Colored alkali aluminosilicate glass articles

Abstract

A glass article including at least about 40 mol % SiO 2 and, optionally, a colorant imparting a preselected color is disclosed. In general, the glass includes, in mol %, from about 40-70 SiO 2 , 0-25 Al 2 O 3 , 0-10 B 2 O 3 ; 5-35 Na 2 O, 0-2.5 K 2 O, 0-8.5 MgO, 0-2 ZnO, 0-10% P 2 O 5 and 0-1.5 CaO. As a result of ion exchange, the glass includes a compressive stress (σ s ) at at least one surface and, optionally, a color. In one method, communicating a colored glass with an ion exchange bath imparts σ s while in another; communicating imparts σ s and a preselected color. In the former, a colorant is part of the glass batch while in the latter; it is part of the bath. In each, the colorant includes one or more metal containing dopants formulated to impart to a preselected color. Examples of one or more metal containing dopants include one or more transition and/or rare earth metals.

1 . A colored glass formulated to be ion exchangeable comprising:
 a. one or more metal containing dopants formulated to impart a preselected color;   b. following an ion exchange treatment (IOX) up to about 64 hours:
 i. having at least one surface under a compressive stress (σ s ) comprising at least about 500 MPa; 
 ii. the at least one surface under the compressive stress (σ s ) exhibiting a depth of layer (DOL) comprising at least about 15 μm; and 
 iii. a color difference (ΔE) in the CIELAB color coordinates space of the preselected color of the colored glass after IOX treatment and before IOX treatment determined from specular transmittance measurements using a spectrophotometer comprising:
 7. up to about 8.2 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 8. up to about 9.1 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 9. up to about 8.4 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65; or 
 10. up to about 5.2 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 11. up to about 6.3 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 12. up to about 6.5 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65; and 
 
   c. SiO 2  comprising at least about 40 mol %.   
     
     
         2 . The colored glass of  claim 1 , further comprising Al 2 O 3 ; at least one alkali metal oxide of the form R 2 O, wherein R comprises one or more of Li, Na, K, Rb, and Cs; and one or more of B 2 O 3 , K 2 O, MgO, ZnO, and P 2 O 5 . 
     
     
         3 . The colored glass of  claim 1 , wherein:
 c. SiO 2  comprises from about 40 mol % to about 70 mol %;   d. Al 2 O 3  comprises from about 0 mol % to about 25 mol %;   e. B 2 O 3  comprises from 0 mol % to about 10 mol %;   f. Na 2 O comprises from about 5 mol % to about 35 mol %;   g. K 2 O comprises from 0 mol % to about 2.5 mol %;   h. MgO comprises from 0 mol % to about 8.5 mol %;   i. ZnO comprises from 0 mol % to about 2 mol %;   j. P 2 O 5  comprises from about 0 to about 10%;   k. CaO comprises from 0 mol % to about 1.5 mol %;   l. Li 2 O comprises from 0 mol % to about 20 mol %;   m. Rb 2 O comprises from 0 mol % to about 20 mol %; and   n. Cs 2 O comprises from 0 mol % to about 20 mol %.   
     
     
         4 . The colored glass of  claim 1 , wherein one or more metal containing dopants formulated to impart a preselected color comprises one or more of transition metals, one or more of rare earth metals, or one or more of transition metals and one or more of rare earth metals. 
     
     
         5 . The colored glass of  claim 4 , wherein one or more metal containing dopants sources comprises one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 
     
     
         6 . The colored glass of  claim 1 , wherein one or more metal containing dopants formulated to impart a preselected color comprises one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V. 
     
     
         7 . The colored glass of  claim 2 , wherein a sum of the mol % of R 2 O+Al 2 O 3 +MgO+ZnO comprises at least about 25 mol %. 
     
     
         8 . The colored glass of  claim 1 , wherein the ion exchange treatment (IOX) is at between about 350° C. and 500° C. for between about 1 hours and 64 hours. 
     
