COLORED GLASS ARTICLES HAVING IMPROVED MECHANICAL DURABILITY
20220402806 · 2022-12-22
Inventors
- Xiaoju Guo (Pittsford, NY, US)
- Karl William Koch, III (Elmira, NY, US)
- Liping Xiong Smith (Painted Post, NY, US)
Cpc classification
C03C21/00
CHEMISTRY; METALLURGY
C03C21/002
CHEMISTRY; METALLURGY
International classification
C03C21/00
CHEMISTRY; METALLURGY
Abstract
A colored glass article includes greater than or equal to 50 mol % and less than or equal to 70 mol % SiO.sub.2, greater than or equal to 10 mol % and less than or equal to 17.5 mol % Al.sub.2O.sub.3, greater than or equal to 3 mol % and less than or equal to 10 mol % B.sub.2O.sub.3, greater than or equal to 8.8 mol % and less than or equal to 14 mol % Li.sub.2O, greater than or equal to 1.5 mol % and less than or equal to 8 mol % Na.sub.2O, and greater than 0 mol % and less than or equal to 2 mol % Cr.sub.2O.sub.3. R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 0.5 mol % and less than or equal to 6 mol %. Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to 12 mol % and less than or equal to 22 mol %.
Claims
1. A colored glass article comprising: greater than or equal to 50 mol % and less than or equal to 70 mol % SiO.sub.2; greater than or equal to 10 mol % and less than or equal to 17.5 mol % Al.sub.2O.sub.3; greater than or equal to 3 mol % and less than or equal to 10 mol % B.sub.2O.sub.3; greater than or equal to 8.8 mol % and less than or equal to 14 mol % Li.sub.2O; greater than or equal to 1.5 mol % and less than or equal to 8 mol % Na.sub.2O; and greater than 0 mol % and less than or equal to 2 mol % Cr.sub.2O.sub.3herein: R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 0.5 mol % and less than or equal to 6 mol %, wherein R.sub.2O is the sum of Li.sub.2O, Na.sub.2O, and K.sub.2O and RO is the sum of MgO, ZnO, and Ca0; and Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to 12 mol % and less than or equal to 22 mol %.
2. The colored glass article of claim 1, wherein the colored glass article has a transmittance color coordinate in the CIELAB color space, as measured at an article thickness of 1.5 mm under F2 illumination and a 10° standard observer angle, of: L* greater than or equal to 0 and less than or equal to 100; a* greater than or equal to −18 and less than or equal to 0; and b* greater than or equal to 0 and less than or equal to 82.
3. The colored glass article of claim 1, wherein MgO+ZnO is greater than or equal to 0 mol % and less than or equal to 4.5 mol %.
4. The colored glass article of claim 1, wherein R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 1 mol % and less than or equal to 5.5 mol %.
5. The colored glass article of claim 1, wherein Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to is greater than or equal to 13 mol % and less than or equal to 21.5 mol %.
6. The colored glass article of claim 1, wherein the colored glass article comprises greater than or equal to 0.001 mol % and less than or equal to 1.5 mol % Cr.sub.2O.sub.3.
7. The colored glass article of claim 1, wherein the colored glass article comprises greater than or equal to 12 mol % and less than or equal to 17.25 mol % Al.sub.2O.sub.3.
8. The colored glass article of claim 1, wherein the colored glass article comprises greater than or equal to 3.5 mol % and less than or equal to 9 mol % B.sub.2O.sub.3.
9. The colored glass article of claim 1, wherein the colored glass article comprises NiO, CuO, Co.sub.3O.sub.4, or combinations thereof.
10. The colored glass article of claim 1, wherein the colored glass article has a K.sub.1C fracture toughness as measured by a chevron notch short bar method of greater than or equal to 0.7 MPa*m.sup.0.5.
11. The colored glass article of claim 1, wherein the colored glass article is a chemically strengthened glass article.
12. The colored glass article of claim 11, wherein the colored glass article has a surface compressive stress greater than or equal to 300 MPa.
13. The colored glass article of claim 11, wherein the colored glass article has a maximum central tension greater than or equal to 40 MPa.
14. The colored glass article of claim 11, wherein the colored glass article has a depth of compression greater than or equal to 0.15t.
15. A glass composition comprising: greater than or equal to 50 mol % and less than or equal to 70 mol % SiO.sub.2; greater than or equal to 10 mol % and less than or equal to 17.5 mol % Al.sub.2O.sub.3; greater than or equal to 3 mol % and less than or equal to 10 mol % B.sub.2O.sub.3; greater than or equal to 8.8 mol % and less than or equal to 14 mol % Li.sub.2O; greater than or equal to 1.5 mol % and less than or equal to 8 mol % Na.sub.2O; and greater than 0 mol % and less than or equal to 0.2 mol % Cr.sub.2O.sub.3, wherein: R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 0.5 mol % and less than or equal to 6 mol %, wherein R.sub.2O is the sum of Li.sub.2O, Na.sub.2O, and K.sub.2O and RO is the sum of MgO, ZnO, and CaO; and Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to 12 mol % and less than or equal to 22 mol %.
16. The glass composition of claim 15, wherein MgO+ZnO is greater than or equal to 0 mol % and less than or equal to 4.5 mol %.
17. The glass composition of claim 15, wherein R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 1 mol % and less than or equal to 5.5 mol %.
18. The glass composition of claim 15, wherein Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to is greater than or equal to 14 mol % and less than or equal to 20 mol %.
19. The glass composition of claim 15, wherein the glass composition comprises greater than or equal to 0.001 mol % and less than or equal to 1.5 mol % Cr.sub.2O.sub.3.
20. The glass composition of claim 15, wherein the glass composition comprises greater than or equal to 12 mol % and less than or equal to 17 mol % Al.sub.2O.sub.3.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0076] Reference will now be made in detail to various embodiments of glass compositions and colored glass articles formed therefrom having a desired color. According to embodiments, a colored glass article includes greater than or equal to 50 mol % and less than or equal to 70 mol % SiO.sub.2, greater than or equal to 10 mol % and less than or equal to 17.5 mol % Al.sub.2O.sub.3, greater than or equal to 3 mol % and less than or equal to 10 mol % B.sub.2O.sub.3, greater than or equal to 8.8 mol % and less than or equal to 14 mol % Li.sub.2O, greater than or equal to 1.5 mol % and less than or equal to 8 mol % Na.sub.2O, and greater than 0 mol % and less than or equal to 2 mol % Cr.sub.2O.sub.3. R.sub.2O+RO−Al.sub.2O.sub.3 is greater than or equal to 0.5 mol % and less than or equal to 6 mol %. R.sub.2O is the sum of Li.sub.2O, Na.sub.2O, and K.sub.2O and RO is the sum of MgO, ZnO, and CaO. Al.sub.2O.sub.3+MgO+ZnO is greater than or equal to 12 mol % and less than or equal to 22 mol %. Various embodiments of colored glass articles and methods of making the same will be described herein with specific reference to the appended drawings.
[0077] Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
[0078] Directional terms as used herein—for example up, down, right, left, front, back, top, bottom—are made only with reference to the figures as drawn and are not intended to imply absolute orientation.
[0079] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order, nor that with any apparatus specific orientations be required. Accordingly, where a method claim does not actually recite an order to be followed by its steps, or that any apparatus claim does not actually recite an order or orientation to individual components, or it is not otherwise specifically stated in the claims or description that the steps are to be limited to a specific order, or that a specific order or orientation to components of an apparatus is not recited, it is in no way intended that an order or orientation be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps, operational flow, order of components, or orientation of components; plain meaning derived from grammatical organization or punctuation, and; the number or type of embodiments described in the specification.
[0080] As used herein, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” component includes aspects having two or more such components, unless the context clearly indicates otherwise.
[0081] In the embodiments of the glass compositions described herein, the concentrations of constituent components (e.g., SiO.sub.2, Al.sub.2O.sub.3, and the like) are specified in mole percent (mol %) on an oxide basis, unless otherwise specified.
[0082] The term “fracture toughness,” as used herein, refers to the K.sub.1C value, and is measured by the chevron notched short bar method. The chevron notched short bar (CNSB) method is disclosed in Reddy, K.P.R. et al, “Fracture Toughness Measurement of Glass and Ceramic Materials Using Chevron-Notched Specimens,” J. Am. Ceram. Soc., 71 [6], C-310-C-313 (1988) except that Y*.sub.m is calculated using equation 5 of Bubsey, R. T. 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).
[0083] The term “melting point,” as used herein, refers to the temperature at which the viscosity of the glass composition is 200 poise.
[0084] The term “softening point,” as used herein, refers to the temperature at which the viscosity of the glass composition is 1×10.sup.76 poise. The softening point is measured according to the parallel plate viscosity method which measures the viscosity of inorganic glass from 10.sup.7 to 10.sup.9 poise as a function of temperature, similar to ASTM C1351M.
[0085] The terms “annealing point” as used herein, refer to the temperature at which the viscosity of the glass composition is 1×10.sup.13.18 poise.
[0086] The term “strain point,” as used herein, refers to the temperature at which the viscosity of the glass composition is 1×10.sup.14.68 poise.
[0087] The term “linear coefficient of thermal expansion” and “CTE,” as described herein, is measured in accordance with ASTM E228-85 over the temperature range of 25° C. to 300° C. and is expressed in terms of “x 10.sup.−7/° C.”
[0088] The term “liquidus viscosity,” as used herein, refers to the viscosity of the glass composition at the onset of devitrification (i.e., at the liquidus temperature as determined with the gradient furnace method according to ASTM C829-81).
[0089] The term “liquidus temperature,” as used herein, refers to the temperature at which the glass composition begins to devitrify as determined with the gradient furnace method according to ASTM C829-81.
[0090] Surface compressive stress is measured with a surface stress meter (FSM) such as commercially available instruments such as the FSM-6000, manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely upon the measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass article. SOC, in turn, 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. Depth of compression (DOC) is also measured with the FSM. The maximum central tension (CT) values are measured using a scattered light polariscope (SCALP) technique known in the art.
[0091] The phrase “depth of compression” (DOC), as used herein, refers to the position in the article where compressive stress transitions to tensile stress.
