Synthesis of Cobalt Oxide Free Black Color Spinel Pigment

Spinel pigments, developing black color in high temperature glazes at oxidation or reduction atmosphere, without CoO because of its high price were synthesized by solid solution method. Ten mixed compositions consisted of NiO, MnO, $Fe_2O_3 and $Mn_2O_3$ were fired at $1250^{\circ}C$ for 1h. The resulting pigments were characterized by using XRD, FT-IR, SEM and UV-vis spectrometer. Structure of the pigments are spinel and particles' shape are spherical or cubic. Glazed tiles containing 5 wt% pigments were fired at $1260^{\circ}C$ and $1240^{\circ}C$ in reduction atmosphere. Color in glazes were analyzed by UV-vis spectrometer. Colors of NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole% in lime glaze showed black in oxidation, in reduction NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.55{\cdot}Mn_2O_3$ 0.0125 mole% showed black. In case of lime-barium glaze, NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.975 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black color in oxidation and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.725 MnO $0.275{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black one in reduction.

CoO가 첨가되지 않은 스피넬계 흑색안료의 합성