstress, Estonia). In cases where the stress in the glass article is generated by exchanging potassium ions into the substrate, the depth of compression is measured using a surface stress meter, such as the FSM-6000 (Orihara Industrial Co., Ltd., Japan). Unless otherwise stated, compressive stress (including surface CS) is measured by a surface stress meter (FSM) using a commercially available instrument manufactured by Orihara Corporation (e.g., FSM-6000). Surface stress measurements rely on accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. Unless otherwise stated, SOC is measured according to Procedure C (Glass Disc Method) described in 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. When stress is generated by exchanging sodium ions into the glass article and the thickness of the glass article exceeds about 400 μm, SCALP is used to measure the depth of compression and the central tension (CT). When stress in the glass article is generated by exchanging both potassium and sodium ions into the glass article and the thickness of the measured article exceeds about 400 μm, SCALP is used to measure the depth of compression and the CT. Without wishing to be bound by theory, the depth of exchange for sodium may indicate the depth of compression, while the depth of exchange for potassium ions may indicate a change in the magnitude of compressive stress (rather than a change in stress from compression to tension).A graphical representation of the stress distribution can also be derived using a refractive near-field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled "Systems and methods formeasuring a profile characteristic of a glass sample," which is incorporated herein by reference in its entirety) method. When the RNF method is utilized to derive the graphical representation of the stress distribution, the maximum central tension value provided by SCALP is utilized in the RNF method. The graphical representation of the stress distribution derived by RNF is force balanced and calibrated to the maximum central tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) means the depth in a glass article at which ion (e.g., sodium, potassium) exchange occurs. Throughout this disclosure, DOL is measured according to ASTM C-1422. Without wishing to be bound by theory, the DOL is typically greater than or equal to the corresponding DOC. Throughout this disclosure, when the maximum central tension cannot be measured directly by SCALP (for example, when the thickness of the measured article is less than about 400 μm), the maximum central tension can be approximated by dividing the product of the maximum compressive stress and the compression depth by the difference between the thickness of the glass article and twice the compression depth, where the compressive stress and the compression depth are measured by FSM.

[0169] In various aspects, the glass article 350 and / or 511 can include a first compressive stress region extending from the first major surface 332 and / or 513 to a first compression depth. In various aspects, the glass article 350 and / or 511 can include a second compressive stress region extending from the second major surface 330 and / or 515 to a second compression depth. In various aspects, the first compression depth and / or the second compression depth, expressed as a percentage of the thickness 337 and / 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. In various aspects, the first compression depth and / or the second compression depth, expressed as a percentage of the thickness 337 and / or 517, can range from about 5% to about 30%, about 10% to about 25%, about 10% to about 22%, about 12% to about 20%, about 12% to about 17%, about 15% to about 17%, or any range or sub-range therebetween. In various aspects, the first compression depth and / or the second compression depth can be about 10 μm or more, about 20 μm or more, about 30 μm or more, about 40 μm or more, about 50 μm or more, about 60 μm or more, about 500 μm or less, about 200 μm or less, about 150 μm or less, about 100 μm or less, about 90 μm or less, or about 80 μm or less. In various aspects, the first compression depth and / or the second compression depth can range from about 10 μm to about 500 μm, about 20 μm to about 200 μm, about 30 μm to about 150 μm, about 40 μm to about 100 μm, about 50 to about 90 μm, about 60 μm to about 80 μm, or any range or sub-range therebetween.

[0170] In various aspects, the glass article 350 and / or 511 can include a first depth of layer having one or more alkali metal ions associated with a first compressive stress region, and / or the glass article 350 and / or 511 can include a second depth of layer having one or more alkali metal ions associated with a second compressive stress region and a second compressive depth. As used herein, the one or more alkali metal ions in the depth of the layer having one or more alkali metal ions can include sodium, potassium, rubidium, cesium, and / or francium. In various aspects, the one or more alkali metal ions in the first depth of the layer having one or more alkali metal ions and / or the one or more alkali metal ions in the second depth of the layer having one or more alkali metal ions include potassium. In various aspects, the first depth of the layer and / or the second depth of the layer, expressed 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. In various aspects, the first depth of the layer and / or the second depth of the layer, expressed as a percentage of the thickness 517, can 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 sub-range therebetween. In various aspects, the first depth of the layer having one or more alkali metal ions and / or the second depth of the layer having one or more alkali metal ions can be about 1 μm or greater, about 10 μm or greater, about 15 μm or greater, about 20 μm or greater, about 25 μm or greater, about 30 μm or greater, about 200 μm or less, about 150 μm or less, about 100 μm or less, about 60 μm or less, about 45 μm or less, about 30 μm or less, or about 20 μm or less. In various aspects, the first depth of the layer having one or more alkali metal ions and / or the second depth of the layer having one or more alkali metal ions can range from about 1 μm to about 200 μm, about 1 μm to about 150 μm, about 10 μm to about 100 μm, about 15 μm to about 600 μm, about 20 μm to about 45 μm, about 20 μm to about 30 μm, or any range or sub-range therebetween.

[0171] In various aspects, the first compressive stress region can include a maximum first compressive stress, and / or the second compressive stress region can include a maximum second compressive stress. In other aspects, the maximum first compressive stress and / or the maximum second compressive stress can be about 100 MPa (megapascals) or greater, about 300 MPa or greater, 400 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less. In other aspects, the maximum first compressive stress and / or the maximum second compressive stress can range from about 100 MPa to about 1,500 MPa, about 300 MPa to about 1,200 MPa, about 400 MPa to about 1,000 MPa, about 500 MPa to about 1,000 MPa, about 600 MPa to about 900 MPa, about 700 MPa to about 800 MPa, or any range or sub-range therebetween.

[0172] In various aspects, the glass article 350 and / or 511 can include a tensile stress region. In other aspects, the tensile stress region can be disposed between the first compressive stress region and the second compressive stress region. In other aspects, the tensile stress region can include a maximum tensile stress. In still other aspects, the maximum tensile stress can be about 10 MPa or greater, about 30 MPa or greater, about 50 MPa or greater, about 60 MPa or greater, about 80 MPa or greater, 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. In still other aspects, the maximum tensile stress can range from about 10 MPa to about 250 MPa, about 30 MPa to about 200 MPa, about 50 MPa to about 100 MPa, about 60 MPa to about 80 MPa, or any range or sub-range therebetween.

[0173] In various aspects, the glass article 350 and / or 511 has an average transmittance over a wavelength range of 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. In various aspects, the glass article 350 and / or 511 has an average transmittance over the wavelength range of 400 nm to 750 nm of 10% to 92%, 15% to 92%, 20% to 91%, 20% to 91%, 25% to 91%, 30% to 90%, 40% to 90%, 60% to 89%, 70% to 88%, 75% to 87%, 80% to 86%, 82% to 85%, or any range or sub-range therebetween.

[0174] In various aspects, the glass article 350 and / or 511 can exhibit a color corresponding to at least one 10 nm band having a transmittance lower than the average transmittance within the visible spectrum (e.g., 380 nm to 750 nm). In various aspects, the glass article 350 and / or 511 can exhibit a total transmittance of 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 for at least one 10 nm band within the wavelength range of 380 nm to 750 nm. In various aspects, the glass articles 350 and / or 511 can exhibit a total transmittance in at least one 10 nm band within the wavelength range of 380 nm to 750 nm in a range of 3% to 80%, 5% to 78%, 8% to 75%, 10% to 72%, 20% to 70%, 40% to 68%, 50% to 65%, or any range or sub-range therebetween.

[0175] In various aspects, the glass articles 350 and / or 511 can have a CIE L* value of 50 or greater, 70 or greater, 75 or greater, 85 or greater, 90 or greater, 96.5 or less, 96 or less, 95 or less, 94 or less, 93 or less, or 92 or less. In various aspects, the glass articles 350 and / or 511 can have a CIE L* value of 50 to 96.5, 70 to 96, 75 to 95, 75 to 94, 85 to 93, 90 to 92, or any range or sub-range therebetween. Providing a CIE L* value of 50 to 96.5 can provide the glass articles with an aesthetically pleasing bright color. Without wishing to be bound by theory, it is believed that glass having a CIE L* value range of 50 to 96.5 CIELAB color coordinates is transparent, rather than opaque, to visible wavelengths (i.e., wavelengths of light from 380 nm to 750 nm, inclusive), while still providing a noticeable color. Glass articles having a CIE L* value greater than 96.5 may appear colorless.

[0176] In various aspects, the glass article 350 and / or 511 may comprise an absolute value of a CIE a* value (i.e., |a*|) of 0.3 or greater, 0.5 or greater, 0.8 or greater, 1 or greater, 3 or greater, 5 or greater, 10 or greater, 15 or greater, 18 or greater, 20 or greater, 25 or greater, or 30 or greater. In various aspects, the CIE a* value can be about -35 or greater, -20 or greater, -18 or greater, -15 or greater, -10 or greater, -5 or greater, -3 or greater, -1 or greater, 0.3 or greater, 0.5 or greater, 0.8 or greater, 1 or greater, 5 or greater, 8 or greater, 10 or greater, 18 or greater, 20 or greater, 25 or greater, 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 greater, -0.5 or greater, -0.8 or greater, -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. In various aspects, the CIE a* values (excluding the value of -0.3 to 0.3) can range from about -35 to 65, -20 to 40, -18 to 25, -15 to 20, -10 to 18, -5 to 10, -3 to 5, -1 to 3, -0.8 to 1, or any range or subrange therebetween. For example, the CIE a* values (excluding the value of -0.3 to 0.3) can range from -35 to 60, -20 to 60, -10 to 25, -5 to 25, or any range or subrange therebetween. Alternatively, the CIE a* values can range from -35 to -0.3, -18 to -0.3, -15 to -0.3, -10 to -0.3, -8 to -0.5, -5 to -1, or any range or subrange therebetween. Alternatively, the CIE a* value can range from 0.3 to 65, 0.3 to 25, 0.3 to 18, 0.3 to 10, 0.5 to 8, 1 to 5, or any range or sub-range therebetween. In various aspects, the CIE a* value can range from about -3 or less, for example, from about -35 to about -3, from about -20 to about -3, from about -18 to about -3, from about -15 to about -3, from about -10 to about -5, or any range or sub-range therebetween.

[0177] In various aspects, the glass article 350 and / or 511 may comprise an absolute CIE b* value (i.e., |b*|) of 0.2 or greater, 0.3 or greater, 0.5 or greater, 1 or greater, 3 or greater, 5 or greater, 8 or greater, 10 or greater, 20 or greater, 50 or greater, 70 or greater, or 80 or greater. In various aspects, the CIE b* value can be -90 or greater, -85 or greater, -75 or greater, -50 or greater, -35 or greater, -20 or greater, -5 or greater, -1 or greater, 0.2 or greater, 0.3 or greater, 0.5 or greater, 1 or greater, 3 or greater, 5 or greater, 8 or greater, 10 or greater, 20 or greater, 50 or greater, 70 or greater, 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. In various aspects, the CIE b* values (excluding -0.2 to 0.2) can range from -90 to 120, -85 to 75, -50 to 50, -35 to 35, -20 to 20, -5 to 8, -1 to 5, 0.2 to 3, 0.3 to 1, or any range or subrange therebetween. For example, the CIE b* values can range from -20 to 5, -10 to 5, -5 to 5, -5 to 3, -5 to 1, -5 to -0.2, -3 to -0.3, -1 to -0.5, or any range or subrange therebetween. Alternatively, the CIE b* values can range from 0.2 to 90, 0.5 to 82, 1 to 75, 1 to 20, 1 to 5, or any range or subrange therebetween. Alternatively, the CIE b* value can range from -90 to -0.2, -85 to -0.5, -20 to -1, -10 to -1, -1 to -5, or any range or sub-range therebetween. In various aspects, the CIE b* value can range from about 5 or greater, for example, from about 5 to about 120, from about 5 to about 90, from about 5 to about 75, from about 5 to about 50, from about 5 to about 35, from about 5 to about 25, from about 5 to about 20, from about 5 to about 8, or any range or sub-range therebetween.

[0178] As used herein, the "molar ratio" of a polyvalent colorant in a glass article refers to the amount of the reduced form of the polyvalent colorant divided by the total amount of the polyvalent colorant (i.e., the sum of the amount of the reduced form of the polyvalent colorant and the sum of the amount of the oxidized form of the polyvalent colorant). As used herein, the oxidized form has a higher oxidation state, corresponding to fewer electrons than the reduced form. For example, chromium can be Cr 3+ and Cr 6+ There are Cr 6+ is in oxidized form and Cr 3+is in a reduced form. Additionally, as discussed above, as used herein, a polyvalent colorant comprises at least two oxidation states, wherein the oxidation state of the colorant is non-zero valent and two or more of the at least two oxidation states exhibit color as measured by absorbance at 400 nm to 750 nm or CIE a* and / or b* values. The molar ratio can be determined by X-ray photoelectron spectroscopy (XPS) or by correlation of transmittance or absorption spectra with known reference samples.

