Transparent, near infrared-shielding glass ceramic

Abstract

Optically transparent glass ceramic materials comprising a glass phase containing and a crystalline tungsten bronze phase comprising nanoparticles and having the formula M x WO 3 , where M includes at least one H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0<x<1. Aluminosilicate and zinc-bismuth-borate glasses comprising at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 are also provided.

1 . A glass ceramic, the glass ceramic comprising
 a silicate glass phase; and   from about 0.1 mol % to about 10 mol % of a crystalline M x WO 3  phase comprising nanoparticles, where M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and 0<x<1.   
     
     
         2 . The glass ceramic of  claim 1 , wherein the glass ceramic has a transmittance of at least 10%/mm over a wavelength band over at least one 50 nm-wide wavelength band of light for light having a wavelength in a range from about 400 nm to about 700 nm. 
     
     
         3 . The glass ceramic of  claim 1 , wherein the glass ceramic has transmittance of less than 1%/mm for light having a wavelength of about 370 nm or less. 
     
     
         4 . The glass ceramic of  claim 1 , wherein the glass ceramic has a transmittance of less than 5%/mm over at least one 50 nm-wide wavelength band of light for light having a wavelength in a range from about 700 nm to about 2500 nm. 
     
     
         5 . The glass ceramic of  claim 4 , wherein the transmittance of the glass ceramic between about 500 nm and about 2500 nm changes by less than 10%/mm when the glass ceramic is heated at a temperature in a range from about 200° C. to about 300° C. 
     
     
         6 . The glass ceramic of  claim 1 , wherein the glass ceramic is ion exchangeable. 
     
     
         7 . The glass ceramic of  claim 6 , wherein the glass ceramic is ion exchanged and has a compressive layer extending from a surface of the glass ceramic to a depth of at least about 10 μm within the glass ceramic, the compressive layer having a compressive stress of at least about 100 MPa and less than about 1500 MPa at the surface. 
     
     
         8 . The glass ceramic of  claim 1 , wherein the glass ceramic is bleachable by thermal treatment. 
     
     
         9 . The glass ceramic of  claim 1 , wherein the glass ceramic has a coefficient of thermal expansion of less than or equal to about 75×10 −7 ° C. −1  at temperatures ranging from 0° C. to about 300° C. 
     
     
         10 . The glass ceramic of  claim 1 , wherein the silicate glass phase is a borosilicate glass phase. 
     
     
         11 . The glass ceramic of  claim 1 , wherein the glass ceramic comprises from about 0.1 mol % to about 5 mol % of the crystalline M x WO 3  phase. 
     
     
         12 . The glass ceramic of  claim 1 , wherein M is at least one alkali metal. 
     
     
         13 . The glass ceramic of  claim 12 , wherein the glass ceramic comprises: from about 56 mol % to about 78 mol % SiO 2 ; from about 8 mol % to about 27 mol % B 2 O 3 ; from about 0.5 mol % to about 14 mol % Al 2 O 3 ; from greater than 0 mol % to about 10 mol % of at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O; from about 1 mol % to about 10 mol % WO 3 ; and from 0 mol % to about 0.5 SnO 2 . 
     
     
         14 . The glass ceramic of  claim 12 , wherein M is Cs and wherein the glass ceramic comprises from greater than 0 mol % to about 10 mol % Cs 2 O. 
     
     
         15 . The glass ceramic of  claim 12 , wherein −10 mol %≦R 2 O (mol %)−Al 2 O 3  (mol %)≦0.1 mol %, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O. 
     
     
         16 . The glass ceramic of  claim 12 , wherein 0<R 2 O (mol %)/WO 3  (mol %)≦2.61, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O. 
     
     
         17 . The glass ceramic of  claim 12 , wherein 0.66≦Al 2 O 3  (mol %)/WO 3  (mol %)≦6. 
     
     
         18 . The glass ceramic of  claim 12 , wherein 1≦(R 2 O (mol %)+Al 2 O 3  (mol %))/WO 3  (mol %)≦6, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O. 
     
     
         19 . The glass ceramic of  claim 12 , wherein the glass ceramic further comprises at least one of: up to about 0.5 mol % MgO; up to about 2 mol % P 2 O 5 ; and up to about 1 mol %. 
     
     
         20 . The glass ceramic of  claim 1 , wherein the glass ceramic comprises: from about 80 mol % to about 97 mol % SiO 2 ; from 0 mol % to about 5 mol % Al 2 O 3 ; from greater than 0 mol % to about 2 mol % Cs 2 O; and from about 0.2 mol % to about 2 mol % WO 3 . 
     