[0092] The term “CIELAB color space,” as used herein, refers to a color space defined by the International Commission on Illumination (CIE) in 1976. It expresses color as three values: L* for the lightness from black (0) to white (100), a* from green (-) to red (+), and B* from blue (−) to yellow (+).
[0093] The term “color gamut,” as used herein, refers to the pallet of colors that may be achieved by the colored glass articles within the CIELAB color space.
[0094] The term “projected color gamut,” as used herein, refers to the line, surface, volume, or overlapping volume occupied by the colored glass article within the three-dimensional CIELAB color space and represents the pallet of colors that may be achieved by the colored glass articles within the CIELAB color space based upon the concentration of colorant(s) present in the colored glass article. The projected color gamuts shown herein were produced using the plotting routine Gnuplot Version 5.4. Specifically, Gnuplot was used to display projections of the CIELAB color coordinates for the transmitted colors under F2 illumination for the CIE 1976 10° Standard Observer. The transmittance spectrum through a flat sheet of glass is given by the following expression:
where R is the Fresnel intensity reflection coefficient of the glass, N.sub.i and σ.sub.i represent the number density and absorption cross section, respectively, for the individual dopants, λ is the optical wavelength, and t is the thickness of the glass. The color coordinates were calculated from the transmittance spectra through 1.5-mm of the colored glass article. The expression for the transmittance was evaluated by varying the dopant concentrations (N.sub.i) for the combinations of the colorants from 0 to a maximum value. As described herein, the maximum values for Cr.sub.2O.sub.3, NiO, CuO, and Co.sub.3O.sub.4 were set to 2 mol %, 4 mol %, 20 mol %, and 2 mol %, respectively.
[0095] Colorants have been added to conventional aluminosilicate glass compositions to achieve a colored glass article having a desired color and improved mechanical properties. For example, chromium (Cr) doped glass articles are green. However, simply including colorants in aluminosilicate glass compositions may not produce the desired color. For example, a conventional aluminosilicate glass composition C1 may include 58.4 mol % SiO.sub.2, 17.8 mol % Al.sub.2O.sub.3, 6.07 mol % B.sub.2O.sub.3, 10.7 mol % Li.sub.2O, 1.7 mol % Na.sub.2O, 0.2 mol % K.sub.2O, 4.43 mol % MgO, and 0.57 mol % CaO. Cr.sub.2O.sub.3 added to this conventional aluminosilicate glass composition would have low solubility and would form Cr/Mg/Zn spinel crystals because of the greater amounts of Al.sub.2O.sub.3, MgO, and ZnO present in the composition. The low solubility of Cr.sub.2O.sub.3 limits the color gamut that may be achieved and may, at most, result in a glass article having a faint green hue.
[0096] Disclosed herein are glass compositions and colored glass articles formed therefrom that mitigate the aforementioned problems such that Cr.sub.2O.sub.3 may be added to aluminosilicate glass compositions to produce colored glass articles having the desired color while retaining the superior ion-exchangeability and drop performance of the colored glass articles. Specifically, the glass compositions disclosed herein improve Cr.sub.2O.sub.3 solubility by including a limited amount of Al.sub.2O.sub.3 (e.g., less than or equal to 17.5 mol % Al.sub.2O.sub.3 and/or R.sub.2O+RO−Al.sub.2O.sub.3 greater than or equal to 0.5 mol %) and a limited total amount of Al.sub.2O.sub.3, MgO, and ZnO (e.g., Al.sub.2O.sub.3+MgO+ZnO less than or equal to 22 mol %). Increasing the solubility of Cr.sub.2O.sub.3 expands the color gamut that may be achieved by the resultant colored glass articles.
[0097] The glass compositions and colored glass articles described herein may be described as aluminoborosilicate glass compositions and colored glass articles and comprise SiO.sub.2, Al.sub.2O.sub.3, and B.sub.2O.sub.3. In addition to SiO.sub.2, Al.sub.2O.sub.3, and B.sub.2O.sub.3, the glass compositions and colored glass articles described herein include Cr.sub.2O.sub.3 to produce colored glass articles having the desired color. The glass compositions and colored glass articles described herein also include alkali oxides, such as Li.sub.2O and Na.sub.2O, to enable the ion-exchangeability of the colored glass articles.
[0098] SiO.sub.2 is the primary glass former in the glass compositions described herein and may function to stabilize the network structure of the colored glass articles. The concentration of SiO.sub.2 in the glass compositions and resultant colored glass articles should be sufficiently high (e.g., greater than or equal to 50 mol %) to enhance the chemical durability of the glass composition and, in particular, the resistance of the glass composition to degradation upon exposure to acidic solutions, basic solutions, and in water. The amount of SiO.sub.2 may be limited (e.g., to less than or equal to 70 mol %) to control the melting point of the glass composition, as the melting temperature of pure SiO.sub.2 or high SiO.sub.2 glasses is undesirably high. Thus, limiting the concentration of SiO.sub.2 may aid in improving the meltability and the formability of the resultant colored glass article.
[0099] Accordingly, in embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 50 mol % and less than or equal to 70 mol % SiO.sub.2. In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 53 mol % and less than or equal to 67 mol % SiO.sub.2. In embodiments, the concentration of SiO.sub.2 in the glass composition and the resultant colored glass article may be greater than or equal to 50 mol %, greater than or equal to 53 mol %, greater than or equal to 55 mol %, greater than or equal to 56 mol %, or even greater than or equal to 57 mol %. In embodiments, the concentration of SiO.sub.2 in the glass composition and the colored resultant glass article may be less than or equal to 70 mol %, less than or equal to 67 mol %, less than or equal to 65 mol %, less than or equal to 63 mol %, less than or equal to 60 mol %, or even less than or equal to 59 mol %. In embodiments, the concentration of SiO.sub.2 in the glass composition and the resultant colored glass article may be greater than or equal to 50 mol % and less than or equal to 70 mol %, greater than or equal to 50 mol % and less than or equal to 67 mol %, greater than or equal to 50 mol % and less than or equal to 65 mol %, greater than or equal to 50 mol % and less than or equal to 63 mol %, greater than or equal to 50 mol % and less than or equal to 60 mol %, greater than or equal 50 mol % and less than or equal to 59 mol %, greater than or equal to 53 mol % and less than or equal to 70 mol %, greater than or equal to 53 mol % and less than or equal to 67 mol %, greater than or equal to 53 mol % and less than or equal to 65 mol %, greater than or equal to 53 mol % and less than or equal to 63 mol %, greater than or equal to 53 mol % and less than or equal to 60 mol %, greater than or equal 53 mol % and less than or equal to 59 mol %, greater than or equal to 55 mol % and less than or equal to 70 mol %, greater than or equal to 55 mol % and less than or equal to 67 mol %, greater than or equal to 55 mol % and less than or equal to 65 mol %, greater than or equal to 55 mol % and less than or equal to 63 mol %, greater than or equal to 55 mol % and less than or equal to 60 mol %, greater than or equal 55 mol % and less than or equal to 59 mol %, greater than or equal to 56 mol % and less than or equal to 70 mol %, greater than or equal to 56 mol % and less than or equal to 67 mol %, greater than or equal to 56 mol % and less than or equal to 65 mol %, greater than or equal to 56 mol % and less than or equal to 63 mol %, greater than or equal to 56 mol % and less than or equal to 60 mol %, greater than or equal 56 mol % and less than or equal to 59 mol %, greater than or equal to 57 mol % and less than or equal to 70 mol %, greater than or equal to 57 mol % and less than or equal to 67 mol %, greater than or equal to 57 mol % and less than or equal to 65 mol %, greater than or equal to 57 mol % and less than or equal to 63 mol %, greater than or equal to 57 mol % and less than or equal to 60 mol %, or even greater than or equal 57 mol % and less than or equal to 59 mol %, or any and all sub-ranges formed from these endpoints.
[0100] Like SiO.sub.2, Al.sub.2O.sub.3 may also stabilize the glass network and additionally provides improved mechanical properties and chemical durability to the glass composition and the resultant colored glass article. The amount of Al.sub.2O.sub.3 may also be tailored to control the viscosity of the glass composition. Al.sub.2O.sub.3 may be included such that the resultant glass composition has the desired fracture toughness (e.g., greater than or equal to 0.7 MPa.Math.m.sup.1/2). However, if the amount of Al.sub.2O.sub.3 is too high (e.g., greater than 17.5 mol %), the solubility of Cr.sub.2O.sub.3 may decrease, resulting in the formation of Cr-spinel crystals, and the viscosity of the melt may increase, thereby diminishing the formability of the colored glass article.
[0101] Accordingly, in embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 10 mol % and less than or equal to 17.5 mol % Al.sub.2O.sub.3. In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 12 mol % and less than or equal to 17.25 mol % Al.sub.2O.sub.3. In embodiments, the concentration of Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 10 mol %, greater than or equal to 12 mol %, greater than or equal to 14 mol %, greater than or equal to 14.5 mol %, greater than or equal to 15 mol %, greater than or equal to 15.5 mol %, or even greater than or equal to 16 mol %. In embodiments, the concentration of Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be less than or equal to 17.5 mol %, less than or equal to 17.25 mol %, less than or equal to 17 mol %, or even less than or equal to 16.75 mol %. In embodiments, the concentration of Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 10 mol % and less than or equal to 17.5 mol %, greater than or equal to 10 mol % and less than or equal to 17.25 mol %, greater than or equal to 10 mol % and less than or equal to 17 mol %, greater than or equal to 10 mol % and less than or equal to 16.75 mol %, greater than or equal to 12 mol % and less than or equal to 17.5 mol %, greater than or equal to 12 mol % and less than or equal to 17.25 mol %, greater than or equal to 12 mol % and less than or equal to 17 mol %, greater than or equal to 12 mol % and less than or equal to 16.75 mol %, greater than or equal to 14 mol % and less than or equal to 17.5 mol %, greater than or equal to 14 mol % and less than or equal to 17.25 mol %, greater than or equal to 14 mol % and less than or equal to 17 mol %, greater than or equal to 14 mol % and less than or equal to 16.75 mol %, greater than or equal to 14.5 mol % and less than or equal to 17.5 mol %, greater than or equal to 14.5 mol % and less than or equal to 17.25 mol %, greater than or equal to 14.5 mol % and less than or equal to 17 mol %, greater than or equal to 14.5 mol % and less than or equal to 16.75 mol %, greater than or equal to 15 mol % and less than or equal to 17.5 mol %, greater than or equal to 15 mol % and less than or equal to 17.25 mol %, greater than or equal to 15 mol % and less than or equal to 17 mol %, greater than or equal to 15 mol % and less than or equal to 16.75 mol %, greater than or equal to 15.5 mol % and less than or equal to 17.5 mol %, greater than or equal to 15.5 mol % and less than or equal to 17.25 mol %, greater than or equal to 15.5 mol % and less than or equal to 17 mol %, greater than or equal to 15.5 mol % and less than or equal to 16.75 mol %, greater than or equal to 16 mol % and less than or equal to 17.5 mol %, greater than or equal to 16 mol % and less than or equal to 17.25 mol %, greater than or equal to 16 mol % and less than or equal to 17 mol %, or even greater than or equal to 16 mol % and less than or equal to 16.75 mol %, or any and all sub-ranges formed from any of these endpoints.