[0179] In various aspects, the molar ratio of the multivalent colorant in the glass article can be about 0.1 or greater, about 0.2 or greater, about 0.3 or greater, about 0.4 or greater, about 0.5 or greater, about 0.55 or greater, about 0.6 or greater, about 0.7 or greater, about 0.9 or less, about 0.8 or less, about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.5 or less, or about 0.4 or less. In various aspects, the molar ratio of the multivalent colorant in the glass article can range from about 0.1 to about 0.9, about 0.2 to about 0.9, about 0.3 to about 0.9, about 0.4 to about 0.9, about 0.5 to about 0.9, about 0.55 to about 0.8, about 0.6 to about 0.75, about 0.6 to about 0.7, about 0.6 to about 0.65, or any range or sub-range therebetween. Alternatively, in various aspects, the molar ratio of the multivalent colorant can range from about 0.3 to about 0.9, from about 0.4 to about 0.8, from about 0.5 to about 0.75, from about 0.5 to about 0.7, from about 0.5 to about 0.65, from about 0.5 to about 0.6, or any range or sub-range therebetween. Controlling the molar ratio of the multivalent colorant enables the glass article to reliably produce a predetermined color (e.g., CIE color coordinates). Controlling the molar ratio of the multivalent colorant can increase the color gamut and / or resolution of the color obtained from a predetermined colorant package containing the multivalent colorant.

[0180] Aspects of the method of manufacturing the glass article and / or the primary glass housing according to aspects of the present disclosure will be referred to Figure 6 The flowchart and Figure 7 The example method steps illustrated in FIG.

[0181] In a first step 601 of the method of the present disclosure, the method may begin by obtaining raw materials for glass products and / or unglazed glass products, which may be obtained, for example, by purchasing or otherwise acquiring the raw materials.

[0182] After step 601, the method may proceed to step 603, which includes melting the raw materials together to form a glass article. The precursor material includes at least one multivalent colorant. The amount of the raw materials (e.g., mol %, and / or wt % calculated as oxide) may be within one or more of the ranges discussed above with respect to the composition of the glass article. In various aspects, one or more raw materials may change the molar ratio of the multivalent colorant in the precursor material to obtain a molar ratio of the multivalent colorant in the glass article. For example, the precursor material may include an iron source (e.g., Fe2O3), a zinc source (e.g., ZnO), and / or an antimony source (e.g., Sb2O3), which may be configured to increase the redox ratio of the multivalent colorant. In various aspects, the precursor material may contain 0.02 wt % or more of an iron source, a zinc source, or a combination thereof. In other aspects, the amount of iron in the precursor material may be within one or more of the ranges discussed above with respect to the amount of iron (e.g., Fe2O3) in the glass article. In other aspects, the amount of iron (e.g., Fe2O3) in the precursor material can be about 200 ppm or more, about 250 ppm or more, about 300 ppm or more, about 350 ppm or more, about 400 ppm or more, about 600 ppm or more, about 800 ppm or more, about 1,000 ppm or more, about 1,500 ppm or less, about 1,300 ppm or less, 1,000 ppm or less, about 800 ppm or less, about 600 ppm or less, about 550 ppm or less, about 500 ppm or less, about 450 ppm or less, or about 400 ppm or less. In other aspects, the amount of iron (e.g., Fe2O3) in the precursor material can range from about 200 ppm to about 1,500 ppm, from about 250 ppm to about 1,300 ppm, from about 300 ppm to about 1,300 ppm, from about 300 ppm to about 1,000 ppm, from about 350 ppm to about 800 ppm, from about 350 ppm to about 600 ppm, from about 400 ppm to about 550 ppm or less, from about 400 ppm to about 500 ppm, or any range or sub-range therebetween. In other aspects, the amount of zinc (e.g., ZnO) in the precursor material can be within one or more of the ranges discussed above for the amount of zinc (e.g., ZnO) in the glass article. In other aspects, the amount of zinc (e.g., ZnO) in the precursor material can be about 0.2 wt % or more, about 0.25 wt % or more, about 0.4 wt % or more, about 0.5 wt % or more, about 0.6 wt % or less, about 1.5 wt % or less, about 1 wt % or less, about 0.8 wt % or less, about 0.7 wt % or less, or about 0.5 wt % or less.In other aspects, the amount of zinc (e.g., ZnO) in the precursor material can range from about 0.2 wt% to about 1.5 wt%, about 0.25 wt% to about 1 wt%, about 0.4 wt% to about 0.8 wt%, about 0.5 wt% to about 0.7 wt%, or any range or sub-range therebetween. In various aspects, the amount of antimony (e.g., Sb2O3) in the precursor material can be within one or more of the ranges discussed above with respect to the amount of antimony (e.g., Sb2O3) in the glass article. In various aspects, the amount of antimony (e.g., Sb2O3) in the precursor material can be about 0.005 wt% or more, about 0.01 wt% or more, about 0.02 wt% or more, about 0.05 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 1 wt% or less, about 0.5 wt% or less, about 0.4 wt% or less, about 0.3 wt% or less, about 0.2 wt% or less, or about 0.1 wt% or less. In various aspects, the amount of antimony (e.g., Sb2O3) in the glass article can range from about 0.005 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, about 0.02 wt% to about 0.4 wt%, about 0.05 wt% to about 0.3 wt%, about 0.1 wt% to about 0.2 wt%, or any range or sub-range therebetween.

[0183] In various aspects, the precursor material melted together in step 603 may include a component that volatilizes during step 603 but can change the molar ratio of the polyvalent colorant. In other aspects, the precursor material may include a sulfate source, a carbon source, a nitrate source, or a combination thereof. For example, the carbon source may be graphite, charcoal, or carbon black; the nitrate source may be an alkali metal nitrate (e.g., NaNO3, KNO3); and / or the sulfate source may be an alkali metal sulfate (e.g., Na2SO4, K2SO4). In other aspects, the amount of sulfate source in the precursor material may be about 0.01% by weight or more, about 0.02% by weight or more, about 0.05% by weight or more, about 0.1% by weight or more, about 0.15% by weight or more, about 0.2% by weight or more, about 1% by weight or less, about 0.5% by weight or less, about 0.3% by weight or less, about 0.25% by weight or less, or about 0.2% by weight or less. In other aspects, the amount of the sulfate source in the precursor material can range from about 0.01% to about 1% by weight, from about 0.02% to about 1% by weight, from about 0.05% to about 0.5% by weight, from about 0.1% to about 0.3% by weight, from about 0.15% to about 0.25% by weight, from about 0.2% to about 0.25% by weight, or any range or subrange therebetween. In other aspects, the amount of the carbon source in the precursor material can range from about 0.001% by weight or more, from about 0.004% by weight or more, from about 0.006% by weight or more, from about 0.01% by weight or more, from about 0.02% by weight or more, from about 0.1% by weight or less, from about 0.05% by weight or less, from about 0.04% by weight or less, from about 0.03% by weight or less, from about 0.02% by weight or less, or from about 0.01% by weight or less. In other aspects, the amount of the carbon source in the precursor material can range from about 0.001% to about 0.1% by weight, about 0.004% to about 0.05% by weight, about 0.006% to about 0.04% by weight, about 0.01% to about 0.03% by weight, or any range or subrange therebetween. In other aspects, the amount of the nitrate source in the precursor material can be about 0.05% by weight or more, about 0.1% by weight or more, about 0.2% by weight or more, about 0.3% by weight or more, about 0.5% by weight or more, about 1% by weight or more, about 5% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.8% by weight or less, or about 0.5% by weight or less. In other aspects, the amount of nitrate source in the precursor material can range from about 0.05 wt % to about 5 wt %, about 0.1 wt % to about 3 wt %, about 0.2 wt % to about 2 wt %, about 0.3 wt % to about 1 wt %, about 0.4 wt % to about 0.8 wt %, or any range or sub-range therebetween.

[0184] In various aspects, step 603 may include exposing the molten precursor material to an oxidizing environment, which will reduce the molar ratio of the polyvalent colorant by increasing the amount of oxidized polyvalent colorant. For example, the oxidizing environment may include a greater oxygen partial pressure than found in air. In other aspects, the molten precursor material may be exposed to an environment comprising an oxygen partial pressure of about 25 kPa (kilopascals) or more, about 30 kPa or more, about 35 kPa or more, about 40 kPa or more, about 50 kPa or more, about 100 kPa or less, about 80 kPa or less, about 70 kPa or less, about 60 kPa or less, about 50 kPa or less, about 45 kPa or less, or about 40 kPa or less. In other aspects, the molten precursor material can be exposed to an environment comprising an oxygen partial pressure in the range of about 25 kPa to about 100 kPa, about 30 kPa to about 80 kPa, about 35 kPa to about 70 kPa, about 40 kPa to about 60 kPa, about 40 kPa to about 50 kPa, or any range or sub-range therebetween.

[0185] In various aspects, the glass article can be formed from the molten precursor material by forming the glass article using a variety of ribbon forming methods, such as slot drawing, down drawing, fusion down drawing, up drawing, press rolls, redrawing, or floating, in step 603. In other aspects, after the glass article is formed in step 603, the method can proceed to step 607 (arrow 602) or step 611 (arrow 604).

[0186] In various aspects, after step 603, the method may proceed to step 605, which includes controlling the temperature of the molten precursor material and / or the rate of temperature change of the molten precursor material when forming a glass article from the molten precursor material. The molten precursor material may be heated to a first temperature of about 1500°C or higher to form a melt. In other aspects, the melt may be cooled from the first temperature at a predetermined rate. In still other aspects, the melt may be rapidly cooled (e.g., quenched at greater than 20°C / minute or greater than 50°C / minute) from the first temperature to a temperature below 1400°C (e.g., below the liquidus temperature), thereby preventing subsequent changes in the molar ratio of the multivalent colorant. In still other aspects, the predetermined rate of decrease from the first temperature to about 1400°C or less can be about 0.1°C / min (°C / min) or more, about 0.3°C / min or more, about 0.5°C / min, about 0.8°C / min or more, about 1°C / min or more, about 1.5°C / min or more, about 2°C / min or more, about 5°C / min or more, about 10°C / min or less, about 5°C / min or less, about 2°C / min or less, about 1.8°C / min or less, about 1.5°C / min or less, about 1.2°C / min or less, or about 1°C / min or less. In yet other aspects, the predetermined rate of cooling from the first temperature to about 1400° C. or less can be in the range of about 0.1° C. / min to about 10° C. / min, about 0.3° C. / min to about 5° C. / min, about 0.5° C. / min to about 2° C. / min, about 0.8° C. / min to about 1.8° C. / min, about 1° C. / min to about 1.5° C. / min, about 1° C. / min to about 1.2° C. / min, or any range or sub-range therebetween. Cooling the melt at a predetermined rate within the above ranges can reduce the molar ratio of the multivalent colorant. In other aspects, the glass article can be formed from the melt in step 605 by forming the glass article using a variety of ribbon forming methods, such as slot drawing, down drawing, fusion down drawing, up drawing, press rolls, redrawing, or floating.

[0187] After step 603 or 605, if Figure 6As shown in , the method can proceed to step 607, which includes chemically strengthening the glass product. In various aspects, as shown in the figure, step 607 may include contacting at least a portion of the glass product 511 with a molten salt solution 703 (e.g., contained in a tank 701). For example, as shown in the figure, the glass product 511 can be immersed in the molten salt solution 703 contained in the tank 701. In various aspects, step 607 can produce the first compressive stress zone, the second compressive stress zone and / or the tensile stress zone discussed above, and the corresponding region may include the maximum stress and / or compression depth within one or more corresponding ranges discussed above. In various aspects, the molten salt solution includes sodium ions and / or potassium ions (e.g., from KNO3 and / or NaNO3). In various aspects, the temperature of the molten salt solution 703 can be about 300°C or higher, about 360°C or higher, about 400°C or higher, about 500°C or lower, about 460°C or lower, or about 420°C or lower. In various aspects, the temperature of the molten salt solution 703 can be in the range of about 300° C. to about 500° C., about 360° C. to about 460° C., about 400° C. to about 420° C., or any range or sub-range therebetween. In various aspects, the glass article 511 can be in contact with the molten salt solution 703 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 various aspects, the glass article 511 can be in contact with the molten salt solution 703 for a time in the range of about 30 minutes to about 8 hours, about 45 minutes to about 4 hours, about 1 hour to about 2 hours, about 1 hour to about 1.5 hours, or any range or sub-range therebetween.

[0188] After step 607, the method may proceed to step 609, which includes assembling the glass article 511 into a natural glass housing, an electronic device (e.g., a consumer electronic device). In various aspects, step 609 may include placing and / or attaching the glass article to a reflector (e.g., in a natural glass housing).

[0189] After step 605, 607 or 609, the method may be completed when reaching step 611. In various aspects, the method of manufacturing the glass article and / or the natural glass housing according to various aspects of the present disclosure may be along the following steps: Figure 6601, 603, 605, 607, 609, and 611 of the flowchart are performed sequentially, as discussed above. In various aspects, the method may proceed from step 603 along arrow 602 to step 607, for example, if the glass article is formed from molten precursor material without the heat treatment of step 605. In various aspects, the method may proceed from step 603 along arrow 604 to step 611, for example, if the method is completed at the end of step 603. In various aspects, the method may proceed from step 605 along arrow 606 to step 611, for example, if the method is completed at the end of step 605. In various aspects, the method may proceed from step 607 along arrow 608 to step 611, for example, if the method is completed at the end of step 607. According to embodiments of the present disclosure, any of the above options may be combined to manufacture a foldable device.

[0190] In various aspects, the glass article can exhibit CIEL*, a*, and / or b* values within one or more of the corresponding ranges discussed above. The glass article is a silicate glass having a multivalent colorant. In other aspects, the multivalent colorant can be cerium, titanium, chromium, cobalt, copper, nickel, vanadium, or a combination thereof. In still other aspects, the multivalent colorant can be cerium, chromium, titanium, or a combination thereof. The glass article can include a molar ratio of the multivalent colorant within one or more of the corresponding ranges discussed above.