     
         9 . The colored glass of  claim 1 , wherein:
 iii. the color difference (ΔE) in the CIELAB color coordinate space of the preselected color of the colored glass after IOX treatment and before IOX treatment determined from specular transmittance measurements using a spectrophotometer comprises:
 7. up to about 3.5 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 8. up to about 3.6 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 9. up to about 3.3 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65; or 
 10. up to about 5.2 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 11. up to about 6.3 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 12. up to about 6.5 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65; and 
   
     
     
         10 . The colored glass of  claim 1 , wherein the colored glass comprises a glass article comprising a thickness of up to about 1 mm. 
     
     
         11 . The colored glass of  claim 1 , further comprising at least one fining agent comprising one or more of F, Cl, Br, I, As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , and combinations thereof. 
     
     
         12 . A method of making a glass article having at least one surface under a compressive stress (σ s ), the at least one surface under the compressive stress (σ s ) exhibiting a depth of layer (DOL), and a preselected colored at least one surface, the method comprising communicating at least one surface of an aluminosilicate glass article comprising SiO 2  comprising at least about 40 mol % and a bath comprising one or more metal containing dopant sources and formulated to impart the preselected color to the aluminosilicate glass article by an ion exchange treatment of the aluminosilicate glass article at a temperature between about 350° C. and about 500° C. for a sufficient time up to about 64 hours to impart the compressive stress (σ s ), the depth of layer (DOL), and the preselected color at least one surface of the aluminosilicate glass. 
     
     
         13 . The method of  claim 12 , wherein the compressive stress (σ s ) comprising at least about 500 MPa and the at least one surface under the compressive stress (σ s ) exhibits a depth of layer (DOL) comprising at least about 15 μm. 
     
     
         14 . The method of  claim 12 , wherein the aluminosilicate glass comprises:
 a. SiO 2  comprises from about 40 mol % to about 70 mol %;   b. Al 2 O 3  comprises from about 0 mol % to about 25 mol %;   c. B 2 O 3  comprises from 0 mol % to about 10 mol %;   d. Na 2 O comprises from about 5 mol % to about 35 mol %;   e. K 2 O comprises from 0 mol % to about 2.5 mol %;   f. MgO comprises from 0 mol % to about 8.5 mol %;   g. ZnO comprises from 0 mol % to about 2 mol %;   h. P 2 O 5  comprises from about 0 to about 10%;   i. CaO comprises from 0 mol % to about 1.5 mol %;   j. Li 2 O comprises from 0 mol % to about 20 mol %;   k. Rb 2 O comprises from 0 mol % to about 20 mol %; and   l. Cs 2 O comprises from 0 mol % to about 20 mol %.   
     
     
         15 . The method of  claim 12 , wherein the bath comprises a composition comprising (1) one or more salts comprising a strengthening ion source, optionally: (a) when the aluminosilicate glass comprises a lithium aluminosilicate glass the one or more strengthening ion sources comprise one or more ions of sodium (Na + ), potassium (K + ), rubidium (Rb + ), and/or cesium (Cs + ) exchangeable for lithium (Li + ) ions; or (b) when the aluminosilicate glass comprises a sodium aluminosilicate glass the one or more strengthening ion sources comprise one or more ions of potassium (K + ), rubidium (Rb + ), and/or cesium (Cs + ) exchangeable for sodium (Na + ) ions; or (c) when the aluminosilicate glass comprises a potassium aluminosilicate glass the one or more strengthening ion sources comprise one or more ions of rubidium (Rb + ), and/or cesium (Cs + ) exchangeable for potassium (K + ); (2) the one or more metal containing dopant sources, and (3) a melting temperature less than or equal to the ion exchange treatment temperature. 
     
     
         16 . The method of  claim 12 , wherein the one or more metal containing dopants sources comprises one or more of transition metals, one or more of rare earth metals, or one or more of transition metals and one or more of rare earth metals. 
     
     
         17 . The method of  claim 16 , wherein the one or more metal containing dopants sources comprises one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 
     
     
         18 . The method of  claim 12 , wherein the one or more metal containing dopants sources comprises one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V. 
     