[0102] B.sub.2O.sub.3 decreases the melting temperature of the glass composition and may also improve the damage resistance of the resultant colored glass article. In addition, B.sub.2O.sub.3 is added to reduce the formation of non-bridging oxygen, the presence of which may reduce fracture toughness. The concentration of B.sub.2O.sub.3 should be sufficiently high (e.g., greater than or equal to 3 mol %) to improve the formability and increase the fracture toughness of the colored glass article. However, if B.sub.2O.sub.3 is too high (e.g., greater than 10 mol %), the annealing point and strain point may decrease, which increases stress relaxation and reduces overall strength of the colored glass article.
[0103] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 3 mol % and less than or equal to 10 mol % B.sub.2O.sub.3. In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 3.5 mol % and less than or equal to 9 mol % B.sub.2O.sub.3. In embodiments, the concentration of B.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 3 mol %, greater than or equal to 3.5 mol %, greater than or equal to 4 mol %, greater than or equal to 4.5 mol %, greater than or equal to 5 mol %, or even greater than or equal to 5.5 mol %. In embodiments, the concentration of B.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be less than or equal to 10 mol %, less than or equal to 9 mol %, less than or equal to 8 mol %, less than or equal to 7.5 mol %, less than or equal to 7 mol %, or even less than or equal to 6.5 mol %. In embodiments, the concentration of B.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 3 mol % and less than or equal to 10 mol %, greater than or equal to 3 mol % and less than or equal to 9 mol %, greater than or equal to 3 mol % and less than or equal to 8 mol %, greater than or equal to 3 mol % and less than or equal to 7.5 mol %, greater than or equal to 3 mol % and less than or equal to 7 mol %, greater than or equal to 3 mol % and less than or equal to 6.5 mol %, greater than or equal to 3.5 mol % and less than or equal to 10 mol %, greater than or equal to 3.5 mol % and less than or equal to 9 mol %, greater than or equal to 3.5 mol % and less than or equal to 8 mol %, greater than or equal to 3.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 3.5 mol % and less than or equal to 7 mol %, greater than or equal to 3.5 mol % and less than or equal to 6.5 mol %, greater than or equal to 4 mol % and less than or equal to 10 mol %, greater than or equal to 4 mol % and less than or equal to 9 mol %, greater than or equal to 4 mol % and less than or equal to 8 mol %, greater than or equal to 4 mol % and less than or equal to 7.5 mol %, greater than or equal to 4 mol % and less than or equal to 7 mol %, greater than or equal to 4 mol % and less than or equal to 6.5 mol %, greater than or equal to 4.5 mol % and less than or equal to 10 mol %, greater than or equal to 4.5 mol % and less than or equal to 9 mol %, greater than or equal to 4.5 mol % and less than or equal to 8 mol %, greater than or equal to 4.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 4.5 mol % and less than or equal to 7 mol %, greater than or equal to 4.5 mol % and less than or equal to 6.5 mol %, greater than or equal to 5 mol % and less than or equal to 10 mol %, greater than or equal to 5 mol % and less than or equal to 9 mol %, greater than or equal to 5 mol % and less than or equal to 8 mol %, greater than or equal to 5 mol % and less than or equal to 7.5 mol %, greater than or equal to 5 mol % and less than or equal to 7 mol %, greater than or equal to 5 mol % and less than or equal to 6.5 mol %, greater than or equal to 5.5 mol % and less than or equal to 10 mol %, greater than or equal to 5.5 mol % and less than or equal to 9 mol %, greater than or equal to 5.5 mol % and less than or equal to 8 mol %, greater than or equal to 5.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 5.5 mol % and less than or equal to 7 mol %, or even greater than or equal to 5.5 mol % and less than or equal to 6.5 mol %, or any and all sub-ranges formed from any of these endpoints.
[0104] As described hereinabove, the glass compositions and the resultant colored glass articles may contain alkali oxides, such as Li.sub.2O and Na.sub.2O, to enable the ion-exchangeability of the colored glass articles.
[0105] Li.sub.2O aids in the ion-exchangeability of the colored glass article and also reduces the softening point of the glass composition, thereby increasing the formability of the colored glass articles. The concentration of Li.sub.2O in the in the glass compositions and resultant colored glass articles should be sufficiently high (e.g., greater than or equal to 8.8 mol %) to achieve the desired maximum central tension (e.g., greater than or equal to 40 MPa). However, if the amount of Li.sub.2O is too high (e.g., greater than 14 mol %), the liquidus temperature may increase, thereby diminishing the manufacturability of the colored glass article.
[0106] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 8.8 mol % and less than or equal to 14 mol % Li.sub.2O. In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 9 mol % and less than or equal to 13.5 mol % Li.sub.2O. In embodiments, the concentration of Li.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 8.8 mol %, greater than or equal to 9 mol %, greater than or equal to 9.2 mol %, greater than or equal to 9.4 mol %, greater than or equal to 9.6 mol %, greater than or equal to 9.8 mol %, or even greater than or equal to 10 mol %. In embodiments, the concentration of Li.sub.2O in the glass composition and the resultant colored glass article may be less than or equal to 14 mol %, less than or equal to 13.5 mol %, less than or equal to 13 mol %, less than or equal to 12.5 mol %, less than or equal to 12 mol %, or even less than or equal to 11.5 mol %. In embodiments, the concentration of Li.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 8.8 mol % and less than or equal to 14 mol %, greater than or equal to 8.8 mol % and less than or equal to 13.5 mol %, greater than or equal to 8.8 mol % and less than or equal to 13 mol %, greater than or equal to 8.8 mol % and less than or equal to 12.5 mol %, greater than or equal to 8.8 mol % and less than or equal to 12 mol %, greater than or equal to 8.8 mol % and less than or equal to 11.5 mol %, greater than or equal to 9 mol % and less than or equal to 14 mol %, greater than or equal to 9 mol % and less than or equal to 13.5 mol %, greater than or equal to 9 mol % and less than or equal to 13 mol %, greater than or equal to 9 mol % and less than or equal to 12.5 mol %, greater than or equal to 9 mol % and less than or equal to 12 mol %, greater than or equal to 9 mol % and less than or equal to 11.5 mol %, greater than or equal to 9.2 mol % and less than or equal to 14 mol %, greater than or equal to 9.2 mol % and less than or equal to 13.5 mol %, greater than or equal to 9.2 mol % and less than or equal to 13 mol %, greater than or equal to 9.2 mol % and less than or equal to 12.5 mol %, greater than or equal to 9.2 mol % and less than or equal to 12 mol %, greater than or equal to 9.2 mol % and less than or equal to 11.5 mol %, greater than or equal to 9.4 mol % and less than or equal to 14 mol %, greater than or equal to 9.4 mol % and less than or equal to 13.5 mol %, greater than or equal to 9.4 mol % and less than or equal to 13 mol %, greater than or equal to 9.4 mol % and less than or equal to 12.5 mol %, greater than or equal to 9.4 mol % and less than or equal to 12 mol %, greater than or equal to 9.4 mol % and less than or equal to 11.5 mol %, greater than or equal to 9.6 mol % and less than or equal to 14 mol %, greater than or equal to 9.6 mol % and less than or equal to 13.5 mol %, greater than or equal to 9.6 mol % and less than or equal to 13 mol %, greater than or equal to 9.6 mol % and less than or equal to 12.5 mol %, greater than or equal to 9.6 mol % and less than or equal to 12 mol %, greater than or equal to 9.6 mol % and less than or equal to 11.5 mol %, greater than or equal to 9.8 mol % and less than or equal to 14 mol %, greater than or equal to 9.8 mol % and less than or equal to 13.5 mol %, greater than or equal to 9.8 mol % and less than or equal to 13 mol %, greater than or equal to 9.8 mol % and less than or equal to 12.5 mol %, greater than or equal to 9.8 mol % and less than or equal to 12 mol %, greater than or equal to 9.8 mol % and less than or equal to 11.5 mol %, greater than or equal to 10 mol % and less than or equal to 14 mol %, greater than or equal to 10 mol % and less than or equal to 13.5 mol %, greater than or equal to 10 mol % and less than or equal to 13 mol %, greater than or equal to 10 mol % and less than or equal to 12.5 mol %, greater than or equal to 10 mol % and less than or equal to 12 mol %, or even greater than or equal to 10 mol % and less than or equal to 11.5 mol %, or any and all sub-ranges formed from any of these endpoints.
[0107] Na.sub.2O improves diffusivity to reduce ion-exchange time and helps achieve the desired surface compressive stress (e.g., greater than or equal to 300 MPa). Na.sub.2O also decreases the melting point and improves formability of the colored glass article. However, if too much Na.sub.2O is added to the glass composition, the melting point may be too low. As such, in embodiments, the concentration of Li.sub.2O present in the glass composition and the resultant colored glass article may be greater than the concentration of Na.sub.2O present in the glass composition and the resultant colored glass article.