[0191] The polyvalent colorant of the precursor material includes a precursor molar ratio, which is defined as the amount of the reduced form of the polyvalent colorant in the precursor material divided by the total amount of the polyvalent colorant (i.e., the sum of the amount of the reduced form of the polyvalent colorant in the precursor material and the sum of the amount of the oxidized form of the polyvalent colorant in the precursor material). In various aspects, the precursor molar ratio of the polyvalent colorant in the precursor material can be about 0.1 or more, about 0.2 or more, about 0.3 or more, about 0.4 or more, about 0.5 or more, about 0.55 or more, about 0.6 or more, about 0.7 or more, about 0.9 or less, about 0.8 or less, about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.5 or less, or about 0.4 or less. In various aspects, the precursor molar ratio of the multivalent colorant in the precursor material can range from about 0.1 to about 0.9, about 0.2 to about 0.9, about 0.3 to about 0.9, about 0.4 to about 0.9, about 0.5 to about 0.9, about 0.55 to about 0.8, about 0.6 to about 0.75, about 0.6 to about 0.7, about 0.6 to about 0.65, or any range or sub-range therebetween. Alternatively, in various aspects, the molar ratio of the multivalent colorant can range from about 0.3 to about 0.9, about 0.4 to about 0.8, about 0.5 to about 0.75, about 0.5 to about 0.7, about 0.5 to about 0.65, about 0.5 to about 0.6, or any range or sub-range therebetween.

[0192] In various aspects, the molar ratio of the precursor of the polyvalent colorant in the precursor material can be different from the molar ratio of the polyvalent colorant in the glass article. In other aspects, the absolute value of the difference between the molar ratio of the precursor of the polyvalent colorant in the precursor material and the molar ratio of the polyvalent colorant in the glass article can be about 0.1 or more, about 0.15 or more, about 0.2 or more, about 0.25 or more, about 0.3 or more, about 0.5 or less, about 0.45 or less, about 0.4 or less, about 0.35 or less, about 0.3 or less, about 0.25 or less, or about 0.2 or less. In other aspects, the absolute value of the difference between the molar ratio of the precursor of the multivalent colorant in the precursor material and the molar ratio of the multivalent colorant in the glass article can range from about 0.1 to about 0.5, from about 0.1 to about 0.45, from about 0.15 to about 0.4, from about 0.15 to about 0.35, from about 0.2 to about 0.3, from about 0.2 to about 0.25, or any range or sub-range therebetween.

[0193] In other aspects, the molar ratio of the precursor of the multivalent colorant in the precursor material can be greater than the molar ratio of the multivalent colorant in the glass article. In yet other aspects, the precursor material can include a sulfate source, a nitrate source, a zinc source (e.g., ZnO), or a combination thereof, which can reduce the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material. The amount of the sulfate source, nitrate source, zinc source, or combination thereof can be about 0.02% by weight, for example, within one or more of the corresponding ranges discussed above for the amounts of the corresponding materials in the precursor material. In yet other aspects, the precursor material can include a sulfate source within one or more of the corresponding ranges discussed above, which can reduce the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material. In yet other aspects, the precursor material can include a nitrate source within one or more of the corresponding ranges discussed above, which can reduce the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material. In still other aspects, the precursor material can include a zinc source within one or more of the corresponding ranges discussed above, which can reduce the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material.

[0194] In other aspects, the molar ratio of the multivalent colorant in the glass article may be greater than the molar ratio of the precursor of the multivalent colorant in the precursor material. In yet other aspects, the precursor material may include an iron source (e.g., Fe2O3), an antimony source (Sb2O3), a carbon source, or a combination thereof. In yet other aspects, the precursor material may include 0.01 wt% or more of an iron source (e.g., Fe2O3), an antimony source (Sb2O3), a carbon source, or a combination thereof. In yet other aspects, the precursor material may include antimony (e.g., Sb2O3) in an amount within one or more of the corresponding ranges discussed above, which may increase the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material. In yet other aspects, the precursor material may include an amount of a carbon source within one or more of the corresponding ranges discussed above, which may increase the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material. In other aspects, the melt formed from the molten precursor material can be cooled at a rate of 0.5°C / min or more (e.g., 0.5°C / min to 2°C / min), thereby increasing the molar ratio of the multivalent colorant in the glass article relative to the molar ratio of the precursor of the multivalent colorant in the precursor material.

[0195] As discussed above, the colorant package in the glass composition can include one or more multivalent colorants and, optionally, one or more additional color-enhancing compounds. For example, the concentrations of NiO + Co3O4 + Cr2O3 + CuO + CeO2 + TiO2 are discussed above. Within the corresponding above-described ranges for these concentrations, as well as within other aspects of the present disclosure, the following more specific combinations are also encompassed. In various aspects, the colorant package can include more than one multivalent colorant, such as both TiO2 and NiO. Providing more than one multivalent colorant can increase the color gamut achievable with the composition, for example, by adjusting the redox ratio as discussed herein. In other aspects, the colorant package may include TiO2 in an amount of about 0.001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.05 mol% or more, about 0.1 mol% or more, about 0.5 mol% or more, about 1.0 mol% or more, about 1.2 mol% or more, about 1.5 mol% or more, about 2.0 mol% or less, about 1.8 mol% or less, about 1.4 mol% or less, about 1.0 mol% or less, about 0.6 mol% or less, about 0.4 mol% or less, about 0.2 mol% or less, about 0.1 mol% or less, or about 0.04 mol% or less. In other aspects, the colorant package can include TiO in an amount ranging from about 0.001 mol% to about 2.0 mol%, from about 0.005 mol% to about 1.8 mol%, from about 0.01 mol% to about 1.8 mol%, from about 0.05 mol% to about 1.4 mol%, from about 0.1 mol% to about 1.0 mol%, from about 0.5 mol% to about 1.0 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include TiO in an amount of about 0.5 mol% or less, for example, in a range from about 0.001 mol% to about 0.4 mol%, from about 0.005 mol% to about 0.1 mol%, from about 0.01 mol% to about 0.04 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include TiO2 in an amount of about 0.2 mol% or greater, for example, in an amount within a range from about 0.2 mol% to about 2.0 mol%, about 0.5 mol% to about 1.8 mol%, about 1.0 mol% to about 1.8 mol%, about 1.2 mol% to about 1.4 mol%, or any range or sub-range therebetween.In other aspects, the colorant package may include NiO in an amount of about 0.001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.05 mol% or more, about 0.07 mol% or more, about 0.09 mol% or more, about 0.11 mol% or more, about 0.13 mol% or more, about 0.15 mol% or more, about 0.2 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 0.6 mol% or more, about 0.7 mol% or more, about 0.8 mol% or more, about 0.9 mol% or more, about 1.1 mol% or more, about 1.2 mol% or more, about 1.3 mol% or more, about 1.4 mol% or more, about 1.6 mol% or more, about 1.7 mol% or more, about 1.8 mol% or more, about 1.9 mol% or more, about 2.3 mol% or more, about 2.4 mol% or more, about 2.5 mol% or more, about 2.6 mol% or more, about 2.7 mol% or more, about 2.8 mol% or more, about 2.9 mol% or more, about 3.4 mol% or more, about 3.5 mol% or more, about 3.6 mol% or more, about 3.7 mol% or more, about 3.5 mol% or more, about 3. About 0.6 mol% or more, about 0.7 mol% or more, about 1.0 mol% or less, about 0.8 mol% or less, about 0.7 mol% or less, about 0.5 mol% or less, about 0.4 mol% or less, about 0.25 mol% or less, about 0.20 mol% or less, about 0.17 mol% or less, about 0.15 mol% or less, about 0.13 mol% or less, about 0.10 mol% or less, or about 0.08 mol% or less. In other aspects, the colorant package may include NiO in an amount ranging from about 0.001 mol% to about 1.0 mol%, about 0.005 mol% to about 1.0 mol%, about 0.01 mol% to about 1.0 mol%, about 0.05 mol% to about 0.8 mol%, about 0.07 mol% to about 0.7 mol%, about 0.09 mol% to about 0.5 mol%, about 0.11 mol% to about 0.4 mol%, about 0.13 mol% to about 0.25 mol%, about 0.15 mol% to about 0.20 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include NiO in an amount of about 0.5 mol% or less, such as in a range from about 0.001 mol% to about 0.5 mol%, about 0.005 mol% to about 0.5 mol%, about 0.01 mol% to about 0.5 mol%, about 0.05 mol% to about 0.5 mol%, about 0.07 mol% to about 0.40 mol%, about 0.09 mol% to about 0.25 mol%, about 0.11 mol% to about 0.17 mol%, about 0.13 mol% to about 0.15 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include NiO in an amount of about 0.1 mol% or greater, such as in a range of about 0.1 mol% to about 1.0 mol%, about 0.2 mol% to about 1.0 mol%, about 0.4 mol% to about 1.0 mol%, about 0.5 mol% to about 0.8 mol%, about 0.6 mol% to about 0.7 mol%, or any range or sub-range therebetween.In other aspects, the colorant package may include one or more of: Fe2O3, MnO2, or a combination thereof, which may act as a redox couple to alter the redox ratio of the multivalent colorant, without being defined as a multivalent colorant itself within the scope of the present disclosure. In other aspects, the colorant package (in addition to TiO2 and NiO within one or more ranges mentioned in this paragraph) can optionally include Fe2O3 in an amount of about 0.0001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.02 mol% or more, about 0.05 mol% or more, about 0.07 mol% or more, about 0.10 mol% or more, about 0.12 mol% or more, about 1.0 mol% or less, about 0.4 mol% or less, about 0.20 mol% or less, about 0.15 mol% or less, about 0.13 mol% or less, about 0.10 mol% or less, about 0.08 mol% or less, about 0.05 mol% or less, about 0.03 mol% or less, or about 0.01 mol% or less. In other aspects, the colorant package (in addition to TiO2 and NiO within one or more of the corresponding ranges mentioned in this paragraph) can optionally include Fe2O3 within the range of about 0.001 mol% to about 1.0 mol%, about 0.001 mol% to about 0.4 mol%, about 0.005 mol% to about 0.20 mol%, about 0.01 mol% to about 0.15 mol%, about 0.02 mol% to about 0.13 mol%, about 0.05 mol% to about 0.10 mol%, about 0.07 mol% to about 0.08 mol%, or any range or sub-range therebetween. In other aspects, the colorant package (in addition to TiO2 and NiO within one or more of the corresponding ranges mentioned in this paragraph, and optionally Fe2O3) can optionally include MnO2 in an amount of 0.0001 mol% or more, about 0.0002 mol% or more, about 0.0004 mol% or more, about 0.002 mol% or more, about 0.01 mol% or more, about 0.02 mol% or more, about 0.03 mol% or more, about 0.04 mol% or more, about 0.05 mol% or more, about 0.10 % or less, about 0.05 mol% or less, about 0.04 mol% or less, about 0.03 mol% or less, about 0.02 mol% or less, about 0.01 mol% or less, or about 0.005 mol% or less.In other aspects, the colorant package (in addition to TiO2 and NiO within one or more of the respective ranges mentioned in this paragraph, and optionally Fe2O3) may optionally include MnO2 within the range of about 0.0001 mol% to about 0.20 mol%, about 0.0002 mol% to about 0.17 mol%, about 0.0004 mol% to about 0.15 mol%, about 0.002 mol% to about 0.12 mol%, about 0.01 mol% to about 0.10 mol%, about 0.02 mol% to about 0.07 mol%, about 0.03 mol% to about 0.05 mol%, or any range or sub-range therebetween. In other aspects, the colorant package (in addition to TiO2 and NiO and optionally Fe2O3 within one or more of the corresponding ranges mentioned in this paragraph) can optionally include MnO2 in an amount of 0.01 mol% or more, such as in a range of 0.01 mol% to about 0.2 mol%, about 0.02 mol% to about 0.17 mol%, about 0.03 mol% to about 0.17 mol%, about 0.04 mol% to about 0.15 mol%, about 0.05 mol% to about 0.15 mol%, about 0.10 mol% to about 0.12 mol%, or any range or sub-range therebetween. Exemplary ranges for the colorant packages discussed in this paragraph are presented in Table 1. Ranges R1-R5 include TiO2 and NiO, but do not include Fe2O3 and MnO2. Ranges R6-R10 include TiO2, NiO, and Fe2O3. Ranges R9-R12 include TiO2, NiO, and MnO2. Although CIE L*, a*, and b* values are provided in Table 1, it should be understood that these values are not necessarily limited to the ranges R2-R5, R7-R8, R10, and / or R12, e.g., the CIE values of R1, R6, R10, and / or R12 may be applicable to any range shown in Table 1.