     
         19 . The method of  claim 12 , wherein the one or more salts comprises a formulation comprising one or more of a halide, cyanide, carbonate, chromate, a nitrogen oxide radical, manganate, molybdate, chlorate, sulfide, sulfite, sulfate, vanadyl, vanadate, tungstate, and combinations of two or more of the proceeding. 
     
     
         20 . The method of  claim 19 , wherein the one or more salts comprises a formulation comprising one or more of a metal halide, carbonate, chromate, a nitrate, manganate, sulfide, sulfite, sulfate, vanadyl, vanadate, and combinations of two or more of the proceeding. 
     
     
         21 . A method of making a colorfast, ion exchangeable glass comprising:
 a. forming a glass composition comprising:
 i. SiO 2  comprising at least about 40 mol %; 
 ii. Al 2 O 3 ; and 
 iii. one or more metal containing dopants in amounts formulated to impart a preselected color, 
   wherein following an ion exchange treatment (10×) up to about 64 hours, the ion exchanged glass article comprises
 1. at least one surface under a compressive stress (σ s ) comprising at least about 500 MPa; 
 2. the at least one surface under the compressive stress (σ s ) exhibiting a depth of layer (DOL) comprising at least about 15 μm; and 
 3. a color difference (ΔE=[{ΔL*} 2 +{Δ*} 2 +{Δb*} 2 ] 0.5 ) in the CIELAB color space coordinates of the preselected color of the colored glass after IOX treatment and before IOX treatment determined from specular transmittance measurements using a spectrophotometer comprising:
 a. up to about 8.2 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 b. up to about 9.1 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 c. up to about 8.4 when measurement results obtained between about 200 nm-2500 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65; or 
 d. up to about 5.2 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant A; or 
 e. up to about 6.3 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02; or 
 f. up to about 6.5 when measurement results obtained between about 360 nm-750 nm are presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant D65. 
 
   
     
     
         22 . The method of making the colorfast, ion exchangeable glass of  claim 21 , wherein the glass composition further comprising at least one alkali metal oxide of the form R 2 O, wherein R comprises one or more of Li, Na, K, Rb, and Cs; and one or more of B 2 O 3 , K 2 O, MgO, ZnO, and P 2 O 5 . 
     
     
         23 . The method of making the colorfast, ion exchangeable glass of  claim 21 , wherein:
 i. SiO 2  comprises from about 40 mol % to about 70 mol %;   ii. Al 2 O 3  comprises from about 0 mol % to about 25 mol %;   iii. B 2 O 3  comprises from 0 mol % to about 10 mol %;   iv. Na 2 O comprises from about 5 mol % to about 35 mol %;   v. K 2 O comprises from 0 mol % to about 2.5 mol %;   vi. MgO comprises from 0 mol % to about 8.5 mol %;   vii. ZnO comprises from 0 mol % to about 2 mol %;   viii. P 2 O 5  comprises from about 0 to about 10%;   ix. CaO comprises from 0 mol % to about 1.5 mol %;   x. Li 2 O comprises from 0 mol % to about 20 mol %;   xi. Rb 2 O comprises from 0 mol % to about 20 mol %; and   xii. Cs 2 O comprises from 0 mol % to about 20 mol %.   
     
     
         24 . The method of making the colorfast, ion exchangeable glass of  claim 21 , wherein the one or more metal containing dopants formulated to impart a preselected color comprises one or more of transition metals, one or more of rare earth metals, or one or more of transition metals and one or more of rare earth metals. 
     
     
         25 . The method of making the colorfast, ion exchangeable glass of  claim 24 , wherein the one or more metal containing dopants sources comprises one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 
     
     
         26 . The method of making the colorfast, ion exchangeable glass of  claim 21 , wherein the one or more metal containing dopants formulated to impart a preselected color comprises one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V. 
     
     
         27 . The method of making the colorfast, ion exchangeable glass of  claim 22 , wherein a sum of the mol % of R 2 O+Al 2 O 3 +MgO+ZnO comprises at least about 25 mol %.