[0108] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 1.5 mol % and less than or equal to 8 mol % Na.sub.2O. In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 2 mol % and less than or equal to 7.5 mol % Na.sub.2O. In embodiments, the concentration of Na2O in the glass composition and the resultant colored glass article may be greater than or equal to 1.5 mol %, greater than or equal to 2 mol %, greater than or equal to 2.5 mol %, greater than or equal to 3 mol %, greater than or equal to 3.5 mol %, greater than or equal to 4 mol %, or even greater than or equal to 4.5 mol %. In embodiments, the concentration of Na.sub.2O in the glass composition and the resultant colored glass article may be less than or equal to 8 mol %, less than or equal to 7.5 mol %, less than or equal to 7 mol %, less than or equal to 6.5 mol %, or even less than or equal to 6 mol %. In embodiments, the concentration of Na.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 1.5 mol % and less than or equal to 8 mol %, greater than or equal to 1.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 7 mol %, greater than or equal to 1.5 mol % and less than or equal to 6.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 6 mol %, greater than or equal to 2 mol % and less than or equal to 8 mol %, greater than or equal to 2 mol % and less than or equal to 7.5 mol %, greater than or equal to 2 mol % and less than or equal to 7 mol %, greater than or equal to 2 mol % and less than or equal to 6.5 mol %, greater than or equal to 2 mol % and less than or equal to 6 mol %, greater than or equal to 2.5 mol % and less than or equal to 8 mol %, greater than or equal to 2.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 2.5 mol % and less than or equal to 7 mol %, greater than or equal to 2.5 mol % and less than or equal to 6.5 mol %, greater than or equal to 2.5 mol % and less than or equal to 6 mol %, greater than or equal to 3 mol % and less than or equal to 8 mol %, greater than or equal to 3 mol % and less than or equal to 7.5 mol %, greater than or equal to 3 mol % and less than or equal to 7 mol %, greater than or equal to 3 mol % and less than or equal to 6.5 mol %, greater than or equal to 3 mol % and less than or equal to 6 mol %, greater than or equal to 3.5 mol % and less than or equal to 8 mol %, greater than or equal to 3.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 3.5 mol % and less than or equal to 7 mol %, greater than or equal to 3.5 mol % and less than or equal to 6.5 mol %, greater than or equal to 3.5 mol % and less than or equal to 6 mol %, greater than or equal to 4 mol % and less than or equal to 8 mol %, greater than or equal to 4 mol % and less than or equal to 7.5 mol %, greater than or equal to 4 mol % and less than or equal to 7 mol %, greater than or equal to 4 mol % and less than or equal to 6.5 mol %, greater than or equal to 4 mol % and less than or equal to 6 mol %, greater than or equal to 4.5 mol % and less than or equal to 8 mol %, greater than or equal to 4.5 mol % and less than or equal to 7.5 mol %, greater than or equal to 4.5 mol % and less than or equal to 7 mol %, greater than or equal to 4.5 mol % and less than or equal to 6.5 mol %, or even greater than or equal to 4.5 mol % and less than or equal to 6 mol %, or any and all of these sub-ranges formed from any of these endpoints.
[0109] The glass compositions and the resultant colored glass articles described herein may further comprise alkali metal oxides other than Li.sub.2O and Na.sub.2O, such as K.sub.2O. K.sub.2O, when included, promotes ion-exchange and may increase the depth of compression and decrease the melting point to improve the formability of the colored glass article. However, adding too much K.sub.2O may cause the surface compressive stress and melting point to be too low. Accordingly, in embodiments, the amount of K.sub.2O added to the glass composition may be limited.
[0110] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 3 mol % K.sub.2O. In embodiments, the concentration of K.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.2 mol %, or even greater than or equal to 0.4 mol %. In embodiments, the concentration of K.sub.2O in the glass composition and the resultant colored glass article may be less than or equal to 3 mol %, less than or equal to 2.5 mol %, less than or equal to 2 mol %, less than or equal to 1.5 mol %, less than or equal to 1 mol %, less than or equal to 0.75 mol %, or even less than or equal to 0.5 mol %. In embodiments, the concentration of K.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 3 mol %, greater than or equal to 0 mol % and less than or equal to 2.5 mol %, greater than or equal to 0 mol % and less than or equal to 2 mol %, greater than or equal to 0 mol % and less than or equal to 1.5 mol %, greater than or equal to 0 mol % and less than or equal to 1 mol %, greater than or equal to 0 mol % and less than or equal to 0.75 mol %, greater than or equal to 0 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.2 mol % and less than or equal to 3 mol %, greater than or equal to 0.2 mol % and less than or equal to 2.5 mol %, greater than or equal to 0.2 mol % and less than or equal to 2 mol %, greater than or equal to 0.2 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.2 mol % and less than or equal to 1 mol %, greater than or equal to 0.2 mol % and less than or equal to 0.75 mol %, greater than or equal to 0.2 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.4 mol % and less than or equal to 3 mol %, greater than or equal to 0.4 mol % and less than or equal to 2.5 mol %, greater than or equal to 0.4 mol % and less than or equal to 2 mol %, greater than or equal to 0.4 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.4 mol % and less than or equal to 1 mol %, greater than or equal to 0.4 mol % and less than or equal to 0.75 mol %, or even greater than or equal to 0.4 mol % and less than or equal to 0.5 mol %, or any and all sub-ranges formed from any of these endpoints.
[0111] The sum of all alkali oxides is expressed herein as R.sub.2O. Specifically, R.sub.2O is the sum (in mol %) of Li.sub.2O, Na.sub.2O, and K.sub.2O present in the glass composition and the resultant colored glass article (i.e., R.sub.2O=Li.sub.2O (mol %)+Na.sub.2O (mol %)+K.sub.2O (mol %). Like B.sub.2O.sub.3, the alkali oxides aid in decreasing the softening point and molding temperature of the glass composition, thereby offsetting the increase in the softening point and molding temperature of the glass composition due to higher amounts of SiO.sub.2 in the glass composition, for example. The softening point and molding temperature may be further reduced by including combinations of alkali oxides (e.g., two or more alkali oxides) in the glass composition, a phenomenon referred to as the “mixed alkali effect.” However, it has been found that if the amount of alkali oxide is too high, the average coefficient of thermal expansion of the glass composition increases to greater than 100×10.sup.−7/° C., which may be undesirable.
[0112] In embodiments, the concentration of R.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 10.3 mol %, greater than or equal to 11 mol %, greater than or equal to 12 mol %, greater than or equal to 13 mol %, or even greater than or equal to 14 mol. In embodiments, the concentration of R.sub.2O in the glass composition and the resultant colored glass article may be less than or equal to 22 mol %, less than or equal to 21 mol %, less than or equal to 20 mol %, less than or equal to 19 mol %, or even less than or equal to 18 mol %. In embodiments, the concentration of R.sub.2O in the glass composition and the resultant colored glass article may be greater than or equal to 10.3 mol % and less than or equal to 22 mol %, greater than or equal to 10.3 mol % and less than or equal to 21 mol %, greater than or equal to 10.3 mol % and less than or equal to 20 mol %, greater than or equal to 10.3 mol % and less than or equal to 19 mol %, greater than or equal to 10.3 mol % and less than or equal to 18 mol %, greater than or equal to 11 mol % and less than or equal to 22 mol %, greater than or equal to 11 mol % and less than or equal to 21 mol %, greater than or equal to 11 mol % and less than or equal to 20 mol %, greater than or equal to 11 mol % and less than or equal to 19 mol %, greater than or equal to 11 mol % and less than or equal to 18 mol %, greater than or equal to 12 mol % and less than or equal to 22 mol %, greater than or equal to 12 mol % and less than or equal to 21 mol %, greater than or equal to 12 mol % and less than or equal to 20 mol %, greater than or equal to 12 mol % and less than or equal to 19 mol %, greater than or equal to 12 mol % and less than or equal to 18 mol %, greater than or equal to 13 mol % and less than or equal to 22 mol %, greater than or equal to 13 mol % and less than or equal to 21 mol %, greater than or equal to 13 mol % and less than or equal to 20 mol %, greater than or equal to 13 mol % and less than or equal to 19 mol %, greater than or equal to 13 mol % and less than or equal to 18 mol %, greater than or equal to 14 mol % and less than or equal to 22 mol %, greater than or equal to 14 mol % and less than or equal to 21 mol %, greater than or equal to 14 mol % and less than or equal to 20 mol %, greater than or equal to 14 mol % and less than or equal to 19 mol %, or even greater than or equal to 14 mol % and less than or equal to 18 mol %, or any and all sub-ranges formed from any of these endpoints.
[0113] The glass compositions and the resultant colored glass articles described herein may further comprise MgO. MgO lowers the viscosity of the glass compositions, which enhances the formability, the strain point, and the Young's modulus, and may improve the ion-exchangeability. However, when too much MgO is added to the glass composition, the diffusivity of sodium and potassium ions in the glass composition decreases which, in turn, adversely impacts the ion-exchange performance (i.e., the ability to ion-exchange) of the resultant colored glass article.
[0114] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 4.5 mol % MgO. In embodiments, the concentration of MgO in the glass composition may be greater than or equal to 0 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 1.5 mol %, or even greater than or equal to 2 mol %. In embodiments, the concentration of MgO in the glass composition may be less than or equal to 4.5 mol %, less than or equal to 4 mol %, less than or equal to 3.5 mol %, or even less than or equal to 3 mol %. In embodiments, the concentration of MgO in the glass composition may be greater than or equal to 0 mol % and less than or equal to 4.5 mol %, greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0 mol % and less than or equal to 3.5 mol %, greater than or equal to 0 mol % and less than or equal to 3 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 3 mol %, greater than or equal to 1 mol % and less than or equal to 4.5 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 3.5 mol %, greater than or equal to 1 mol % and less than or equal to 3 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4 mol %, greater than or equal to 1.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 3 mol %, greater than or equal to 2 mol % and less than or equal to 4.5 mol %, greater than or equal to 2 mol % and less than or equal to 4 mol %, greater than or equal to 2 mol % and less than or equal to 3.5 mol %, or even greater than or equal to 2 mol % and less than or equal to 3 mol %, or any and all sub-ranges formed from any of these endpoints.
[0115] The glass compositions and the resultant colored glass articles described herein may further comprise ZnO. ZnO lowers the viscosity of the glass compositions, which enhances the formability, the strain point, and the Young's modulus, and may improve the ion-exchangeability. However, when too much ZnO is added to the glass composition, the diffusivity of sodium and potassium ions in the glass composition decreases which, in turn, adversely impacts the ion-exchange performance (i.e., the ability to ion-exchange) of the resultant colored glass article.