[0196] Table 1: Exemplary ranges for colorant packages containing TiO2 and NiO

[0197]

[0198]

[0199] In various aspects, the colorant package can include more than one multivalent colorant, such as both TiO 2 and CeO 2. Providing more than one multivalent colorant can increase the color gamut achievable with the composition, for example by adjusting the redox ratios discussed herein. In other aspects, the colorant package may include TiO2 in an amount of about 0.001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.02 mol% or more, about 0.05 mol% or more, about 0.1 mol% or more, about 0.5 mol% or more, about 1.0 mol% or more, about 1.1 mol% or more, about 1.2 mol% or more, about 2.0 mol% or less, about 1.5 mol% or less, about 1.2 mol% or less, about 1.0 mol% or less, about 0.6 mol% or less, about 0.04 mol% or less, about 0.2 mol% or less, about 0.1 mol% or less, or about 0.04 mol% or less. In other aspects, the colorant package can include TiO in an amount ranging from about 0.001 mol% to about 2.0 mol%, from about 0.005 mol% to 2.0 mol%, from about 0.01 mol% to about 1.5 mol%, from about 0.02 mol% to about 1.2 mol%, from 0.05 mol% to about 1.0 mol%, from about 0.1 mol% to about 1.0 mol%, from about 0.5 mol% to about 1.0 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include TiO in an amount of about 0.5 mol% or less, such as in a range from about 0.001 mol% to about 0.5 mol%, from about 0.005 mol% to about 0.5 mol%, from about 0.01 mol% to about 0.4 mol%, from about 0.02 mol% to about 0.2 mol%, from about 0.05 mol% to about 0.2 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include TiO2 in an amount of about 0.1 mol% or greater, such as in a range of about 0.1 mol% to about 2.0 mol%, about 0.5 mol% to about 1.8 mol%, about 1.0 mol% to about 1.6 mol%, about 1.1 mol% to about 1.4 mol%, or any range or sub-range therebetween.In other aspects, the colorant package may include CeO2 in an amount of about 0.001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.1 mol% or more, about 0.2 mol% or more, about 0.5 mol% or more, about 0.6 mol% or more, about 0.7 mol% or more, about 0.8 mol% or more, about 1.0 mol% or less, about 0.8 mol% or less, about 0.7 mol% or less, about 0.6 mol% or less, about 0.5 mol% or less, about 0.4 mol% or less, about 0.3 mol% or less, about 0.2 mol% or less, about 0.1 mol% or less, about 0.05 mol% or less, or about 0.01 mol% or less. In other aspects, the colorant package may include CeO in an amount ranging from about 0.001 mol% to about 1.0 mol%, about 0.05 mol% to about 1.0 mol%, about 0.1 mol% to about 1.0 mol%, about 0.2 mol% to about 0.8 mol%, about 0.4 mol% to about 0.6 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include CeO in an amount of about 0.1 mol% or more, such as in a range of about 0.1 mol% to about 1.0 mol%, about 0.2 mol% to about 1.0 mol%, about 0.5 mol% to about 0.8 mol%, about 0.5 mol% to about 0.7 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include one or more of FeO, MnO, or a combination thereof, which may act as a redox pair to alter the redox ratio of the polyvalent colorant, but are not defined as polyvalent colorants themselves within the scope of the present disclosure. In other aspects, the colorant package (in addition to TiO2 and CeO2 within one or more ranges mentioned in this paragraph) can optionally include Fe2O3 in an amount of about 0.001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.02 mol% or more, about 0.05 mol% or more, about 0.07 mol% or more, about 0.10 mol% or more, about 0.12 mol% or more, about 0.20 mol% or less, about 0.15 mol% or less, about 0.13 mol% or less, about 0.10 mol% or less, about 0.08 mol% or less, about 0.05 mol% or less, about 0.03 mol% or less, or about 0.01 mol% or less.In other aspects, the colorant package (in addition to TiO2 and CeO2 within one or more of the corresponding ranges mentioned in this paragraph) can optionally include Fe2O3 within the range of about 0.001 mol% to about 0.20 mol%, about 0.005 mol% to about 0.20 mol%, about 0.01 mol% to about 0.15 mol%, about 0.02 mol% to about 0.13 mol%, about 0.05 mol% to about 0.10 mol%, about 0.07 mol% to about 0.08 mol%, or any range or sub-range therebetween. In other aspects, the colorant package (in addition to TiO2 and CeO2 within one or more ranges mentioned in this paragraph, and optionally Fe2O3) can optionally include MnO2 in an amount of about 0.01 mol% or more, about 0.02 mol% or more, about 0.05 mol% or more, about 0.10 mol% or more, about 0.2 mol% or more, about 0.5 mol% or more, about 0.7 mol% or more, about 0.8 mol% or more, about 1.0 mol% or less, about 0.8 mol% or less, about 0.6 mol% or less, about 0.4 mol% or less, about 0.3 mol% or less, about 0.2 mol% or less, about 0.10 mol% or less, or about 0.04 mol% or less. In other aspects, the colorant package (in addition to TiO2 and CeO2 within one or more of the corresponding ranges mentioned in this paragraph, and optionally Fe2O3) can optionally include MnO2 in the range of about 0.01 mol% to about 1.0 mol%, about 0.02 mol% to about 0.8 mol%, about 0.05 mol% to about 0.6 mol%, about 0.10 mol% to about 0.4 mol%, about 0.2 mol% to about 0.3 mol%, or any range or sub-range therebetween. In other aspects, the colorant package (in addition to TiO2 and CeO2 within one or more of the corresponding ranges mentioned in this paragraph, and optionally Fe2O3) can optionally include MnO2 in an amount of 0.10 mol% or more, such as in the range of 0.10 mol% to about 1.0 mol%, about 0.2 mol% to about 0.8 mol%, about 0.5 mol% to about 0.7 mol%, about 0.5 mol% to about 0.6 mol%, or any range or sub-range therebetween. Exemplary ranges for the colorant packages discussed in this paragraph are presented in Table 2. Ranges R13-R17 include TiO2 and CeO2, but do not include Fe2O3 and MnO2. Ranges R18-R22 include TiO2, CeO2, and Fe2O3. Ranges R21-R22 include TiO2, CeO2, and MnO2.Although CIE L*, a*, and b* values are provided in Table 2, it should be understood that these values are not necessarily limited to the ranges R14-R17, R19-R20, and / or R22, for example, CIE values of R13, R18, and / or R21 may be applicable to any range shown in Table 2.

[0200] Table 2: Exemplary Ranges for Colorant Packages Containing TiO2 and CeO2

[0201]

[0202] In various aspects, the colorant package can include more than one multivalent colorant, such as both NiO and CeO2; all of TiO2, CeO2, and NiO; or all of TiO2, CeO2, NiO, and Co3O4. Providing more than one multivalent colorant (e.g., 2 or more, or 3) can increase the color gamut that can be achieved with the composition, for example, by adjusting the redox ratios discussed herein. In other aspects, the colorant package can include NiO in an amount of about 5×10 -5 mol% or more, about 0.0001 mol% or more, about 0.01 mol% or more, about 0.05 mol% or more, about 0.07 mol% or more, about 0.10 mol% or more, about 0.12 mol% or more, about 0.15 mol% or more, about 0.17 mol% or more, about 0.20 mol% or more, about 0.3 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 0.6 mol% or more, about 0.3 mol% or less, about 0.20 mol% or less, about 0.15 mol% or less, about 0.10 mol% or less, or about 0.05 mol% or less, or about 0.01 mol% or less. In other aspects, the colorant package may include NiO in an amount within the range of about 5×10 -5 mol% to about 0.3 mol%, about 0.001 mol% to about 0.20 mol%, about 0.01 mol% to about 0.15 mol%, about 0.05 mol% to about 0.10 mol%. In other aspects, the colorant package may include NiO in an amount of about 0.1 mol% or more, such as in an amount ranging from about 5×10 -5 mol% to about 0.1mol%, about 5×10 -5% or more, about 1.2 mol% or more, about 1.4 mol% or more, about 1.6 mol% or more, about 2.0 mol% or less, about 1.5 mol% or less, about 1.3 mol% or less, about 1.0 mol% or less, about 0.7 mol% or less, about 0.5 mol% or less, about 0.3 mol% or less, about 0.1 mol% or less, or about 0.05 mol% or less. In other aspects, the colorant package can include CeO in an amount ranging from about 0.001 mol% to about 2.0 mol%, from about 0.02 mol% to about 1.5 mol%, from about 0.05 mol% to about 1.3 mol%, from about 0.1 mol% to about 1.0 mol%, from about 0.2 mol% to about 1.0 mol%, from about 0.2 mol% to about 0.5 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include CeO in an amount of about 0.2 mol% or more, for example, in a range from about 0.2 mol% to about 2.0 mol%, from about 0.5 mol% to about 1.5 mol%, from about 1.0 mol% to about 1.5 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include (e.g., in addition to NiO and CeO2) Co3O4 in an amount of about 0.0001 mol% or more, about 0.0003 mol% or more, about 0.0005 mol% or more, about 0.001 mol% or more, about 0.003 mol% or more, about 0.005 mol% or more, about 0.008 mol% or more, about 0.010 mol% or more, about 0.012 mol% or more, about 0.01 % or less, about 0.05 mol% or less, about 0.08 mol% or more, about 0.1 mol% or less, about 0.08 mol% or less, about 0.05 mol% or less, about 0.02 mol% or less, about 0.010 mol% or less, about 0.008 mol% or less, about 0.005 mol% or less, about 0.003 mol% or less, or about 0.0010 mol% or less.In other aspects, the colorant package may include (e.g., in addition to NiO and CeO2) Co3O4 in an amount within the range of about 0.0001 mol% to about 0.1 mol%, about 0.0003 mol% to about 0.08 mol%, about 0.0005 mol% to about 0.05 mol%, about 0.0010 mol% to about 0.02 mol%, about 0.003 mol% to about 0.01 mol%, about 0.005 mol% to about 0.008 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include (e.g., in addition to NiO and CeO2) Co3O4 in an amount of 0.01 mol% or less, such as in a range of about 0.0001 mol% to about 0.01 mol%, about 0.0003 mol% to about 0.008 mol%, about 0.0005 mol% to about 0.005 mol%, about 0.001 mol% to about 0.002 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include (e.g., in addition to NiO and CeO2) Co3O4 in an amount of 0.01 mol% or more, such as in a range of about 0.01 mol% to about 0.10 mol%, about 0.012 mol% to about 0.08 mol%, about 0.015 mol% to about 0.05 mol%, about 0.03 mol% to about 0.05 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include (e.g., in addition to NiO, CeO2, and / or Co3O4) TiO2 in an amount of about 5×10. -5 % or more, about 0.001 mol % or more, about 0.005 mol % or more, about 0.008 mol % or more, about 0.01 mol % or more, about 0.02 mol % or more, about 0.05 mol % or more, about 0.1 mol % or more, about 0.5 mol % or more, about 1.0 mol % or less, about 0.5 mol % or less, about 0.3 mol % or less, about 0.1 mol % or less, about 0.05 mol % or less, about 0.02 mol % or less, or about 0.01 mol % or less. In other aspects, the colorant package may include (e.g., in addition to NiO, CeO 2 and / or Co 3 O 4 ) TiO 2 in an amount within the following ranges: about 5×10 -5 mol% to about 1.0 mol%, about 0.001 mol% to about 0.5 mol%, about 0.005 mol% to about 0.3 mol%, about 0.008 mol% to about 0.1 mol%, about 0.01 mol% to about 0.05 mol%, or any range or sub-range therebetween. In other aspects, the colorant package may include TiO in an amount of about 0.5 mol% or less, such as in an amount ranging from about 5×10 -5mol% to about 0.5 mol%, about 0.001 mol% to about 0.5 mol%, about 0.005 mol% to about 0.5 mol%, about 0.008 mol% to about 0.3 mol%, about 0.01 mol% to about 0.1 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include TiO2 in an amount of about 0.01 mol% or more, such as in the range of about 0.01 mol% to about 1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.05 mol% to about 0.3 mol%, about 0.05 mol% to about 0.1 mol%, or any range or sub-range therebetween. In other aspects, the colorant package can include Fe2O3 and / or MnO2, which can act as a redox couple to change the redox ratio of the multivalent colorant, but are not defined as multivalent colorants themselves within the scope of the present disclosure. In other aspects, the colorant package (in addition to NiO and CeO2; NiO, CeO2, and TiO2; or NiO, CeO2, and / or Co3O4 within one or more of the corresponding ranges mentioned in this paragraph) can optionally include Fe2O3 in an amount of about 0.0001 mol% or more, about 0.005 mol% or more, about 0.01 mol% or more, about 0.02 mol% or more, about 0.05 mol% or more, about 0.07 mol% or more, about 0.10 mol% or more, about 0.12 mol% or more, about 0.20 mol% or less, about 0.15 mol% or less, about 0.13 mol% or less, about 0.10 mol% or less, about 0.08 mol% or less, about 0.05 mol% or less, about 0.03 mol% or less, or about 0.01 mol% or less. In other aspects, the colorant package (in addition to NiO and CeO2; NiO, CeO2 and TiO2; or NiO, CeO2 and / or Co3O4 within one or more of the corresponding ranges mentioned in this paragraph) may optionally include Fe2O3 within the following ranges: from about 0.001 mol% to about 0.20 mol%, from about 0.005 mol% to about 0.20 mol%, from about 0.01 mol% to about 0.15 mol%, from about 0.02 mol% to about 0.13 mol%, from about 0.05 mol% to about 0.10 mol%, from about 0.07 mol% to about 0.08 mol%, or any range or sub-range therebetween.In other aspects, the colorant package (in addition to NiO and CeO2; NiO, CeO2, and TiO2; or NiO, CeO2, and / or Co3O4 within one or more of the corresponding ranges mentioned in this paragraph) can optionally include MnO2 within the following ranges: from about 0.01 mol% to about 1.0 mol%, from about 0.02 mol% to about 0.8 mol%, from about 0.05 mol% to about 0.6 mol%, from about 0.10 mol% to about 0.4 mol%, from about 0.2 mol% to about 0.3 mol%, or any range or sub-range therebetween. In other aspects, the colorant package (in addition to NiO and CeO2; NiO, CeO2 and TiO2; or NiO, CeO2 and / or Co3O4 within one or more of the corresponding ranges mentioned in this paragraph) can optionally include MnO2 in an amount of 0.10 mol% or more, such as in a range of 0.10 mol% to about 1.0 mol%, about 0.2 mol% to about 0.8 mol%, about 0.5 mol% to about 0.7 mol%, about 0.5 mol% to about 0.6 mol%, or any range or subrange therebetween. Exemplary ranges for the colorant packages discussed in this paragraph are presented in Table 3. Ranges R25-R30 include NiO and CeO2, but not TiO2 and Fe2O3. Ranges R37-R38 and R42 include Co3O4 and at least NiO. Ranges R31-R36 include NiO, CeO2, and TiO2. Ranges R37-R42 include NiO and Fe2O3. Range R35-R36 includes NiO, CeO 2 , TiO 2 , and Fe 2 O 3 . Although CIE L*, a*, and b* values are provided in Table 3, it should be understood that these values are not necessarily limited to ranges R26-R30, R32-R34, and / or R36-R41 , e.g., the CIE values of R25, R31 , R35, and / or R42 may be applicable to any range shown in Table 3.