     
         21 . The glass ceramic of  claim 1 , wherein the crystalline M x WO 3  phase comprises at least one of a plurality of platelet-shaped M x WO 3  nanoparticles and a plurality of M x WO 3  nanorods. 
     
     
         22 . The glass ceramic of  claim 21 , wherein the plurality of platelet-shaped M x WO 3  nanoparticles has an average diameter in a range from about 10 nm to 5 m. 
     
     
         23 . The glass ceramic of  claim 21 , wherein the plurality of M x WO 3  nanorods has an average length in a range from about 10 nm to about 1000 nm and an average width ranging in a range from about 2 nm to about 75 nm. 
     
     
         24 . The glass ceramic of  claim 23 , wherein the plurality of M x WO 3  nanorods has an average length in a range from about 10 nm to about 200 nm and an average width ranging in a range from about 2 nm to about 30 nm. 
     
     
         25 . The glass ceramic of  claim 1 , wherein the glass ceramic is at least a portion of a thermal shield, an optical filter, an architectural element, an automotive component, or a housing for an electronic display. 
     
     
         26 . A glass ceramic, the glass ceramic comprising
 a silicate glass phase; and   from about 0.1 mol % to about 10 mol % of a crystalline M x WO 3  phase comprising nanoparticles, where M is at least one alkali metal, and 0<x<1.   
     
     
         27 . The glass ceramic of  claim 26 , wherein the glass ceramic comprises from about 0.1 mol % to about 5 mol % of the crystalline M x WO 3  phase. 
     
     
         28 . The glass ceramic of  claim 26 , wherein the silicate glass phase is a borosilicate glass phase. 
     
     
         29 . The glass ceramic of  claim 26 , wherein the glass ceramic comprises: from about 56 mol % to about 78 mol % SiO 2 ; from about 9 mol % to about 27 mol % B 2 O 3 ; from about 0.5 mol % to about 14 mol % Al 2 O 3 ; from greater than 0 mol % to about 9 mol % of at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O; from about 1 mol % to about 10 mol % WO 3 ; and from 0 mol % to about 0.5 SnO 2 . 
     
     
         30 . The glass ceramic of  claim 26 , wherein M is Cs and wherein the glass ceramic comprises from greater than 0 mol % to about 10 mol % Cs 2 O. 
     
     
         31 . The glass ceramic of  claim 26 , wherein −10 mol %≦R 2 O (mol %)−Al 2 O 3  (mol %)≦0.1 mol %, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O. 
     
     
         32 . The glass ceramic of  claim 26 , wherein 0<R 2 O (mol %)/WO 3  (mol %)≦2.61, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O. 
     
     
         33 . The glass ceramic of  claim 26 , wherein 0.66≦Al 2 O 3  (mol %)/WO 3  (mol %)≦6. 
     
     
         34 . The glass ceramic of  claim 26 , wherein the glass ceramic further comprises at least one of: up to about 0.5 mol % MgO; up to about 2 mol % P 2 O 5 ; and up to about 1 mol %. 
     
     
         35 . The glass ceramic of  claim 26 , wherein the glass ceramic has a transmission of at least 1%/mm over a wavelength band over at least one 50 nm-wide wavelength band of light for light having a wavelength in a range from about 400 nm to about 700 nm. 
     
     
         36 . The glass ceramic of  claim 26 , wherein the glass ceramic has a transmittance of less than 1%/mm for light having a wavelength of about 370 nm or less. 
     
     
         37 . The glass ceramic of  claim 26 , wherein the glass ceramic has a transmittance of less than 5%/mm over at least one 50 nm-wide wavelength band of light for light having a wavelength in a range from about 700 nm to about 2500 nm. 
     
     
         38 . The glass ceramic of  claim 37 , wherein the transmittance of the glass ceramic between about 500 nm and about 2500 nm changes by less than 10%/mm when the glass ceramic is heated at a temperature in a range from about 200° C. to about 300° C. 
     
     
         39 . The glass ceramic of  claim 26 , wherein the glass ceramic is ion exchangeable. 
     
     
         40 . The glass ceramic of  claim 39 , wherein the glass ceramic is ion exchanged and has a compressive layer extending from a surface of the glass ceramic to a depth of at least about 10 μm within the glass ceramic, the compressive layer having a maximum compressive stress of at least about 100 MPa and less than about 1500 MPa at the surface. 
     