[0116] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 4.5 mol % ZnO. In embodiments, the concentration of ZnO in the glass composition may be greater than or equal to 0 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 1.5 mol %, or even greater than or equal to 2 mol %. In embodiments, the concentration of ZnO in the glass composition may be less than or equal to 4.5 mol %, less than or equal to 4 mol %, less than or equal to 3.5 mol %, or even less than or equal to 3 mol %. In embodiments, the concentration of ZnO in the glass composition may be greater than or equal to 0 mol % and less than or equal to 4.5 mol %, greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0 mol % and less than or equal to 3.5 mol %, greater than or equal to 0 mol % and less than or equal to 3 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 3 mol %, greater than or equal to 1 mol % and less than or equal to 4.5 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 3.5 mol %, greater than or equal to 1 mol % and less than or equal to 3 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4 mol %, greater than or equal to 1.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 3 mol %, greater than or equal to 2 mol % and less than or equal to 4.5 mol %, greater than or equal to 2 mol % and less than or equal to 4 mol %, greater than or equal to 2 mol % and less than or equal to 3.5 mol %, or even greater than or equal to 2 mol % and less than or equal to 3 mol %, or any and all sub-ranges formed from any of these endpoints.
[0117] In embodiments, the sum of MgO and ZnO present in the glass composition and the resultant colored glass article (i.e., MgO (mol %) +ZnO (mol %)) may be greater than or equal to 0 mol % and less than or equal to 4.5 mol % to avoid the formation of Cr-spinel crystals, thereby increasing Cr.sub.2O.sub.3 solubility and expanding the color gamut that may be achieved by the resultant colored glass articles.
[0118] In embodiments, the sum of MgO and ZnO in the glass compositions and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 1 mol %. In embodiments, the sum of MgO and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 1 mol % and less than or equal to 4.5 mol %. In embodiments, the sum of MgO and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2 mol %, greater than or equal to 2.5 mol %, or even greater than or equal to 3 mol %. In embodiments, the sum of MgO and ZnO in the glass composition and the resultant colored glass article may be less than or equal to 4.5 mol %, less than or equal to 4.25 mol %, or even less than or equal to 4 mol %. In embodiments, the sum of MgO and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 4.5 mol %, greater than or equal to 0 mol % and less than or equal to 4.25 mol %, greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.25 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 4.5 mol %, greater than or equal to 1 mol % and less than or equal to 4.25 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.25 mol %, greater than or equal to 1.5 mol % and less than or equal to 4 mol %, greater than or equal to 2 mol % and less than or equal to 4.5 mol %, greater than or equal to 2 mol % and less than or equal to 4.25 mol %, greater than or equal to 2 mol % and less than or equal to 4 mol %, greater than or equal to 2.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 2.5 mol % and less than or equal to 4.25 mol %, greater than or equal to 2.5 mol % and less than or equal to 4 mol %, greater than or equal to 3 mol % and less than or equal to 4.5 mol %, greater than or equal to 3 mol % and less than or equal to 4.25 mol %, or even greater than or equal to 3 mol % and less than or equal to 4 mol %, or any and all sub-ranges formed from any of these endpoints.
[0119] In embodiments, the sum of Al.sub.2O.sub.3, MgO, and ZnO present in the glass composition and the resultant colored glass article (i.e., Al.sub.2O.sub.3 (mol %)+MgO (mol %)+ZnO (mol %)) may be greater than or equal to 12 mol % and less than or equal to 22 mol % to avoid the formation of Cr-spinel crystals, thereby increasing Cr.sub.2O.sub.3 solubility and expanding the color gamut that may be achieved by the resultant colored glass articles.
[0120] In embodiments, the sum of Al.sub.2O.sub.3, MgO, and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 13 mol % and less than or equal to 21.5 mol %. In embodiments, the sum of Al.sub.2O.sub.3, MgO, and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 12 mol %, greater than or equal to 13 mol %, greater than or equal to 14 mol %, greater than or equal to 15 mol %, or even greater than or equal to 16 mol %. In embodiments, the sum of Al.sub.2O.sub.3, MgO, and ZnO in the glass composition and the resultant colored glass article may be less than or equal to 22 mol %, less than or equal to 21.5 mol %, less than or equal to 21 mol %, less than or equal to 20.5 mol %, or even less than or equal to 20 mol %. In embodiments, the sum of Al.sub.2O.sub.3, MgO, and ZnO in the glass composition and the resultant colored glass article may be greater than or equal to 12 mol % and less than or equal to 22 mol %, greater than or equal to 12 mol % and less than or equal to 21.5 mol %, greater than or equal to 12 mol % and less than or equal to 21 mol %, greater than or equal to 12 mol % and less than or equal to 20.5 mol %, greater than or equal to 12 mol % and less than or equal to 20 mol %, greater than or equal to 13 mol % and less than or equal to 22 mol %, greater than or equal to 13 mol % and less than or equal to 21.5 mol %, greater than or equal to 13 mol % and less than or equal to 21 mol %, greater than or equal to 13 mol % and less than or equal to 20.5 mol %, greater than or equal to 13 mol % and less than or equal to 20 mol %, greater than or equal to 14 mol % and less than or equal to 22 mol %, greater than or equal to 14 mol % and less than or equal to 21.5 mol %, greater than or equal to 14 mol % and less than or equal to 21 mol %, greater than or equal to 14 mol % and less than or equal to 20.5 mol %, greater than or equal to 15 mol % and less than or equal to 20 mol %, greater than or equal to 15 mol % and less than or equal to 22 mol %, greater than or equal to 15 mol % and less than or equal to 21.5 mol %, greater than or equal to 15 mol % and less than or equal to 21 mol %, greater than or equal to 15 mol % and less than or equal to 20.5 mol %, greater than or equal to 15 mol % and less than or equal to 20 mol %, greater than or equal to 16 mol % and less than or equal to 22 mol %, greater than or equal to 16 mol % and less than or equal to 21.5 mol %, greater than or equal to 16 mol % and less than or equal to 21 mol %, greater than or equal to 16 mol % and less than or equal to 20.5 mol %, or even greater than or equal to 16 mol % and less than or equal to 20 mol %, or any and all sub-ranges formed from any of these endpoints.
[0121] The glass compositions and the resultant colored glass articles described herein may further comprise CaO. CaO lowers the viscosity of a glass composition, which enhances the formability, the strain point and the Young's modulus, and may improve the 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, adversely impacts the ion-exchange performance (i.e., the ability to ion-exchange) of the resultant glass.
[0122] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 2 mol % CaO. In embodiments, the concentration of CaO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.25 mol %, greater than or equal to 0.5 mol %, or even greater than or equal to 0.75 mol %. In embodiments, the concentration of CaO in the glass composition and the resultant colored glass article may be less than or equal to 2 mol %, less than or equal to 1.75 mol %, less than or equal to 1.5 mol %, less than or equal to 1.25 mol %, or even less than or equal to 1 mol %. In embodiments, the concentration of CaO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 2 mol %, greater than or equal to 0 mol % and less than or equal to 1.75 mol %, greater than or equal to 0 mol % and less than or equal to 1.5 mol %, greater than or equal to 0 mol % and less than or equal to 1.25 mol %, greater than or equal to 0 mol % and less than or equal to 1 mol %, greater than or equal to 0.25 mol % and less than or equal to 2 mol %, greater than or equal to 0.25 mol % and less than or equal to 1.75 mol %, greater than or equal to 0.25 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.25 mol % and less than or equal to 1.25 mol %, greater than or equal to 0.25 mol % and less than or equal to 1 mol %, greater than or equal to 0.5 mol % and less than or equal to 2 mol %, greater than or equal to 0.5 mol % and less than or equal to 1.75 mol %, greater than or equal to 0.5 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 1.25 mol %, greater than or equal to 0.5 mol % and less than or equal to 1 mol %, greater than or equal to 0.75 mol % and less than or equal to 2 mol %, greater than or equal to 0.75 mol % and less than or equal to 1.75 mol %, greater than or equal to 0.75 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.75 mol % and less than or equal to 1.25 mol %, or even greater than or equal to 0.75 mol % and less than or equal to 1 mol %, or any and all sub-ranges formed from any of these endpoints.
[0123] The sum of all divalent cation oxides is expressed herein as RO. Specifically, RO is the sum (in mol %) of MgO, ZnO, and CaO (i.e. RO=MgO (mol %)+ZnO (mol %)+CaO (mol %)). In embodiments, the concentration of RO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 1.5 mol %, greater than or equal to 2 mol %, or even greater than or equal to 2.5 mol %. In embodiments, the concentration of RO in the glass composition and the resultant colored glass article may be less than or equal to 5 mol %, less than or equal to 4.5 mol %, less than or equal to 4 mol %, or even less than or equal to 3.5 mol %. In embodiments, the concentration of RO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 5 mol %, greater than or equal to 0 mol % and less than or equal to 4.5 mol %, greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0 mol % and less than or equal to 3.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 1 mol % and less than or equal to 5 mol %, greater than or equal to 1 mol % and less than or equal to 4.5 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 3.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4 mol %, greater than or equal to 1.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 2 mol % and less than or equal to 5 mol %, greater than or equal to 2 mol % and less than or equal to 4.5 mol %, greater than or equal to 2 mol % and less than or equal to 4 mol %, greater than or equal to 2 mol % and less than or equal to 3.5 mol %, greater than or equal to 2.5 mol % and less than or equal to 5 mol %, greater than or equal to 2.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 2.5 mol % and less than or equal to 4 mol %, or even greater than or equal to 2.5 mol % and less than or equal to 3.5 mol %, or any and all sub-ranges formed from any of these endpoints.
[0124] In embodiments, the glass compositions and the resultant colored glass articles are per-alkali (i.e., R.sub.2O (mol %)+RO (mol %)−Al.sub.2O.sub.3 (mol %) is greater than or equal to 0.5 mol %) to increase the solubility of Cr.sub.2O.sub.3 and avoid Cr-spinel crystal formation. However, when the glass composition has an excessive amount of alkali after charge balancing Al.sub.2O.sub.3, the alkali may form non-bridging oxygen around SiO.sub.2, which degrades fracture toughness. Accordingly, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be limited (e.g., less than or equal to 6 mol %) to prevent a reduction in fracture toughness.