[0203] Table 3: Exemplary ranges for colorant packages containing NiO, CeO2 and / or TiO2

[0204]

[0205] Other example aspects of the present disclosure are described below, and it should be understood that any features of the various aspects may be used alone or in combination with each other.

[0206] Aspect 48. The method of any one of aspects 1 to 25, wherein the multivalent colorant comprises:

[0207] 0.001 mol% to 2.0 mol% TiO2; and

[0208] 0.001 mol% to 1.0 mol% NiO.

[0209] Aspect 49. The method of aspect 48, wherein the multivalent colorant comprises 0.01 mol% to 0.05 mol% of the TiO2.

[0210] Aspect 50. The method of aspect 48, wherein the multivalent colorant comprises 0.2 mol% to 2.0 mol% of the TiO2.

[0211] Aspect 51. The method of any one of aspects 48 to 50, wherein the multivalent colorant comprises 0.05 mol% to 0.5 mol% of the NiO.

[0212] Aspect 52. The method of any one of aspects 48 to 51, wherein the glass article exhibits a CIE a* value of −12 to 4 and a CIE b* value of −35 to 35.

[0213] Aspect 52. The method according to aspect 52, wherein the CIE a* value is 0.1 to 0.8, and the CIE b* value is 12 to 18.

[0214] Aspect 53. The method of any one of aspects 1 to 25, wherein the multivalent colorant comprises:

[0215] 0.01 mol% to 2.0 mol% TiO2; and

[0216] 0.01 mol% to 1.0 mol% CeO2.

[0217] Aspect 54. The method of aspect 53, wherein the multivalent colorant comprises 0.005 mol% to 0.5 mol% of the TiO2.

[0218] Aspect 55. The method of aspect 53, wherein the multivalent colorant comprises 0.1 mol% to 1.0 mol% of the TiO2.

[0219] Aspect 56. The method of any one of aspects 53 to 55, wherein the multivalent colorant comprises 0.1 mol% to 1.0 mol% of the CeO2.

[0220] Aspect 57. The method of any one of aspects 53 to 56, wherein the glass article exhibits a CIE a* value of −6 to 5 and a CIE b* value of −5 to 35.

[0221] Aspect 58. The method according to aspect 57, wherein the CIE a* value is -1 to 5, and the CIE b* value is 0 to 15.

[0222] Aspect 59. The method of any one of aspects 1 to 25, wherein the multivalent colorant comprises:

[0223] 5×10 -5 mol% to 0.3mol% NiO; and

[0224] 0.0001 mol% to 2.0 mol% CeO2.

[0225] Aspect 60. The method according to aspect 59, wherein the multivalent colorant comprises 5×10 -5 mol% to 0.05mol% of said NiO.

[0226] Aspect 61. The method of aspect 59, wherein the multivalent colorant comprises 0.05 mol% to 0.3 mol% of the NiO.

[0227] Aspect 62. The method of any one of aspects 59 to 61, wherein the multivalent colorant comprises 0.001 mol% to 0.2 mol% of the CeO2.

[0228] Aspect 63. The method of any one of aspects 59 to 61, wherein the multivalent colorant comprises 0.2 mol% to 2 mol% of the CeO2.

[0229] Aspect 64. The method of any one of aspects 59 to 63, wherein the glass article exhibits a CIE a* value of −15 to 20 and a CIE b* value of 1 to 80.

[0230] Aspect 65. The method according to aspect 64, wherein the CIE a* value is 0.3 to 16.

[0231] Aspect 66. The method of aspect 64, wherein the CIE a* value is -11 to -0.1.

[0232] Aspect 67. The method according to any one of aspects 59 to 66, wherein the multivalent colorant further comprises one or more of the following:

[0233] 5×10 -5 mol% to 1.0mol% TiO2;

[0234] 0.0001 mol% to 0.1 mol% Co3O4; or

[0235] A combination of them.

[0236] Aspect 68. A primary colored glass housing for a consumer electronic device, the primary colored glass housing comprising a glass article, the glass article including a thickness defined between a first major surface and a second major surface, the second major surface opposite the first major surface, the thickness being from 200 μm to 5 mm, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, and having a total transmittance through the thickness of 3% to 80% in at least one 10 nm band within a wavelength range of 380 nm to 750 nm, wherein the multivalent colorant comprises:

[0237] 0.001 mol% to 2.0 mol% TiO2; and

[0238] 0.001 mol% to 1.0 mol% NiO.

[0239] Aspect 69. The primary colored glass enclosure of any one of aspects 26 to 47, wherein the multivalent colorant comprises:

[0240] 0.001 mol% to 2.0 mol% TiO2; and

[0241] 0.001 mol% to 1.0 mol% NiO.

[0242] Aspect 70. The natural color glass enclosure of aspect 68 or 69, wherein the multivalent colorant comprises 0.01 mol% to 0.05 mol% of the TiO2.

[0243] Aspect 71. The natural color glass enclosure of aspect 68 or 69, wherein the multivalent colorant comprises 0.2 mol% to 2.0 mol% of the TiO2.

[0244] Aspect 72. The primary colored glass enclosure of any one of aspects 68 to 71, wherein the multivalent colorant comprises 0.05 mol% to 0.5 mol% of the NiO.

[0245] Aspect 73. The natural glass enclosure of any one of aspects 68 to 72, wherein the glass article exhibits a CIE a* value of -12 to 4 and a CIE b* value of -35 to 35.

[0246] Aspect 74. The natural glass enclosure of aspect 73, wherein the CIE a* value is 0.1 to 0.8, and the CIE b* value is 12 to 18.

[0247] Aspect 75. A primary colored glass housing for a consumer electronic device, the primary colored glass housing comprising a glass article, the glass article including a thickness defined between a first major surface and a second major surface, the second major surface opposite the first major surface, the thickness being from 200 μm to 5 mm, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, and having a total transmittance through the thickness of 3% to 80% in at least one 10 nm band within a wavelength range of 380 nm to 750 nm, wherein the multivalent colorant comprises:

[0248] 0.01 mol% to 2.0 mol% TiO2; and

[0249] 0.01 mol% to 1.0 mol% CeO2.

[0250] Aspect 76. The primary colored glass enclosure of any one of aspects 26 to 47, wherein the multivalent colorant comprises:

[0251] 0.01 mol% to 2.0 mol% TiO2; and

[0252] 0.01 mol% to 1.0 mol% CeO2.

[0253] Aspect 77. The natural color glass enclosure of aspect 75 or 76, wherein the multivalent colorant comprises 0.005 mol% to 0.5 mol% of the TiO2.

[0254] Aspect 78. The primary colored glass enclosure of aspect 75 or 76, wherein the multivalent colorant comprises 0.1 mol% to 1.0 mol% of the TiO2.

[0255] Aspect 79. The primary colored glass envelope of any one of aspects 75 to 78, wherein the multivalent colorant comprises 0.1 mol% to 1.0 mol% of the CeO 2 .

[0256] Aspect 80. The natural glass enclosure of any one of aspects 75 to 79, wherein the glass article exhibits a CIE a* value of -6 to 5 and a CIE b* value of -5 to 35.

[0257] Aspect 81. The natural glass enclosure of aspect 80, wherein the CIE a* value is -1 to 5, and the CIE b* value is 0 to 15.

[0258] Aspect 82. A natural color glass housing for a consumer electronic device, the natural color glass housing comprising a glass article, the glass article including a thickness defined between a first major surface and a second major surface, the second major surface opposite the first major surface, the thickness being from 200 μm to 5 mm, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, and having a total transmittance through the thickness of 3% to 80% in at least one 10 nm band within a wavelength range of 380 nm to 750 nm, wherein the multivalent colorant comprises:

[0259] 5×10 -5 mol% to 0.3mol% NiO; and

[0260] 0.0001 mol% to 2.0 mol% CeO2.

[0261] Aspect 83. The primary colored glass enclosure of any one of aspects 26 to 47, wherein the multivalent colorant comprises:

[0262] 5×10 -5 mol% to 0.3mol% NiO; and

[0263] 0.0001 mol% to 2.0 mol% CeO2.

[0264] Aspect 84. The primary color glass enclosure according to aspect 81 or 83, wherein the multivalent colorant comprises 5×10 - 5 mol% to 0.05mol% of said NiO.

[0265] Aspect 85. The primary colored glass enclosure of aspect 82, wherein the multivalent colorant comprises 0.05 mol% to 0.3 mol% of the NiO.

[0266] Aspect 86. The primary color glass enclosure of any one of aspects 82 to 85, wherein the multivalent colorant comprises 0.001 mol% to 0.2 mol% of the CeO 2 .

[0267] Aspect 87. The primary colored glass enclosure of any one of aspects 82 to 86, wherein the multivalent colorant comprises 0.2 mol% to 2 mol% of the CeO2.

[0268] Aspect 88. The natural glass enclosure of any one of aspects 81 to 86, wherein the glass article exhibits a CIE a* value of -15 to 20 and a CIE b* value of 1 to 80.

[0269] Aspect 89. The natural glass enclosure of aspect 88, wherein the CIE a* value is 0.3 to 16.

[0270] Aspect 90. The natural glass enclosure of aspect 88, wherein the CIE a* value is -11 to -0.1.

[0271] Aspect 91. The method of any one of aspects 82 to 90, wherein the multivalent colorant further comprises one or more of:

[0272] 5×10 -5 mol% to 1.0mol% TiO2;

[0273] 0.0001 mol% to 0.1 mol% Co3O4; or

[0274] A combination of them.

[0275] Examples

[0276] Each aspect will be further illustrated by the following examples. Examples AA-DD correspond to chromium-containing raw materials having the properties of Examples AA-BB shown in Table 4. Examples 1-50 are glass products having the compositions and properties of Examples 1-50 provided in Tables 5-12. Unless otherwise specified in Tables 5-12, the composition refers to the mol% of the glass product. The amounts of chromium (e.g., Cr2O3), iron (e.g., Fe2O3), and antimony (e.g., Sb2O3) are stated in parts per million (ppm) of the glass product. However, the amounts of nitrate, carbon, and nitrate refer to the weight% of the raw materials used to form the glass product. Unless otherwise specified, Examples 7-50, in addition to the components of each example described in Tables 6-12, also include approximately 57.4 mol% SiO2, approximately 24.8 mol% Al2O3, approximately 6.5 mol% B2O3, approximately 4.5 mol% Li2O, approximately 0.1 mol% K2O, approximately 1.2 mol% MgO, and approximately 3.7 mol% CaO. Examples 1-50 included a nominal thickness of 3.6 mm.

[0277] Table 4 presents the properties of various commercially available chromium-containing materials. Examples AA-BB were analyzed using XPS to determine the presence of Cr at the surface of these materials after fracture under ultrahigh vacuum. 3+ Oxidized (reduced) and Cr 6+All X-ray photoelectron spectroscopy (XPS) measurements were performed using a Physical Electronics PHI Quantum 2000 XPS instrument equipped with monochromated Al Kα radiation and using a combination of low-energy electrons and argon ions for charge neutralization. During the XPS measurement, a monochromated Al Kα beam with a width of approximately 100 μm and a beam energy of approximately 25 W was raster-irradiated onto a detection area of 1 mm × 0.5 mm.

[0278] The raw materials of Examples AA and BB were melted into rods measuring approximately 5 mm x 5 mm x 10 mm. The rods were notched approximately 5 mm from the end along a height of 10 mm to create a known location from which the fracture started. The rods were each placed in a custom-made ultra-high vacuum fracture cell attached to an XPS unit. During the ultra-high vacuum fracture, the base pressure of the ultra-high vacuum fracture cell was 2×10 -9 This vacuum fracture ensures that ambient gases (such as oxygen and water vapor, which have extremely low concentrations in ultra-high vacuum) do not have sufficient time to react with the fracture surface and change the oxidation state of chromium. After ultra-high vacuum fracture, the fractured rod is directly transferred to the analysis chamber of the XPS instrument within 120 seconds without being exposed to air.