     
         41 . The glass ceramic of  claim 26 , wherein the glass ceramic is bleachable by thermal treatment. 
     
     
         42 . The glass ceramic of  claim 26 , wherein the glass ceramic is impervious to moisture and oxygen. 
     
     
         43 . The glass ceramic of  claim 26 , wherein M includes Cs and the glass ceramic comprises: from about 80 mol % to about 97 mol % SiO 2 ; from 0 mol % to about 5 mol % Al 2 O 3 ; from greater than 0 mol % to about 2 mol % Cs 2 O; and from about 0.2 mol % to about 2 mol % WO 3 . 
     
     
         44 . The glass ceramic of  claim 26 , wherein the crystalline M x WO 3  phase comprises at least one of a plurality of platelet-shaped M x WO 3  nanoparticles and a plurality of M x WO 3  nanorods. 
     
     
         45 . The glass ceramic of  claim 44 , wherein the plurality of platelet-shaped M x WO 3  nanoparticles has an average diameter in a range from about 10 nm to 5 m. 
     
     
         46 . The glass ceramic of  claim 44 , wherein the plurality of M x WO 3  nanorods has an average length in a range from about 10 nm to about 1000 nm and an average width ranging in a range from about 2 nm to about 75 nm. 
     
     
         47 . The glass ceramic of  claim 46 , wherein the plurality of M x WO 3  nanorods has an average length in a range from about 10 nm to about 200 nm and an average width ranging in a range from about 2 nm to about 30 nm. 
     
     
         48 . The glass ceramic of  claim 26 , wherein the glass ceramic is at least a portion of a thermal shield, an optical filter, an architectural element, an automotive component, or a protective element for an electronic display. 
     
     
         49 . An aluminosilicate glasses comprising from about 8 mol % to about 45 mol % Al 2 O 3 , from about 40 mol % to about 72 mol % SiO 2  and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , wherein Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ≦30 mol %. 
     
     
         50 . The aluminosilicate glass of  claim 49 , further comprising at least one alkaline earth oxide and B 2 O 3 , wherein 0 mol %≦MgO+CaO+BaO≦24 mol % and 0 mol %≦B 2 O 3 ≦6 mol %. 
     
     
         51 . The aluminosilicate glass of  claim 49 , wherein the glass comprises up to about 30 mol % Pr 2 O 3 . 
     
     
         52 . The aluminosilicate glass of  claim 49 , wherein the glass comprises up to about 28 mol % Sm 2 O 3 . 
     
     
         53 . The aluminosilicate glass of  claim 49 , wherein the aluminosilicate glass has less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm. 
     
     
         54 . A zinc-bismuth-borate glass comprising from about 20 mol % to about 30 mol % ZnO, from about 4 mol % to about 20 mol % Bi 2 O 3 , from about 40 mol % to about 50 mol % B 2 O 3 , and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , wherein Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ≦10 mol %. 
     
     
         55 . The zinc-bismuth-borate glass of  claim 54 , further comprising at least one of Na 2 O and TeO 2 , wherein 0 mol %≦TeO 2 ≦6 mol % and 0 mol %≦Na 2 O≦15 mol %. 
     
     
         56 . The zinc-bismuth-borate glass of  claim 54 , wherein the glass comprises up to about 10 mol % Pr 2 O 3 . 
     
     
         57 . The zinc-bismuth-borate glass of  claim 54 , wherein the glass comprises up to about 10 mol % Sm 2 O 3 . 
     
     
         58 . The zinc-bismuth-borate glass of  claim 54 , wherein the zinc-bismuth-borate glass has less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm. 
     
     
         59 . A phosphate glass comprising at least one rare earth oxide Ln 2 O 3  and having a molar ratio 25Ln 2 O 3 :75P 2 O 5 , where Ln 2 O 3  comprises at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 . 
     
     
         60 . The phosphate glass of  claim 59 , wherein the phosphate glass comprises: from about 6 mol % to about 25% Ln 2 O 3 ; from about 5 mol % to about 27% Al 2 O 3 ; and from about 67 mol % to about 74 mol % P 2 O 5 . 
     
     
         61 . The phosphate glass of  claim 59 , wherein the phosphate glass comprises: from about 6 mol % to about 22.5% Sm 2 O 3 ; from about 5 mol % to about 27% Al 2 O 3 ; and from about 67 mol % to about 74 mol % P 2 O 5 .