[0125] In embodiments, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 0.5 mol % and less than or equal to 6 mol %. In embodiments, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 1 mol % and less than or equal to 5.5 mol %. %. In embodiments, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the colored resultant glass article may be greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 1.5 mol %, or even greater than or equal to 2 mol %. In embodiments, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be less than or equal to 6 mol %, less than or equal to 5.5 mol %, less than or equal to 5 mol %, less than or equal to 4.5 mol %, less than or equal to 4 mol %, less than or equal to 3.5 mol %, or even less than or equal to 3 mol %. In embodiments, R.sub.2O+RO−Al.sub.2O.sub.3 in the glass composition and the resultant colored glass article may be greater than or equal to 0.5 mol % and less than or equal to 6 mol %, greater than or equal to 0.5 mol % and less than or equal to 5.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 0.5 mol % and less than or equal to 3 mol %, greater than or equal to 1 mol % and less than or equal to 6 mol %, greater than or equal to 1 mol % and less than or equal to 5.5 mol %, greater than or equal to 1 mol % and less than or equal to 5 mol %, greater than or equal to 1 mol % and less than or equal to 4.5 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 3.5 mol %, greater than or equal to 1 mol % and less than or equal to 3 mol %, greater than or equal to 1.5 mol % and less than or equal to 6 mol %, greater than or equal to 1.5 mol % and less than or equal to 5.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 4 mol %, greater than or equal to 1.5 mol % and less than or equal to 3.5 mol %, greater than or equal to 1.5 mol % and less than or equal to 3 mol %, greater than or equal to 2 mol % and less than or equal to 6 mol %, greater than or equal to 2 mol % and less than or equal to 5.5 mol %, greater than or equal to 2 mol % and less than or equal to 5 mol %, greater than or equal to 2 mol % and less than or equal to 4.5 mol %, greater than or equal to 2 mol % and less than or equal to 4 mol %, greater than or equal to 2 mol % and less than or equal to 3.5 mol %, or even greater than or equal to 2 mol % and less than or equal to 3 mol %, or any and all sub-ranges formed from any of these endpoints.
[0126] In embodiments, the glass compositions and the resultant colored glass articles described herein may satisfy only one of the following conditions and achieve the desired color: (1) less than or equal to 17.5 mol % Al.sub.2O.sub.3 and/or R.sub.2O+RO−Al.sub.2O.sub.3 greater than or equal to 0.5 mol %; (2) Al.sub.2O.sub.3+MgO+ZnO less than or equal to 22 mol %; and (3) MgO+ZnO less than or equal to 4.5 mol %.
[0127] The glass compositions and the resultant colored glass articles described herein further comprise Cr.sub.2O.sub.3 as a colorant to achieve the desired color. As described herein, the glass compositions and the resultant colored glass articles described herein improve the solubility of Cr.sub.2O.sub.3, thereby expanding the color gamut achievable by the resultant colored glass articles.
[0128] In embodiments, the glass composition and the resultant colored glass article may comprise greater than 0 mol % and less than or equal to 2 mol % Cr.sub.2O.sub.3. In embodiments, the glass composition and the resultant colored glass article may comprise greater than 0.001 mol % and less than or equal to 1.5 mol % Cr.sub.2O.sub.3. In embodiments, the concentration of Cr.sub.2O3 in the glass composition and the resultant colored glass article may be greater than 0 mol %, greater than or equal to 0.001 mol %, greater than or equal to 0.005 mol %, greater than or equal to 0.01 mol %, or even greater than or equal to 0.05 mol %. In embodiments, the concentration of Cr.sub.2O3 in the glass composition and the resultant colored glass article may be less than or equal to 2 mol %, less than or equal to 1.5 mol %, less than or equal to 1 mol %, less than or equal to 0.5 mol %, or even less than or equal to 0.1 mol %. In embodiments, the concentration of Cr.sub.2O3 in the glass composition and the resultant colored glass article may be greater than 0 mol % and less than or equal to 2 mol %, greater than 0 mol % and less than or equal to 1.5 mol %, greater than 0 mol % and less than or equal to 1 mol %, greater than 0 mol % and less than or equal to 0.5 mol %, greater than 0 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.001 mol % and less than or equal to 2 mol %, greater than or equal to 0.001 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.001 mol % and less than or equal to 1 mol %, greater than or equal to 0.001 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.001 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.005 mol % and less than or equal to 2 mol %, greater than or equal to 0.005 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.005 mol % and less than or equal to 1 mol %, greater than or equal to 0.005 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.005 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.01 mol % and less than or equal to 2 mol %, greater than or equal to 0.01 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.01 mol % and less than or equal to 1 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.05 mol % and less than or equal to 2 mol %, greater than or equal to 0.05 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.05 mol % and less than or equal to 1 mol %, greater than or equal to 0.05 mol % and less than or equal to 0.5 mol %, or even greater than or equal to 0.05 mol % and less than or equal to 0.1 mol %, or any and all sub-ranges formed from any of these endpoints.
[0129] Different color gamuts may be achieved by including other colorants in addition to Cr.sub.2O.sub.3. Accordingly, in embodiments, the glass composition and resultant colored glass article may comprise NiO, Co.sub.3O.sub.4, CuO, or combinations thereof.
[0130] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 4 mol % NiO. In embodiments, the concentration of NiO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.01 mol %, or even greater than or equal to 0.05 mol %. In embodiments, the concentration of NiO in the glass composition and the resultant colored glass article may be less than or equal to 4 mol %, less than or equal to 3 mol %, less than or equal to 2 mol %, less than or equal to 1 mol %, less than or equal to 0.5 mol %, less than or equal to 0.25 mol %, or even less than or equal to 0.1 mol %. In embodiments, the concentration of NiO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0 mol % and less than or equal to 3 mol %, greater than or equal to 0 mol % and less than or equal to 2 mol %, greater than or equal to 0 mol % and less than or equal to 1 mol %, greater than or equal to 0 mol % and less than or equal to 0.5 mol %, greater than or equal to 0 mol % and less than or equal to 0.25 mol %, greater than or equal to 0 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.01 mol % and less than or equal to 4 mol %, greater than or equal to 0.01 mol % and less than or equal to 3 mol %, greater than or equal to 0.01 mol % and less than or equal to 2 mol %, greater than or equal to 0.01 mol % and less than or equal to 1 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.25 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.05 mol % and less than or equal to 4 mol %, greater than or equal to 0.05 mol % and less than or equal to 3 mol %, greater than or equal to 0.05 mol % and less than or equal to 2 mol %, greater than or equal to 0.05 mol % and less than or equal to 1 mol %, greater than or equal to 0.05 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.05 mol % and less than or equal to 0.25 mol %, or even greater than or equal to 0.05 mol % and less than or equal to 0.1 mol %, or any and all sub-ranges formed between any of these endpoints.
[0131] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or equal to 0 mol % and less than or equal to 2 mol % Co.sub.3O.sub.4. In embodiments, the concentration of Co.sub.3O.sub.4 in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol %, greater than or equal to 0.001 mol %, greater than or equal to 0.005 mol %, or even greater than or equal to 0.01 mol %. In embodiments, the concentration of Co.sub.3O.sub.4 in the glass composition and the resultant colored glass article may be less than or equal to 2 mol %, less than or equal to 1.5 mol %, less than or equal to 1 mol %, less than or equal to 0.5 mol %, less than or equal to 0.1 mol %, or even less than or equal to 0.05 mol %. In embodiments, the concentration of Co.sub.3O.sub.4 in the glass composition and the resultant colored glass article may greater than or equal to 0 mol % and less than or equal to 2 mol %, greater than or equal to 0 mol % and less than or equal to 1.5 mol %, greater than or equal to 0 mol % and less than or equal to 1 mol %, greater than or equal to 0 mol % and less than or equal to 0.5 mol %, greater than or equal to 0 mol % and less than or equal to 0.1 mol %, greater than or equal to 0 mol % and less than or equal to 0.05 mol %, greater than or equal to 0.001 mol % and less than or equal to 2 mol %, greater than or equal to 0.001 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.001 mol % and less than or equal to 1 mol %, greater than or equal to 0.001 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.001 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.001 mol % and less than or equal to 0.05 mol %, greater than or equal to 0.005 mol % and less than or equal to 2 mol %, greater than or equal to 0.005 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.005 mol % and less than or equal to 1 mol %, greater than or equal to 0.005 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.005 mol % and less than or equal to 0.1 mol %, greater than or equal to 0.005 mol % and less than or equal to 0.05 mol %, greater than or equal to 0.01 mol % and less than or equal to 2 mol %, greater than or equal to 0.01 mol % and less than or equal to 1.5 mol %, greater than or equal to 0.01 mol % and less than or equal to 1 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.5 mol %, greater than or equal to 0.01 mol % and less than or equal to 0.1 mol %, or even greater than or equal to 0.01 mol % and less than or equal to 0.05 mol %, or any and all sub-ranges formed from any of these endpoints.
