Dark-Colored, Low-Expansion Fillers
Colored CTE modifiers may be added to a glass frit system to modify the CTE of a resulting fired enamel. The CTE modifier is colored. The colored CTE modifier may include a modified Pseudo-Brookite type material having a formula Al 2 TiO 5 , where Al and/or Ti are partially substituted with one or more coloring ions including Fe, Cr, Mn, Co, Ni, and Cu; a modified Cordierite type material having a formula Mg 2 Al 4 Si 5 O 18 , wherein Mg and/or Al is partially substituted with one or more of the coloring ions; a Perovskite type material having a formula Sm 1−x Sr x MnO 3−δ , where x=0.0-0.5 and δ=0.0-0.25, or a modified version of the Perovskite type material wherein Sr is partially substituted with Ba and/or Ca; a modified magnesium pyrophosphate type material having a formula Mg 2 P 2 O 7 wherein Mg is substituted with Co and/or Zn ions; or combinations thereof.
1 - 15 . (canceled)
16 . A glass frit system comprising a vehicle, a glass frit, and a colored CTE modifier, the colored CTE modifier comprising:
a Pseudo-Brookite type material having a formula Al 2 TiO 5 , wherein at least one of Al and Ti is partially substituted with at least one coloring ion selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu; or
a modified Cordierite type material having a formula Mg 2 Al 4 Si 5 O 18 , wherein at least one of Mg and Al is partially substituted with at least one coloring ion selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu; or
a Perovskite type material having a formula Sm 1−x Sr x MnO 3−δ , wherein x is within the range of 0.0 to 0.5 and δ is within the range of 0.0 to 0.25, wherein δ represents a degree of oxygen vacancy; or the modified Perovskite type material wherein Sr is partially substituted with at least one of Ba and Ca; or
a modified magnesium pyrophosphate type material having a formula Mg 2 P 2 O 7 wherein Mg is at least partially substituted with at least one of Co and Zn ions; or
a modified eucryptite type material having a formula LiAlSiO 4 wherein Al is at least partially substituted with at least one coloring ion selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu; or
combinations of the foregoing.
17 . The glass frit system according to claim 16 , wherein:
the CTE modifier includes the modified Pseudo-Brookite type material; and wherein:
the modified Pseudo-Brookite type material has:
(i) a formula Al 2−x M x TiO 5 , wherein M represents one or more of the coloring ions, and x is 0.1-2, or
(ii) a formula Al 2 Ti 1−x M x O 5 , where M represents one or more of the coloring ions and x is 0.01-0.4.
18 . The glass frit system according to claim 16 , wherein:
the CTE modifier includes the modified Cordierite type material; and wherein
the modified Cordierite type material has a formula Mg 2−x Al 4−y M x+y Si 5 O 18 , wherein M represents one or more of the coloring ions, and x+y is within the range of 0.1 to 3.0.
19 . The glass frit system according to claim 16 , wherein the CTE modifier comprises the Perovskite type material having the formula Sm 1−x Sr x MnO 3−δ , wherein x is within the range of 0.0 to 0.5 and δ is within the range of 0.0 to 0.25.
20 . The glass frit system according to claim 19 , wherein, in the Perovskite type material having the formula Sm 1−x Sr x MnO 3−δ , Sr is partially substituted with at least one of Ba and Ca.
21 . The glass frit system according to claim 16 , wherein the CTE modifier comprises the modified magnesium pyrophosphate type material.
22 . The glass frit system according to claim 16 , wherein the CTE modifier comprises the modified eucryptite type material.
23 . The glass frit system according to claim 16 , wherein relative to the total weight of the glass frit system:
the vehicle is present at 3.5-80 wt. %,
the glass frit is present at 18.5-95 wt. %,
the colored CTE modifier is present at 0.5-50 wt. %, and
the pigment is present at 1-50 wt. %.
24 . The glass frit system according to claim 16 , further including at least one of a filler, a reducing agent, a dispersant, a surfactant, a rheological modifier, a flow aid, an adhesion promoter, and a stabilizer.
25 . A glass substrate bearing the glass frit system of claim 16 fired to adhere to the substrate.
26 . A glass substrate bearing the glass frit system of claim 17 fired to adhere to the substrate.
27 . A method of forming an enameled substrate, comprising:
providing a substrate;
providing a glass frit system including a vehicle, glass frit, a colored CTE modifier, and a pigment, the colored CTE modifier including:
a modified Pseudo-Brookite type material having a formula Al 2 TiO 5 , wherein Al and/or Ti are partially substituted with at least one coloring ion selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu; or
a modified Cordierite type material having a formula Mg 2 Al 4 SiO 18 , wherein Mg and/or Al are partially substituted with one or more of the coloring ions; or
a Perovskite type material having a formula Sm 1−x Sr x MnO 3−δ , wherein x is within the range of 0.0 to 0.5 and δ is within the range of 0.0 to 0.25, or the modified Perovskite type material wherein Sr is partially substituted with at least one of Ba and Ca; or
a modified magnesium pyrophosphate type material having a formula Mg 2 P 2 O 7 wherein Mg is at least partially substituted with at least one of Co and Zn ions; or
a modified eucryptite type material having a formula LiAlSiO 4 wherein Al is at least partially substituted with at least one coloring ion selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu; or
combinations thereof;
applying the glass frit system to the substrate; and
firing the glass frit system to thereby form a colored enamel adhered to the substrate.
28 . The method according to claim 27 , wherein:
the CTE modifier comprises the modified Pseudo-Brookite type material; and
the modified Pseudo-Brookite type material has:
(i) a formula Al 2−x M x TiO 5 , wherein M represents one or more of the coloring ions, and x is 0.1-2, or
(ii) a formula Al 2 Ti 1−x M x O 5 , where M represents one or more of the coloring ions and x is 0.01-0.4.
29 . The method according to claim 27 , wherein:
the CTE modifier comprises the modified Cordierite type material; and
the modified Cordierite type material has a formula Mg 2−x Al 4−y M x+y Si 5 O 18 , wherein M is one or more of the coloring ions, and x+y is in the range of 0.1 to 3.0.
30 . The method according to claim 27 , wherein the CTE modifier comprises the Perovskite type material having the formula Sm 1−x Sr x MnO 3−δ , wherein x is in the range of 0.0 to 0.5 and δ is in the range of 0.0 to 0.25.
31 . The method according to claim 30 , wherein, in the Perovskite type material having the formula Sm 1−x Sr x MnO 3−δ , Sr is partially substituted with at least one of Ba and Ca.
32 . The method according to claim 27 , wherein the CTE modifier comprises the modified magnesium pyrophosphate type material.
33 . The method according to claim 27 , wherein relative to the total weight of the glass frit system:
the vehicle in included at 3.5-80 wt %,
the glass frit is included at 18.5-95 wt %,
the colored CTE modifier is included at 0.5-50 wt %, and
the pigment is included at 1-50 wt %.
34 . The method according to claim 27 , wherein the glass frit system further comprises at least one of a filler, a reducing agent, a dispersant, a surfactant, a rheological modifier, a flow aid, an adhesion promoter, and a stabilizer.
35 . The method according to claim 27 , wherein the substrate is glass.