[0279] For each ultra-high vacuum fracture surface, an area measuring 1 mm × 0.5 mm was selected and XPS measurements were performed using the parameters described above. The spectrometer's throughput was set to a value of 46.95 eV, with a step length of 0.1 eV per step and a dwell time of 50 milliseconds per step. The core levels monitored during the XPS measurements are listed below in the order in which they were measured, and the number of scans used to measure each core level is presented in brackets: Cr 2p (15 scans), O 1s (3 scans), C 1s (3 scans), Si 2p (4 scans), Na 2s (4 scans), and B 1s (6 scans). Data analysis was performed using the MultiPak software package (Version 9.4.0.7) provided and sold by Physical Electronics (Copyright 1994-2011, Ulvac-phi Co., Ltd.). During analysis, the energy scale was referenced to the CC / CH peak of the exogenous hydrocarbons, which was generally accepted at 284.8 eV. Compositional analyses and chromium oxidation states were performed using the atomic sensitivity factors provided in the MultiPak software version referenced above.

[0280] Figure 8-9The observed intensity of the Cr 2p core level energy spectrum of the ultra-high vacuum fracture surface is presented on vertical axes 803 and 903 at different binding energies (in electron volts) on horizontal axes 801 and 901, where curve 805 corresponds to case AA and curve 905 corresponds to case BB. These curves 805 and 905 are fitted to sum-of-Gaussian-Lorentzian models to determine the amount of different forms of chromium-containing compounds. Curves 807 and 907 represent the sum-of-Gaussian-Lorentzian approximation of curves 805 or 905, respectively, where 809 and 907 correspond to the sum of curves 809, 811, and 813 or curves 909, 911, and 913, respectively. Curves 807, 809, 811 and 813 and curves 907, 909, 911 and 913 are shown on a Shirley baseline connecting the average values at each end point of the fitting range. The region with a binding energy of about 573 eV to 581 eV corresponds to the Cr2p3 / 2 spin-orbit splitting and is used to determine the oxidation state of chromium in these two examples. We use a single Gauss-Lorentz peak for each oxidation state of chromium as described in Table 7 of the publication by Beisinger et al. (Surface and Interface Analysis 36 (2004) 1550-1563). Curves 809 and 809 correspond to Cr(OH)3 (i.e., Cr 3+ ) amount; Curves 811 and 911 correspond to Cr2O3 (ie, Cr 3+ and curves 813 and 913 correspond to Cr 6+ Table 4 presents the amount of Cr detected in Examples AA-BB 3+ The total amount and Cr 6+ The total amount of precursors was 0.886 for Example AA, while the precursor molar ratio for Example BB was 0.637. This demonstrates that even precursor materials nominally comprising the same materials can have different molar ratios of multivalent colorants. Additionally, as discussed in Table 5 below, different precursor materials are associated with different CIE color coordinates (and molar ratios of multivalent colorants) in the resulting glass articles.

[0281] Table 4: Oxidation state and molar ratio of chromium-containing raw materials

[0282] Examples AA BB <![CDATA[Cr 3+ (atomic %)]]> 1.09 0.72 <![CDATA[Cr 6+ (atomic %)]]> 0.14 0.41 <![CDATA[Precursor molar ratio (Cr 3+ / Cr 6+ )]]> 0.886 0.637

[0283] Table 5: Composition and properties of Examples 1-6

[0284] Examples 1 2 3 4 5 6 Chromium source AA AA BB CC DD DD <![CDATA[SiO2]]> 60.93 60.88 60.89 60.89 60.93 60.88 <![CDATA[Al2O3]]> 15.56 15.58 15.48 15.48 15.56 15.58 <![CDATA[B2O3]]> 5.97 5.98 6.05 6.05 5.97 5.98 <![CDATA[Li2O]]> 9.64 9.65 9.57 9.57 9.64 9.65 <![CDATA[Na2O]]> 1.55 1.55 1.61 1.61 1.55 1.55 <![CDATA[K2O]]> 0.07 0.07 0.20 0.20 0.07 0.07 MgO 1.98 1.98 1.93 1.93 1.98 1.98 CaO 4.23 4.23 4.27 4.27 4.23 4.23 <![CDATA[Fe2O3]]> 0.034 0.034 0 0 0.034 0.034 <![CDATA[Cr2O3]]> 0.034 0.042 0.013 0.013 0.034 0.042 <![CDATA[SiO2(wt)]]> 57.43 57.32 57.33 57.33 57.43 57.32 <![CDATA[Al2O3(wt)]]> 24.89 24.89 24.74 24.74 24.89 24.89 <![CDATA[B2O3(wt)]]> 6.52 6.52 6.60 6.60 6.52 6.52 <![CDATA[Li2O(wt)]]> 4.52 4.52 4.48 4.48 4.52 4.52 <![CDATA[Na2O(wt)]]> 1.51 1.51 1.56 1.56 1.51 1.51 <![CDATA[K2O(wt)]]> 0.10 0.10 0.29 0.29 0.10 0.10 MgO (wt) 1.25 1.25 1.22 1.22 1.25 1.25 CaO(wt) 3.72 3.72 3.75 3.75 3.72 3.72 <![CDATA[Fe2O3(ppm)]]> 840 840 0 0 840 840 <![CDATA[Cr2O3(ppm)]]> 850 1060 295 290 850 1040 L* 88.8 88.5 94.0 94.2 88.95 87.2 a* -9.35 -11.95 -3.7 -3.2 -8.8 -10.5 b* 14.0 20.45 11.0 8.2 11.05 13.2

[0285] Table 5 presents the composition and properties of Examples 1-6, manufactured using one of the commercially available precursor materials AA-DD, each containing a chromium source (i.e., chromium). Examples 1-2 used source AA (identical to Example AA), Example 3 used source BB (e.g., a sample of Example BB), Example 4 used source CC, and Examples 5-6 used source DD. Example 1 and Example 5 had identical compositions except for the precursor material sources; however, the CIE a* value of Example 1 was approximately 0.55 less than that of Example 5, and the CIE b* value of Example 1 was approximately 3.05 less than that of Example 5. These differences are clearly noticeable when compared visually. Although the compositions other than the source materials differed from one another, the range of CIE color coordinates demonstrates that differences in the precursor molar ratios of the source materials translate into different colors (and therefore different molar ratios) of the resulting source materials, even under identical processing conditions.

[0286] Table 6 presents the compositions of the precursor materials for Examples 7-11 and the properties of the resulting glass articles. Example 7 included 0.29 wt% of a nitrate source in the precursor material, and Examples 9-11 included 0.001 wt% to 0.010 wt% of a carbon source in the precursor material. The only difference between the precursor materials for Examples 7 and 8 is that Example 7 included a nitrate source (0.29 wt%), while Example 8 did not. Compared to Example 8, the CIE a* value for Example 7 was approximately 0.75 lower, and the CIE b* value for Example 7 was approximately 4.7. This indicates that the addition of a nitrate source reduces the molar ratio of the polyvalent colorant (i.e., chromium) because the polyvalent colorant is oxidized by the nitrate.

[0287] The amount of carbon in the precursor material increased from Example 9 to Example 10 and further increased to Example 11. In Examples 9-11, the carbon source was charcoal. The CIE a* value increased by approximately 0.35 from Example 9 to Example 10, while the CIE b* value decreased by approximately 2. This suggests that adding a carbon source increases the molar ratio of the polyvalent colorant (i.e., chromium) because the polyvalent colorant is reduced by the carbon. Compared to the changes in CIE a* and b* values between Examples 9 and 10, the changes in CIE a* and b* values between Examples 10 and 11 are less pronounced. This suggests that the molar ratio of the polyvalent colorant may be more reactive to chromium at lower amounts of carbon (e.g., from about 0.001 wt % to about 0.005 wt %) than at higher amounts of carbon (e.g., more sensitive to marginal changes at lower amounts of carbon), but other polyvalent colorants may have different sensitivities and / or other source materials may have increased sensitivity to other amounts of carbon. For example, for this concentration of chromium and the precursor redox ratio associated with this chromium source, a relatively low amount of carbon may be sufficient to reduce substantially all of the chromium from the 6+ oxidation state to the 3+ oxidation state; however, higher concentrations of chromium, other multivalent colorants, and / or other precursor materials having different precursor redox ratios may have significant reactions at other concentration ranges of carbon.

[0288] Table 6: Composition and properties of Examples 7-11

[0289] Examples 7 8 9 10 11 <![CDATA[Cr2O3(ppm)]]> 370 370 375 390 370 Nitrate (weight %) 0.29 0 0 0 0 Carbon (weight %) 0 0 0.001 0.005 0.010 L* 93.2 93.2 93.55 93.6 93.65 a* -3.7 -2.95 -3.6 -3.25 -3.25 b* 10.4 5.8 7.0 5.0 4.85

[0290] Table 7: Composition and properties of Examples 12-18

[0291]

[0292]

[0293] Figure 10-15 Schematic representation of cross sections of examples including different amounts and types of clarifiers. Figure 10 Corresponding to a composition without a nitrate source, a sulfate source and a sodium chloride source. Figure 11 This corresponds to a composition containing approximately 0.2% by weight of the nitrate source in the precursor material. Figure 13 Contains 0.2% by weight of sodium chloride. Figure 10-11 and 13 contain many bubbles 1001, 1101 and 1301. Figure 12 Corresponding to Example 18, the precursor material contained 0.2 wt% of a sulfate source. Figure 12 As shown in Figure 10-11 Compared to Example 13, the sulfate source can be reduced (e.g., bubbles are eliminated). Examples 16-17 include 0.05 wt. % or 0.10 wt. % of the sulfate source in the precursor material, respectively. Although not shown, Examples 16-17 are visually free of bubbles, which is consistent with Example 18 (e.g., Figure 12 as shown in ). Figure 14-15 Corresponding to Examples 13-14, respectively, 0.01 wt% or 0.02 wt% of the sulfate source was included in the precursor material. Figure 14-15 Both exhibit multiple bubbles; however, Figure 10 Compared with the bubbles 1001 in the sample, the bubbles 1401 are larger, indicating that sulfate promotes the coalescence of bubbles; and Figure 15 Show more Figure 14 Fewer bubbles 1501 indicate that bubbles are removed due to the additional amount of sulfate-containing source material.

[0294] Table 7 presents the amount of sulfate source in the precursor material in Examples 12-18 and the characteristics of the resulting glass products. Examples 13-14 have a large amount of bubbles and / or blisters, which may interfere with the measurement of CIE color coordinates. Visually, it appears that Examples 13-14 with 0.01 wt % to 0.02 wt % sulfate source have colors substantially identical to Example 12. For Examples 15-18 (compared to Example 12), as the amount of sulfate source increases, CIE a* values decrease (from -4.25 to -5.0) and CIE b* values increase (from 4.55 to 7.35). This shows that providing sulfate in the precursor material and / or increasing the amount of source sulfate in the precursor material will reduce the molar ratio of the resulting glass product because sulfate oxidizes the multivalent colorant (chromium). Comparing Examples 12-14 with Examples 15-18, it appears that after a threshold amount of sulfate is reached, e.g., after sufficient sulfate source is present to remove air bubbles, the color and precursor ratio change. It should be understood that other fining agents are expected to have similar effects, which may also have an oxidizing effect.

[0295] Table 8 presents the amount of iron (e.g., Fe2O3) and CIE color coordinates for Examples 19-24. The amount of iron increased from Example 19 to Example 24, ranging from 190 ppm to 590 ppm. As shown in the figure, as the amount of iron increased, the CIE a* value increased and the CIE b* value decreased. This shows that iron can increase the molar ratio of a polyvalent colorant (e.g., chromium) because iron can reduce the polyvalent colorant. In addition, for iron exceeding 500 ppm, the sensitivity of the CIE a* and b* values to iron decreases. This shows that the molar ratio of the polyvalent colorant can have a stronger reaction to chromium at lower amounts of iron (e.g., 190 ppm to 500 ppm) than at higher amounts of iron (e.g., more sensitive to marginal changes at lower amounts of iron), but the sensitivity of other polyvalent colorants may be different and / or other source materials may have increased sensitivity to other amounts of iron. For example, for this concentration of chromium and the precursor redox ratio associated with this chromium source, relatively low amounts of iron may be sufficient to reduce substantially all of the chromium from the 6+ oxidation state to the 3+ oxidation state; however, higher concentrations of chromium, other multivalent colorants, and / or other precursor materials having different precursor redox ratios may have significant reactions at other concentration ranges of iron.

[0296] Figure 16 The percent transmittance of different glass articles is plotted on the vertical axis 1603 at the wavelength of light (in nm) on the horizontal axis 1601. Curve 1605 corresponds to Example 20, curve 1607 corresponds to Example 22, curve 1609 corresponds to Example 23, and curve 1611 corresponds to Example 24. As shown, as the amount of iron increases, the transmittance of blue light and ultraviolet light increases; however, as the amount of iron increases, the transmittance at red light wavelengths (e.g., about 550 nm to about 700 nm) decreases.