[0132] In embodiments, the glass composition and the resultant colored glass article may comprise greater than or 0 mol % and less than or equal to 20 mol % CuO. In embodiments, the concentration of CuO in the glass composition and the resultant colored glass article may be greater than or equal 0 mol %, greater than or equal to 0.05 mol %, greater than or equal to 0.1 mol %, greater than or equal to 0.5 mol %, or even greater than or equal to 1 mol %. In embodiments, the concentration of CuO in the glass composition and the resultant colored glass article may be less than or equal to 20 mol %, less than or equal to 15 mol %, less than or equal to 10 mol %, less than or equal to 5 mol %, less than or equal to 4 mol %, less than or equal to 3 mol %, or even less than or equal to 2 mol %. In embodiments, the concentration of CuO in the glass composition and the resultant colored glass article may be greater than or equal to 0 mol % and less than or equal to 20 mol %, greater than or equal to 0 mol % and less than or equal to 15 mol %, greater than or equal to 0 mol % and less than or equal to 10 mol %, greater than or equal to 0 mol % and less than or equal to 5 mol %, greater than or equal to 0 mol % and less than or equal to 4 mol %, greater than or equal to 0 mol % and less than or equal to 3 mol %, greater than or equal to 0 mol % and less than or equal to 2 mol, greater than or equal to 0.05 mol % and less than or equal to 20 mol %, greater than or equal to 0.05 mol % and less than or equal to 15 mol %, greater than or equal to 0.05 mol % and less than or equal to 10 mol %, greater than or equal to 0.05 mol % and less than or equal to 5 mol %, greater than or equal to 0.05 mol % and less than or equal to 4 mol %, greater than or equal to 0.05 mol % and less than or equal to 3 mol %, greater than or equal to 0.05 mol % and less than or equal to 2 mol %, greater than or equal to 0.1 mol % and less than or equal to 20 mol %, greater than or equal to 0.1 mol % and less than or equal to 15 mol %, greater than or equal to 0.1 mol % and less than or equal to 10 mol %, greater than or equal to 0.1 mol % and less than or equal to 5 mol %, greater than or equal to 0.1 mol % and less than or equal to 4 mol %, greater than or equal to 0.1 mol % and less than or equal to 3 mol %, greater than or equal to 0.1 mol % and less than or equal to 2 mol %, greater than or equal to 0.5 mol % and less than or equal to 20 mol %, greater than or equal to 0.5 mol % and less than or equal to 15 mol %, greater than or equal to 0.5 mol % and less than or equal to 10 mol %, greater than or equal to 0.5 mol % and less than or equal to 5 mol %, greater than or equal to 0.5 mol % and less than or equal to 4 mol %, greater than or equal to 0.5 mol % and less than or equal to 3 mol %, greater than or equal to 0.5 mol % and less than or equal to 2 mol %, greater than or equal to 1 mol % and less than or equal to 20 mol %, greater than or equal to 1 mol % and less than or equal to 15 mol %, greater than or equal to 1 mol % and less than or equal to 10 mol %, greater than or equal to 1 mol % and less than or equal to 5 mol %, greater than or equal to 1 mol % and less than or equal to 4 mol %, greater than or equal to 1 mol % and less than or equal to 3 mol %, or even greater than or equal to 1 mol % and less than or equal to 2 mol %, or any and all sub-ranges formed from any of these endpoints.
[0133] In embodiments, the glass compositions and the resultant colored glass articles described herein may further include tramp materials such as TiO.sub.2, MnO, MoO.sub.3, WO.sub.3, Y.sub.2O.sub.3, CdO, As.sub.2O.sub.3, Sb.sub.2O.sub.3, sulfur-based compounds, such as sulfates, halogens, or combinations thereof. In embodiments, antimicrobial components, chemical fining agents, or other additional components may be included in the glass compositions and the resultant colored glass articles.
[0134] In embodiments, a liquidus temperature of a glass composition may be greater than or equal to 1000° C., greater than or equal to 1050° C., or even greater than or equal to 1100° C. In embodiments, a liquidus temperature of the precursor glass composition may be less than or equal to 1400° C., less than or equal to 1350° C. or even less than or equal to 1300° C. In embodiments, a liquidus temperature of the precursor glass composition may be greater than or equal to 1000° C. and less than or equal to 1400° C., greater than or equal to 1000° C. and less than or equal to 1350° C., greater than or equal to 1000° C. and less than or equal to 1300° C., greater than or equal to 1050° C. and less than or equal to 1400° C., greater than or equal to 1050° C. and less than or equal to 1350° C., greater than or equal to 1000° C. and less than or equal to 1300° C., greater than or equal to 1100° C. and less than or equal to 1400° C., greater than or equal to 1100° C. and less than or equal to 1350° C., or even greater than or equal to 1100° C. and less than or equal to 1300° C., or any and all sub-ranges formed from any of these endpoints.
[0135] The colored glass articles formed from the glass compositions described herein may be any suitable thickness, which may vary depending on the particular application of the colored glass article. In embodiments, the glass sheet embodiments may have a thickness greater than or equal to 250 μm and less than or equal to 6 mm, greater than or equal to 250 μm and less than or equal to 4 mm, greater than or equal to 250 μm and less than or equal to 2 mm, greater than or equal to 250 μm and less than or equal to 1 mm, greater than or equal to 250 μm and less than or equal to 750 μm, greater than or equal to 250 μm and less than or equal to 500 μm, greater than or equal to 500 μm and less than or equal to 6 mm, greater than or equal to 500 μm and less than or equal to 4 mm, greater than or equal to 500 μm and less than or equal to 2 mm, greater than or equal to 500 μm and less than or equal to 1 mm, greater than or equal to 500 μm and less than or equal to 750 μm, greater than or equal to 750 μm and less than or equal to 6 mm, greater than or equal to 750 μm and less than or equal to 4 mm, greater than or equal to 750 μm and less than or equal to 2 mm, greater than or equal to 750 μm and less than or equal to 1 mm, greater than or equal to 1 mm and less than or equal to 6 mm, greater than or equal to 1 mm and less than or equal to 4 mm, greater than or equal to 1 mm and less than or equal to 2 mm, greater than or equal to 2 mm and less than or equal to 6 mm, greater than or equal to 2 mm and less than or equal to 4 mm, or even greater than or equal to 4 mm and less than or equal to 6 mm, or any and all sub-ranges formed from any of these endpoints.
[0136] As discussed hereinabove, colored glass articles formed from the glass compositions described herein may have an increased fracture toughness such that the colored glass articles are more resistant to damage. In embodiments, the colored glass article may have a K.sub.1C fracture toughness as measured by a double torsion method greater than or equal to 0.7 MPa.Math.m.sup.1/2. In embodiments, the colored glass article may have a K.sub.1C fracture toughness as measured by a double torsion method greater than or equal to 0.7 MPa.Math.m.sup.1/2, greater than or equal to 0.8 MPa.Math.m.sup.1/2, greater than or equal to 0.9 MPa.Math.m.sup.1/2, or even greater than or equal to 1.0 MPa.Math.m.sup.1/2.
[0137] In embodiments, the glass compositions described herein are ion-exchangeable to facilitate strengthening the colored glass article made from the glass compositions. In typical ion-exchange processes, smaller metal ions in the glass compositions are replaced or “exchanged” with larger metal ions of the same valence within a layer that is close to the outer surface of the glass article made from the glass composition. The replacement of smaller ions with larger ions creates a compressive stress within the layer of the glass article made from the glass composition. In embodiments, the metal ions are monovalent metal ions (e.g., Li.sup.+, Na.sup.+, K.sup.+, and the like), and ion-exchange is accomplished by immersing the glass article made from the glass composition in a bath comprising at least one molten salt of the larger metal ion that is to replace the smaller metal ion in the glass article. Alternatively, other monovalent ions such as Ag.sup.+, Tl.sup.+, Cu.sup.+, and the like may be exchanged for monovalent ions. The ion-exchange process or processes that are used to strengthen the glass article made from the glass composition may include, but are not limited to, immersion in a single bath or multiple baths of like or different compositions with washing and/or annealing steps between immersions. In embodiments, the glass articles made from the glass compositions may be ion-exchanged by exposure to molten NaNO.sub.3 salt at a temperature of 500° C. In such embodiments, the Na.sup.+ ions replace some portion of the Li.sup.+ ions in the glass article to develop a surface compressive layer and exhibit high crack resistance. The resulting compressive stress layer may have a depth (also referred to as a “depth of compression” or “DOC”) of at least 100 μm on the surface of the glass article in 2 hours. In embodiments, the bath further comprises molten KNO3 salt.
[0138] In embodiments, a colored glass article made from a glass composition may be ion-exchanged to achieve a depth of compression of 10 μm or greater, 20 μm or greater, 30 μm or greater, 40 μm or greater, 50 μm or greater, 60 μm or greater, 70 μm or greater, 80 μm or greater, 90 μm or greater, or 100 μm or greater. In embodiments, the colored glass article made from the glass composition may have a thickness “t” and may be ion-exchanged to achieve a depth of compression greater than or equal to 0.15t, greater than or equal to 0.17t, or even greater than or equal to 0.2t. In embodiments, the colored glass article made from the glass composition may have a thickness “t” and may be ion-exchanged to achieve a depth of compression less than or equal to 0.3t, less than or equal to 0.27t, or even less than or equal to 0.25t. In embodiments, the colored glass article made from the glass composition described herein may have a thickness “t” and may be ion-exchanged to achieve a depth of compression greater than or equal to 0.15t and less than or equal to 0.3t, greater than or equal to 0.15t and less than or equal to 0.27t, greater than or equal to 0.15t and less than or equal to 0.25t, greater than or equal to 0.17t and less than or equal to 0.3t, greater than or equal to 0.17t and less than or equal to 0.27t, greater than or equal to 0.17t and less than or equal to 0.25t, greater than or equal to 0.2t and less than or equal to 0.3t, greater than or equal to 0.2t and less than or equal to 0.27t, or even greater than or equal to 0.2t and less than or equal to 0.25t, or any and all sub-ranges formed from any of these endpoints.
[0139] The development of this surface compression layer is beneficial for achieving a better crack resistance and higher flexural strength compared to non-ion-exchanged materials. The surface compression layer has a higher concentration of the ions exchanged into the colored glass article in comparison to the concentration of the ions exchanged into the colored glass article for the body (i.e., the area not including the surface compression) of the colored glass article. In embodiments, the colored glass article made from the glass composition may have a surface compressive stress after ion-exchange strengthening greater than or equal to 300 MPa, greater than or equal to 400 MPa, greater than or equal to 500 MPa, or even greater than greater than or equal to 600 MPa. In embodiments, the colored glass article made from the glass composition may have a surface compressive stress after ion-exchange strengthening less than or equal to 1 GPa, less than or equal to 900 MPa, or even less than or equal to 800 MPa. In embodiments, the colored glass article made from the glass composition may have a surface compressive stress after ion-exchange strengthening greater than or equal to 300 MPa and less than or equal to 1 GPa, greater than or equal to 300 MPa and less than or equal to 900 MPa, greater than or equal to 300 MPa and less than or equal to 800 MPa, greater than or equal to 400 MPa and less than or equal to 1 GPa, greater than or equal to 400 MPa and less than or equal to 900 MPa, greater than or equal to 400 MPa and less than or equal to 800 MPa, greater than or equal to 500 MPa and less than or equal to 1 GPa, greater than or equal to 500 MPa and less than or equal to 900 MPa, greater than or equal to 500 MPa and less than or equal to 800 MPa, greater than or equal to 600 MPa and less than or equal to 1 GPa, greater than or equal to 600 MPa and less than or equal to 900 MPa, greater than or equal to 600 MPa and less than or equal to 800 MPa,
[0140] In embodiments, the colored glass articles made from the glass composition may have a central tension after ion-exchange strengthening greater than or equal to 40 MPa, greater than or equal to 60 MPa, greater than or equal to 80 MPa, or even greater than or equal to 100 MPa. In embodiments, the colored glass article made from the glass composition may have a central tension after ion-exchange strengthening less than or equal to 250 MPa, less than or equal to 200 MPa, or even less than or equal to 150 MPa. In embodiments, the colored glass article made from the glass composition may have a central tension after ion-exchange strengthening greater than or equal to 40 MPa and less than or equal to 250 MPa, greater than or equal to 40 MPa and less than or equal to 200 MPa, greater than or equal to 40 MPa and less than or equal to 150 MPa, greater than or equal to 60 MPa and less than or equal to 250 MPa, greater than or equal to 60 MPa and less than or equal to 200 MPa, greater than or equal to 60 MPa and less than or equal to 150 MPa, greater than or equal to 80 MPa and less than or equal to 250 MPa, greater than or equal to 80 MPa and less than or equal to 200 MPa, greater than or equal to 80 MPa and less than or equal to 150 MPa, greater than or equal to 100 MPa and less than or equal to 250 MPa, greater than or equal to 100 MPa and less than or equal to 200 MPa, or even greater than or equal to 100 MPa and less than or equal to 150 MPa, or any and all sub-ranges formed from any of these endpoints.
