Well-Dispersed α-Fe2O3 Particles for Lead-Free Red Overglaze Enamels through Hydrothermal Treatment

The traditional Japanese overglaze ceramic, akae porcelain, typically known for Kakiemon-style wares, has been prized around the world for over 400 years. The red color of akae porcelain provides an attractive contrast to white porcelain. In recent years, because the use of leaded frit in making akae has been restricted by law owing to the effects of lead on human health and the environment, lead-free glass frit mixtures for overglaze ceramic wares have been developed in various porcelain production areas throughout Japan. However, current lead-free frit for red overglaze enamels produces a color that is duller than that of conventional leaded frit. Therefore, the development of red pigments that are suitable for use with lead-free frit is strongly desired. In this study, we used a hydrothermal process to prepare nanosized iron oxide and oxyhydroxide powders, which showed good particle dispersion in molten lead-free frit. The precursor paste was prepared by reacting iron nitrate with ammonium hydrogen carbonate and heated in a sealed vessel at 80-150 degrees C. The sample powder prepared at 90 degrees C was almost monophasic alpha-Fe2O3 (hematite) and exhibited the brightest red color (highest L*, a*, and b* values). This powder featured primary particles of similar to 15 nm in diameter that aggregated to form secondary spherical particles of similar to 100 nm in diameter. This powder was mixed with lead-free frit and applied as a red paint to a porcelain test piece. The resultant akae showed a bright red color with high L*, a*, and b* values that exceeded the values of akae prepared using conventional hematite powder. Microscopic analysis revealed that the hematite particles were well dispersed in the resultant glass layer, indicating that the hematite powders have good dispersibility in molten frit.