[0297] Table 8: Composition and properties of Examples 19-24

[0298] Examples 19 20 21 22 23 24 <![CDATA[Cr2O3(ppm)]]> 510 510 500 500 495 495 <![CDATA[Fe2O3(ppm)]]> 190 230 310 390 500 590 L* 89.48 89.28 88.78 88.72 88.86 88.92 a* -5.0 -4.80 -4.75 -4.4 -4.3 -4.25 b* 10.8 8.7 7.0 5.0 3.8 3.7

[0299] Table 9: Composition and properties of Examples 25-30

[0300] Examples 25 26 27 28 29 30 Cr2O3 (weight %) 700 750 700 720 750 760 ZnO (weight %) 0.35 0.68 1.07 0.35 0.68 1.07 Nitrate (weight %) 0 0 0 0.1 0.1 0.1 L* 90.7 90.1 90.3 89.65 89.8 89.6 a* -7.55 -7.95 -8.0 -10.7 -10.55 -10.6 b* 7.65 8.4 8.15 20.5 20.5 20.25

[0301] Table 9 presents the amount of zinc (ZnO) and CIE color coordinates for Examples 25-30. The precursor materials of Examples 28-30 do not contain nitrates, while Examples 25-27 include NaNO as a nitrate source. Comparing Examples 25-27 with Examples 28-30, adding a nitrate source to the precursor material reduces the CIE a* value by more than 2.5 and increases the CIE b* value by more than 12. This is more obvious than Examples 7-8, but consistent with the trend observed here. Although not shown, when adding a considerable amount of nitrate KNO in weight percentage instead of NaNO, a similar but lower effect is observed. Compared with using only a nitrate source, adding zinc can increase the magnitude (e.g., absolute value) of the precursor ratio conversion. In the absence of a nitrate source, increasing the amount of zinc (ZnO) from 0.35 wt % to 0.68 wt % (Examples 25-26) reduces the CIE a* value by 0.45 and increases the CIE b* value by about 0.75. However, further increasing the amount of zinc (ZnO) beyond 0.68 wt% (Examples 26 to 27) had a relatively modest effect on the CIE color coordinates (and the molar ratio of the polyvalent colorant). In the presence of a nitrate source (Examples 28-30), the CIE color coordinates (and the molar ratio of the polyvalent colorant) were largely insensitive to changes in the amount of ZnO from 0.35 wt% to 1.07 wt%.

[0302] Table 10 presents the amounts of antimony, cobalt, and chromium, as well as the CIE color coordinates, for Examples 31-35. The amounts of chromium and cobalt were substantially the same for Examples 31-35. As the amount of antimony increased, the CIE L* value increased, the CIE a* value increased, and the CIE b* value decreased. This indicates that adding an antimony source increases the molar ratio of the polyvalent colorant (i.e., chromium) because the polyvalent colorant is reduced by antimony. Furthermore, the marginal change (i.e., sensitivity) in the CIE color coordinates (and the molar ratio of the polyvalent colorant) to changes in antimony concentration was greater at antimony levels less than 500 ppm than at higher amounts of antimony. For example, for this concentration of chromium and the precursor redox ratio associated with this chromium source, a relatively low amount of antimony (e.g., less than 500 ppm) may be sufficient to reduce substantially all of the chromium from the 6+ oxidation state to the 3+ oxidation state; however, higher concentrations of chromium, other polyvalent colorants, and / or other precursor materials with different precursor redox ratios may have a significant reaction at other antimony concentration ranges.

[0303] Table 10: Composition and properties of Examples 31-35

[0304] Examples 31 32 33 34 35 <![CDATA[Cr2O3(ppm)]]> 453 454 451 450 449 <![CDATA[Co3O4(ppm)]]> 48 46 48 49 50 <![CDATA[Sb2O3(ppm)]]> 64 270 480 990 1530 L* 90.7 90.9 91.0 91.1 91.15 a* -4.4 -4.0 -3.8 -3.75 -3.70 b* 9.45 7.0 5.6 5.15 5.00

[0305] Table 11: Composition and properties of Examples 36-41

[0306] Examples 36 37 38 39 40 41 <![CDATA[Cr2O3(ppm)]]> 780 740 750 740 770 760 <![CDATA[Co3O4(ppm)]]> 0 0 0 0 0 0 <![CDATA[Sb2O3(ppm)]]> 2400 4800 7300 2400 4800 7300 L* 90.3 90.75 90.35 90.15 90.35 89.8 a* -8.25 -7.6 -8.05 -8.15 -8.05 -8.95 b* 8.15 7.5 8.0 8.35 8.1 8.8

[0307] Table 11 presents the amounts of antimony, cobalt, and chromium and the CIE color coordinates for Examples 36-41. Examples 31-35 were pulled down, while Examples 36-41 were formed in a Pt crucible and quenched to form glass products. The amount of antimony in Examples 36-41 was greater than that in Examples 31-35. At these higher amounts of antimony in Examples 36-41, there was no significant trend toward further increasing the amount of antimony. Examples 36-38 did not include a nitrate source in the precursor material, while Examples 39-41 included NaNO3 as a nitrate source in the precursor material. Comparing Examples 36-38 with Examples 39-41, the inclusion of a nitrate source reduced the CIE L* value, decreased the CIE a* value, and increased the CIE b* value. This trend is consistent with the trend observed above for the addition of a nitrate source.

[0308] Table 12 presents the source of the polyvalent colorant (chromium), the cooling rate of the melt from 1500°C to 1400°C, and the CIE values of the resulting glass products. "Quenching" means pouring the melt from the crucible without controlling the cooling rate. Examples 42-44 included source AA. For Examples 42-44, reducing the cooling rate from quenching to 2°C / min and then to 0.5°C / min decreased the CIE L* value and decreased the CIE b* value. Examples 45-47 included source BB. For Examples 45-47, reducing the cooling rate from quenching to 2°C / min and then to 0.5°C / min did not significantly change the CIE color coordinates. Examples 48-50 included source CC. For Examples 48-50, reducing the cooling rate from quenching to 2°C / min and then to 0.5°C / min increased the CIE L* value, increased the CIE a* value, and decreased the CIE b* value. Notably, in Examples 48-49, reducing the cooling rate from 2°C / min to 0.5°C / min had a significant effect on the CIE b* value. The extent to which varying the cooling rate affected the CIE color coordinates (and molar ratio) varied depending on the source material of the polyvalent colorant (chromium). This suggests that precursor materials with different precursor molar ratios will be affected differently by the various factors discussed herein (e.g., cooling rate, other components). For example, a precursor material with a low precursor molar ratio may not be significantly affected by a reduction in cooling rate (which can oxidize the polyvalent colorant), while another precursor material with a higher precursor molar ratio may be significantly reduced by the same change in cooling rate. Similarly, a precursor material with a high precursor molar ratio may not be significantly affected by an increase in cooling rate (which can prevent oxidation of the polyvalent colorant), while another precursor material with a lower precursor molar ratio may be significantly increased by the same change in cooling rate.

[0309] Table 12: Composition and properties of Examples 42-50

[0310]

[0311]

[0312] Tables 13-21 present the compositions and color coordinates of Examples 51-222. Unless otherwise specified, in addition to the components of each example described in Tables 13-21, Examples 51-222 also include Composition A, which contains about 60.9 mol% SiO2, about 14.7 mol% Al2O3, about 6.0 mol% B2O3, about 9.0 mol% Li2O, about 2.0 mol% Na2O, about 4.5 mol% MgO, and about 1.5 mol% CaO (e.g., about 57.7 wt% SiO2, about 23.7 wt% Al2O3, about 6.6 wt% B2O3, about 4.2 wt% Li2O, about 0.3 wt% KO, about 2.9 wt% MgO, and about 1.3 wt% CaO). For Examples 51-222, potassium was provided as potassium nitrate, while the other components were provided as oxides or carbonates. The redox ratio of the colorant package can be varied by varying the amount of nitrate (e.g., varying the amount of potassium added in the form of potassium nitrate), by adding tin (SnO2), and / or by varying the presence and / or amount of redox couples (e.g., Fe2O3, MnO2). Additionally, varying the amount of polyvalent colorant and the concentration of the polyvalent colorant can produce different redox ratios. Examples 51-62 comprise a nominal thickness of 3.6 mm. Examples 63-222 were formed in a Pt crucible and quenched to form the glass article, while Examples 51-62 were formed by a down-draw process. Unless otherwise indicated in Tables 13-21, the compositions are in mol% of the glass article, with values in weight % indicated by "(wt)" in the row labels.

[0313] Table 13: Composition and properties of Examples 51-62

[0314]

[0315]

[0316] Examples 59 60 61 62 NiO 0 0 0 0 <![CDATA[CeO2]]> 0.26 0.71 0.29 0.26 <![CDATA[Co3O4]]> 0 0 0 0 <![CDATA[TiO2]]> 0.40 0.009 0.009 0.70 <![CDATA[MnO2]]> 0.71 0.43 1.07 0.40 NiO(wt) 0 0 0 0 <![CDATA[CeO2(wt)]]> 1.91 0.71 1.89 0.76 <![CDATA[Co3O4(wt)]]> 0 0 0 0 <![CDATA[TiO2(wt)]]> 0.49 0.011 0.011 0.87 <![CDATA[MnO2(wt)]]> 0.95 0.58 1.45 0.54 L* 93.11 90.47 92.41 94.02 a* 0.3 1.2 0.06 0.16 b* 8.6 12.9 10.7 6.31

[0317] Table 14: Composition and properties of Examples 63-72

[0318]

[0319] Table 13 presents the colorant packages and CIE color space coordinates for Examples 51-62. Examples 51-59 include at least two polyvalent colorants, namely NiO and TiO2 (where Examples 51-59 also include Co3O4). Examples 54-58 also include CeO2 as another polyvalent colorant. SnO2 is not listed in Table 13 because Examples 51-58 do not contain any tin. Examples 59-62 contain both CeO2 and TiO2 as polyvalent colorants, as well as MnO2. Examples 51-56 and Examples 59-62 have a*>0 and b*>0. Examples 51-58 and Examples 60-61 have b*>10.

[0320] Table 14 presents the colorant packages and CIE color space coordinates for Examples 63-72. Examples 63-72 include two multivalent colorants (i.e., NiO and TiO2) and Fe2O3 as a redox pair. Examples 63-72 include a*Fe2O30 and b*>0, while Examples 64-72 include b*≥10.

[0321] Table 15 presents the colorant packages and CIE color space coordinates for Examples 73-126. Examples 73-126 include NiO and TiO2 (wherein Examples 73-126 also include Co3O4) and Fe2O3 as a redox pair and optionally include SnO2. Examples 73-126 include a*<0. In addition to a*<0, Examples 73-75, Examples 77-86, and Example 88 also include b*<0. In addition to a*<0, Examples 76, Example 87, and Examples 89-126 also include b*>0.

[0322] Table 15: Composition and properties of Examples 73-126

[0323]

[0324]

[0325]

[0326]

[0327] Table 16: Composition and properties of Examples 127-138

[0328]

[0329]

[0330] Table 16 presents the colorant packages and CIE color space coordinates for Examples 127-133. As described above, Examples 127-133 were formed in a Pt crucible. Examples 127-133 included NiO and TiO2 (where Examples 127-133 also included Co3O4) and Fe2O3 as a redox pair and optionally included SnO2. Examples 127-133 included a*<0 and b*<0.

[0331] Table 17 presents the colorant packages and CIE color space coordinates for Examples 139-152. As described above, Examples 139-152 were formed in a Pt crucible. Examples 139-152 included three polyvalent colorants (i.e., NiO, TiO2, and CeO2) and Fe2O3 as a redox pair, and optionally included SnO2. Examples 139-150 included a* < 0 and b* > 0. Examples 140, Examples 142-143, Examples 146-148, and Example 151 included b* > 10. Examples 151-152 included a* > 0 and b* > 0.

[0332] Table 18 presents the colorant packages and CIE color space coordinates for Examples 153-166. As described above, Examples 153-166 were formed in a Pt crucible. Examples 153-166 included three polyvalent colorants (i.e., NiO, TiO2, and CeO2) and Fe2O3 as a redox pair and optionally included SnO2. Examples 153-159, 161, 163, and 165-166 also included Co3O4 as an additional polyvalent colorant. Examples 153-166 included a*<0 and b*>0. Examples 155 and 159-166 included b*>10.

[0333] Table 17: Composition and properties of Examples 139-152

[0334]

[0335] Table 18: Composition and properties of Examples 153-166

[0336]

[0337]

[0338] Table 19: Composition and properties of Examples 167-174

[0339]

[0340]

[0341] Table 19 presents the colorant packages and CIE color space coordinates for Examples 167-174. As described above, Examples 167-174 were formed in a Pt crucible. Examples 167-174 included TiO2 and CeO2 as polyvalent colorants, as well as Fe2O3 and MnO2 as redox pairs, and optionally included SnO2. Examples 167-174 included a*<0 and b*>0.

[0342] Table 20 presents the colorant packages and CIE color space coordinates for Examples 175-205. As described above, Examples 175-205 were formed in a Pt crucible. Examples 175-205 included three polyvalent colorants (i.e., NiO, TiO2, and Co3O4) as well as Fe2O3 and MnO2 as redox pairs and optionally included SnO2. Examples 175-205 included a* < 0. Examples 175-177, 179-190, 194, and 197 included b* > 0 and a* < 0. Example 178, 192-193, 195-196, and 198-205 included b* < 0 and a* < 0.

[0343] Table 20: Composition and properties of Examples 175-205

[0344]

[0345]

[0346]

[0347] Table 21: Composition and properties of Examples 206-222

[0348]

[0349]

[0350] Table 21 presents the colorant packages and CIE color space coordinates for Examples 206-222. As described above, Examples 206-222 were formed in a Pt crucible. Examples 206-222 included three polyvalent colorants (i.e., NiO, TiO2, and Co3O4) as well as Fe2O3 and MnO2 as redox pairs, and optionally included SnO2. Examples 206-222 included a* < 0. Examples 206, 209-209, and 213 included b* > 0 and a* < 0. Examples 207, 210-212, and 214-222 included b* < 0 and a* < 0.