[0141] As described herein, the glass compositions described herein increase the solubility of Cr.sub.2O.sub.3, which increases the amount of Cr.sub.2O.sub.3 present in the resultant colored glass articles, thereby expanding the color gamut achievable by the colored glass articles. Referring now to
[0142] Different color gamuts may be achieved by including other colorants in addition to Cr.sub.2O.sub.3. Referring now to
[0143] Referring now to
[0144] Referring now to
[0145] Referring now to
[0146] Referring now to
[0147] Referring now to
[0148] Referring now to
[0149] The colored glass articles described herein may be used for a variety of applications including, for example, back cover applications in consumer or commercial electronic devices such as smartphones, tablet computers, personal computers, ultrabooks, televisions, and cameras. An exemplary article incorporating any of the colored glass articles disclosed herein is shown in
EXAMPLES
[0150] In order that various embodiments be more readily understood, reference is made to the following examples, which illustrate various embodiments of the colored glass articles described herein.
[0151] Table 1 shows example glass compositions (in terms of mol %) and the transmittance color coordinate in the CIELAB color space, as measured at an article thickness of 1.5 mm under F2 illumination and a 10° standard observer angle, of the resultant colored glass articles.
TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 SiO.sub.2 58.78 58.30 58.52 58.97 58.26 58.52 Al.sub.2O.sub.3 16.68 16.35 16.50 16.41 16.38 16.56 B.sub.2O.sub.3 5.93 5.93 6.01 5.98 5.93 6.04 Li.sub.2O 11.74 9.86 9.93 9.89 9.85 9.89 Na.sub.2O 6.26 4.25 4.27 4.27 4.26 4.30 K.sub.2O 0.48 0.48 0.48 0.49 0.48 0.49 MgO 0.02 2.91 2.95 2.91 2.94 2.93 CaO 0.01 0.01 0.01 0.01 0.01 0.02 ZnO — 1 1.01 1 1 1.05 TiO.sub.2 0.01 0.01 0.01 0.01 0.01 0.01 NiO — — 0.023 0.012 0.043 0.089 Co.sub.3O.sub.4 — 0.001 0.002 0.002 0.03 0.048 CuO — 0.83 0.233 0.037 0.785 0.044 Cr.sub.2O.sub.3 0.098 0.068 0.038 0.002 0.016 0.008 R.sub.2O 18.48 14.59 14.68 14.65 14.59 14.68 RO 0.03 3.92 3.97 3.92 3.95 4 R.sub.2O + 1.83 2.16 2.15 2.16 2.16 2.12 RO − Al.sub.2O.sub.3 MgO + ZnO 0.02 3.91 3.96 3.91 3.94 3.98 Al.sub.2O.sub.3 + 16.7 20.26 20.46 20.32 20.32 20.54 MgO + ZnO Transmittance Color Coordinate L* 83.78 77.06 85.88 94.99 66.99 62.17 a* −12.60 −26.24 −9.49 −0.45 −10.12 −2.12 b* 62.26 8.74 6.26 0.17 −14.19 −20.39 Example 7 8 9 10 11 12 SiO.sub.2 57.09 59.21 58.44 58.12 59.20 58.36 Al.sub.2O.sub.3 16.10 16.64 16.21 16.56 16.58 16.11 B.sub.2O.sub.3 5.90 5.62 5.70 6.07 5.67 5.69 Li.sub.2O 9.68 11.75 11.56 11.83 11.82 11.6 Na.sub.2O 4.21 6.18 6.09 6.21 6.16 6.07 K.sub.2O 0.47 0.47 0.47 0.48 0.45 0.46 MgO 2.86 0.02 0.02 0.02 0.02 0.02 CaO 0.02 0.01 0.01 0.01 0.01 0.01 ZnO 0.98 — — — — — TiO.sub.2 — 0.01 — 0.01 0.01 — NiO 0.014 0.078 0.039 0.071 — — Co.sub.3O.sub.4 0.058 0.001 0.001 0.002 0.002 0.038 CuO 2.598 0.002 1.351 0.563 0.086 1.583 Cr.sub.2O.sub.3 0.006 0.009 0.102 0.051 0.002 0.051 R.sub.2O 14.36 18.4 18.12 18.52 18.43 18.13 RO 3.86 0.03 0.03 0.03 0.03 0.03 R.sub.2O + 2.12 1.79 1.94 1.99 1.88 2.05 RO − Al.sub.2O.sub.3 MgO + ZnO 3.84 0.02 0.02 0.02 0.02 0.02 Al.sub.2O.sub.3 + 19.94 16.66 16.23 16.58 16.6 16.13 MgO + ZnO Transmittance Color Coordinate L* 38.41 89.31 89.27 76.84 94.52 41.28 a* −14.36 −0.65 −0.77 −14.83 −1.14 −18.17 b* −13.36 17.15 17.45 11.73 −2.04 −13.89 Example 13 14 15 16 17 18 SiO.sub.2 58.03 58.39 58.48 58.45 58.58 58.71 Al.sub.2O.sub.3 16.57 16.49 16.53 16.49 16.42 16.54 B.sub.2O.sub.3 6.03 6.01 6.09 6.04 5.97 5.99 Li.sub.2O 11.93 10.02 10.08 10.04 10.5 10.48 Na.sub.2O 6.23 4.28 4.26 4.25 4.71 4.76 K.sub.2O 0.48 0.48 0.49 0.48 0.48 0.49 MgO 0.02 2.95 2.94 2.94 0.96 0.97 CaO 0.01 0.02 0.01 0.02 0.98 0.98 ZnO — 1.01 1.01 1.01 0.99 1.02 TiO.sub.2 0.01 0.01 0.01 0.01 0.01 0.01 NiO 0.093 0.021 — 0.082 0.019 — Co.sub.3O.sub.4 0.072 0.002 0.002 0.048 0.002 0.002 CuO 0.516 0.278 0.091 0.137 0.339 0.054 Cr.sub.2O.sub.3 0.012 0.036 0.001 0.006 0.039 0.001 R.sub.2O 18.64 14.78 14.83 14.77 15.69 15.73 RO 0.03 3.98 3.96 3.97 2.93 2.97 R.sub.2O + 2.1 2.27 2.26 2.25 2.2 2.16 RO − Al.sub.2O.sub.3 MgO + ZnO 0.02 3.96 3.95 3.95 1.95 1.99 Al.sub.2O.sub.3 + 16.59 20.45 20.48 20.44 18.37 18.53 MgO + ZnO Transmittance Color Coordinate L* 38.93 85.89 95.05 62.68 85.25 95.29 a* 1.10 −9.54 −0.84 −2.13 −10.39 −0.68 b* −44.38 5.68 −0.62 −20.72 6.20 −0.90 Example 19 SiO.sub.2 58.51 Al.sub.2O.sub.3 16.49 B.sub.2O.sub.3 6.06 Li.sub.2O 10.47 Na.sub.2O 4.76 K.sub.2O 0.49 MgO 0.97 CaO 0.99 ZnO 1.01 TiO.sub.2 0.01 NiO 0.085 Co.sub.3O.sub.4 0.048 CuO 0.111 Cr.sub.2O.sub.3 0.005 R.sub.2O 15.72 RO 2.97 R.sub.2O + 2.2 RO − Al.sub.2O.sub.3 MgO + ZnO 1.98 Al.sub.2O.sub.3 + 18.47 MgO + ZnO Transmittance Color Coordinate L* 61.08 a* −2.34 b* −22.51
[0152] As indicated by the example glass compositions and colored glass articles in Table 1, the glass compositions described herein improve Cr.sub.2O.sub.3 solubility to form colored glass articles having the desired color. For example, example glass composition 1 including 0.098 mol % Cr.sub.2O3 formed a colored glass article having a transmittance color coordinate in the CIELAB color space of L*=83.78, a*=−12.60, and b*=62.26.
[0153] As further indicated by the example glass compositions and colored glass articles in Table 1, adding other colorants in addition to Cr.sub.2O.sub.3 as described herein allows different color gamuts to be achieved. For example, example glass composition 2 including 0.068 mol % Cr.sub.2O.sub.3, 0.001 mol % Co.sub.3O.sub.4, and 0.83 mol % CuO formed a colored glass article have a transmittance color coordinate in the CIELAB color space of L*=77.06, a*=−26.24, and b*=8.74. Example glass composition 3, including 0.038 mol % Cr.sub.2O.sub.3, 0.023 mol % NiO, 0.002 mol % Co.sub.3O.sub.4, and 0.233 mol % CuO formed a colored glass article have a transmittance color coordinate in the CIELAB color space of L*=85.88, a*=−9.40, and b*=6.26.
[0154] It will be apparent to those skilled in the art that various modifications and variations may be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and
[0155] variations come within the scope of the appended claims and their equivalents.