[0351] The above observations can be combined to provide glass articles comprising polyvalent colorants and pre-colored glass housings containing the glass articles. The glass articles can exhibit high brightness (e.g., CIE L* values greater than 50 or greater than 70 and less than 96.5) colors. A predetermined color of the glass article and / or pre-colored glass can be achieved by controlling the amount of the reduced form of the polyvalent colorant relative to the oxidized form of the polyvalent colorant. Furthermore, by controlling the molar ratio of the reduced form of the polyvalent colorant to the total amount of the polyvalent colorant, colors that were previously unattainable from a given colorant package can be achieved.

[0352] 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., chemically strengthened) that can provide improved crack resistance, puncture resistance, impact resistance, and / or improved flexural strength. Furthermore, minimizing the combination of RO, CaO, MgO, and ZnO in the glass composition can result in a colored glass article having a desirable dielectric constant, for example, when the colored glass article is used as part of an electronic device housing. A dielectric constant of 5.6 to 6.4 at frequencies between 10 GHz and 60 GHz can enable wireless communication through the glass article.

[0353] Providing a natural glass housing with a colored glass article eliminates the need for an additional layer to add color to the housing, which can simplify assembly and provide a more consistent color. Thus, a natural glass housing including a glass article can provide an aesthetically pleasing appearance (e.g., color) while protecting the electronic device from damage and / or allowing wireless communication therethrough.

[0354] The method comprises forming a glass article from a precursor material comprising a polyvalent colorant, wherein the molar ratio of the precursor of the polyvalent colorant is different from the molar ratio of the polyvalent colorant in the resulting glass article. The molar ratio can be reduced by, for example, including a nitrate source, a sulfate source, a zinc source, or a combination thereof in the precursor material. The molar ratio can be increased by, for example, including a carbon source, an iron source, an antimony source, or a combination thereof in the precursor material. Adjusting the cooling rate of the melt formed by melting the precursor material can also be used to control the molar ratio of the polyvalent colorant. Controlling the molar ratio of the polyvalent colorant enables the glass article to reliably produce a predetermined color (e.g., CIE color coordinates). Controlling the molar ratio of the polyvalent colorant can increase the color gamut and / or resolution of the color obtained by a predetermined colorant package comprising the polyvalent colorant.

[0355] As used herein, directional terms such as up, down, right, left, front, back, top, bottom, are made with reference only to the drawings as drawn and are not intended to imply an absolute orientation.

[0356] It should be understood that the various aspects disclosed may involve features, elements or steps described in conjunction with the aspects. It should also be understood that although features, elements or steps are described with respect to one aspect, they can be interchanged or combined with alternative aspects in various combinations or arrangements not shown.

[0357] It should also be understood that, as used herein, the terms "the," "a," or "an" mean "at least one," and should not be limited to "only one" unless clearly indicated to the contrary. For example, reference to "a component" includes aspects having two or more such components unless the context clearly indicates otherwise. Similarly, "plurality" is intended to mean "more than one."

[0358] As used herein, the term "about" means that amount, size, formula, parameter and other quantity and feature are not exact and do not have to be exact, but can be approximate and / or larger or smaller as needed, thereby reflecting tolerance, conversion factor, rounding, measurement error and other factors known to those skilled in the art. In this article, ranges can be expressed as from "about" a specific value and / or to "about" another specific value. When such a range is expressed, each aspect includes from the specific value and / or to the other specific value. Similarly, when a value is expressed as an approximate value by using the antecedent "about", it should be understood that the specific value forms another aspect. Regardless of whether the numerical value or range endpoint in the specification states "about", the numerical value or range endpoint is intended to include two aspects: one modified by "about" and one not modified by "about". It should also be understood that the endpoint of each range is meaningful relative to the other endpoint and independently of the other endpoint.

[0359] As used herein, the terms "substantially," "substantially," and variations thereof are intended to indicate that the characteristic being described is equal to or approximately equal to a value or description. For example, a "substantially flat" surface is intended to indicate a flat or approximately flat surface. Furthermore, as defined above, "substantially similar" is intended to indicate that two values are equal or approximately equal. In various aspects, "substantially similar" can mean values that are within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

[0360] Unless otherwise expressly stated, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a specific order. Therefore, if a method claim does not actually recite the order in which its steps are to be followed, or if the steps are not otherwise specifically recited in the claims or specification as being limited to a specific order, no specific order is intended to be inferred.

[0361] Although the transition phrase "comprising" may be used to disclose various features, elements, or steps of a particular aspect, it should be understood that alternative aspects are implicitly included, including those aspects that may be described using the transition phrases "consisting of" or "consisting essentially of. Thus, for example, a device comprising A+B+C implicitly includes alternative aspects where the device consists of A+B+C and where the device consists essentially of A+B+C. Unless otherwise indicated, as used herein, the terms "comprising" and "including" and variations thereof should be understood to be synonymous and open-ended.

[0362] The above-described aspects and features of these aspects are exemplary and may be provided alone or in any combination with any one or more features of the other aspects provided herein without departing from the scope of the present disclosure.

[0363] It is obvious to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the present disclosure. Therefore, the present disclosure is intended to cover modifications and variations of all aspects herein, provided that they are within the scope of the appended claims and their equivalents.

Claims

1. A method for manufacturing a housing for a consumer electronic device, comprising: melting the precursor materials together to form the glass article, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, the precursor material comprises the multivalent colorant, the multivalent colorant being a metal selected from the group consisting of cerium, titanium, cobalt, copper, nickel, vanadium, chromium, and combinations thereof, and a precursor molar ratio of the oxidized form of the multivalent colorant in the precursor material to the sum of the oxidized and reduced forms of the multivalent colorant in the precursor material is different from a molar ratio of the oxidized form of the multivalent colorant in the glass article to the sum of the oxidized and reduced forms of the multivalent colorant in the glass article.

2. The method of claim 1, wherein the absolute value of the difference between the precursor molar ratio of the precursor material and the molar ratio of the glass article is from about 0.1 to about 0.

5.

3. The method of any one of claims 1 to 2, wherein the precursor molar ratio of the precursor material is greater than the molar ratio of the glass article.

4. The method according to any one of claims 1 to 3, wherein the precursor material further comprises 0.02 wt% or more of a sulfate source, a nitrate source, a zinc source, or a combination thereof.

5. The method of claim 4, wherein the precursor material comprises 0.1 wt% to 0.3 wt% of the sulfate source.

6. The method of any one of claims 4 to 5, wherein the precursor material comprises 0.25 wt% to about 1 wt% of the zinc source.

7. The method according to any one of claims 1 to 6, wherein the precursor material further comprises 0.05 wt% or more of a nitrate source.

8. The method of claim 7, wherein the precursor material comprises 0.1 wt% to 3 wt% of the nitrate source.

9. The method of any one of claims 1 to 2, wherein the molar ratio of the glass article is greater than the precursor molar ratio of the precursor material.

10. The method of claim 9, wherein the precursor material comprises about 0.01 wt% or more of an antimony source, an iron source, or a combination thereof.

11. The method of claim 10, wherein the precursor material comprises 300 ppm to about 1,300 ppm of the iron source.

12. The method of any one of claims 1 to 2 or 10 to 11, wherein the precursor material comprises 0.01 wt% to about 0.5 wt% of an antimony source.

13. The method of any one of claims 1 to 2 or 10 to 12, wherein the precursor material comprises 0.004 wt% to about 0.05 wt% of a carbon source.

14. The method of any one of claims 1 to 13, wherein melting the precursor material comprises heating the precursor material to a first temperature of about 1500° C. or higher to form a melt, and cooling the melt from the first temperature to about 1400° C. at a predetermined rate, and subsequently forming the glass article from the melt.

15. The method of claim 14, wherein the predetermined rate is about 0.5°C / min or higher.

16. The method of any one of claims 14 to 15, wherein the predetermined rate is about 0.5°C / min to about 2°C / min.

17. The method of any one of claims 14 to 16, further comprising exposing the melt to an atmosphere comprising an oxygen partial pressure of about 25 kilopascals or greater.

18. The method of any one of claims 14 to 17, wherein the precursor material comprises an iron source, a zinc source, or a combination thereof.

19. The method according to any one of claims 1 to 18, wherein the polyvalent colorant is chromium.

20. The method of any one of claims 1 to 19, further comprising disposing the glass article on a reflector layer, the reflector layer being opaque and having a CIE L* value of 70 or greater.

21. The method of any one of claims 1 to 20, wherein the glass article has an absolute value of a CIE a* value of about 0.3 or greater, and the glass article has an absolute value of a CIE b* value of about 0.2 or greater.

22. The method of any one of claims 1 to 20, wherein the glass article has a CIE a* value of less than -3.

23. The method of any one of claims 1 to 20, wherein the glass article has a CIE b* value greater than 5.

24. The method of any one of claims 1 to 23, wherein the glass article has a CIE L* value of 70 or greater.

25. The method of any one of claims 1 to 24, wherein the molar ratio of the reduced form to the sum of the reduced form and the oxidized form in the glass article is from 0.5 to 0.

9.

26. A primary color glass housing for a consumer electronic device, the primary color glass housing comprising a glass article, the glass article including a thickness defined between a first major surface and a second major surface, the second major surface opposite the first major surface, the thickness being 200 μm to 5 mm, wherein the glass article comprises a silicate glass having a multivalent colorant, the multivalent colorant having a reduced form and an oxidized form, a molar ratio of the reduced form to the sum of the reduced form and the oxidized form of the multivalent colorant being 0.3 to 0.9, and a total transmittance through the thickness of at least one 10 nm band in the wavelength range of 380 nm to 750 nm being 3% to 80%.

27. The natural glass envelope of claim 26, further comprising a reflector layer covering the second major surface, the reflector layer being opaque and having a CIE L* value of 70 or greater.

28. The natural glass enclosure according to any one of claims 26 to 27, wherein the absolute value of the CIE a* value of the glass article is about 0.3 or greater, and the absolute value of the CIE b* value of the glass article is about 0.2 or greater.

29. The natural glass enclosure according to any one of claims 26 to 28, wherein the glass article has a CIE a* value of less than -3.

30. The natural colored glass enclosure according to any one of claims 26 to 29, wherein the glass article has a CIE b* value greater than 5.

31. The natural glass enclosure of any one of claims 26 to 30, wherein the glass article has a CIE L* value of 70 or greater.

32. The natural glass enclosure of any one of claims 26 to 31, wherein the molar ratio of the reduced form to the sum of the reduced form and the oxidized form is 0.5 to 0.

9.

33. The natural glass enclosure according to any one of claims 26 to 32, wherein the glass article further comprises 200 ppm or more of Fe2O3.

34. The natural glass enclosure of claim 33, wherein the glass article comprises 300 ppm to about 600 ppm Fe2O3.

35. The natural glass enclosure of any one of claims 26 to 34, wherein the glass article comprises 0.25 wt% to about 1 wt% ZnO.

36. The natural glass enclosure of any one of claims 26 to 35, wherein the glass article comprises 0.01 wt% to about 0.5 wt% Sb2O3.

37. The primary colored glass envelope of any one of claims 26 to 36, wherein the multivalent colorant is a metal selected from the group consisting of cerium, titanium, cobalt, copper, nickel, vanadium, chromium, and combinations thereof.

38. The natural glass enclosure of claim 37, wherein the multivalent colorant is chromium.

39. The natural glass enclosure of any one of claims 26 to 38, wherein the glass article comprises, in mol % of the glass article: about 50 mol % to about 75 mol % SiO2; about 7 mol% to about 20 mol% Al2O3; from about 10 mol% to about 20 mol% of at least one alkali metal oxide, the alkali metal oxide comprising Li2O, Na2O, and K2O; 0.001 mol % to about 1 mol % of said polyvalent colorant; and At least one of B2O3 or P2O5.

40. The natural glass enclosure of any one of claims 26 to 38, wherein the glass article comprises, in mol % of the glass article: 60 mol% to 65 mol% SiO2; 12 mol% to 17 mol% Al2O3; 3 mol% to 6 mol% B2O3; 10 mol% to 16 mol% of at least one alkali metal oxide, the alkali metal oxide comprising Li2O, Na2O, and K2O; 3 mol% to 5 mol% CaO; 0 mol% to 1 mol% ZrO2; 0 mol% to 0.25 mol% SnO2; and 0.005 mol% to about 0.2 mol% of said multivalent colorant.

41. A natural glass enclosure according to any one of claims 26 to 40, wherein the glass article comprises at least one crystalline phase.

42. The natural glass housing according to claim 41, wherein the crystallinity of the glass article is 10 wt% or less.

43. The natural glass envelope according to any one of claims 26 to 42, further comprising a first compressive stress region extending from the first compressive stress region to a first compression depth.

44. The natural glass envelope of claim 43, wherein the maximum compressive stress of the first compressive stress region is about 400 MPa or greater.

45. The natural glass enclosure of any one of claims 26 to 44, wherein the glass article has a dielectric constant of about 5.6 to about 6.4 at a frequency of 10 to 60 GHz.

46. A natural glass enclosure according to any one of claims 26 to 45, wherein the glass article exhibits a 0.60 MPa mm 1 / 2 or higher fracture toughness and a Young's modulus of about 50 GPa to about 100 GPa.

47. The primary color glass housing according to any one of claims 26 to 46, further comprising: A circuit comprising an antenna that transmits a signal in the range of 26 GHz to 40 GHz; the primary colored glass housing at least partially surrounding the circuit; as well as a structure formed as an integral part of the glass article, wherein the structure includes a perimeter delimiting a second thickness of the structure, the second thickness differing from a thickness of the glass article by at least 150 μm, The antenna is positioned and oriented so that the signal is transmitted through the structure of the glass sheet of the panel of the housing.

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