No abstract

Akae porcelain, an artistic Japanese traditional overglaze ceramic typically known for Kakiemon-style ware, has fascinated porcelain lovers around the world for over 400 years because of the graceful red color displayed by akae that matches so well with white porcelain bodies. In this work, we clarified the factors that control the color of akae and those that are conventionally controlled by artisans based on empirical experience. Inspired by a recent particle-design method, we also developed a practical facile process to prepare red paints that yields high-quality akae. Various akae samples were prepared from a combination of lead-free alkali borosilicate glass frits with different particle sizes and hematite powders with differing dispersibilities. Polarized light microscopy, scanning electron microscopy, and transmission electron microscopy analyses indicate that considering only the dispersibility of hematite powders is not sufficient, but the frit-particle size must be controlled to obtain high-quality akae with a high reflectance value for ≥580 nm visible light. In addition, we developed a process for preparing high-quality red paints that uses a large-particle frit powder and a strongly aggregated-hematite powder, both of which are easily obtainable. The red paint composed of frit, hematite, and the solvent is mixed until the paint is drying. By adding more solvent and repeating this process three times, we obtained high-quality akae with a higher reflectance value than for the akae prepared from a frit with submicron-sized particles and weakly aggregated-hematite powder. On the basis of transmission electron microscopic observations, we consider the red paint to consist of a core/shell-like composite structure of frit and hematite, forming a three-dimensional network in the akae glass layer. The good dispersibility of these particles leads to high-quality akae.

The Japanese traditional red overglaze ceramic ware, akae, a composite in which hematite particles are dispersed in a glass-frit layer, has become extremely popular with porcelain lovers all over the world. Recently, development of hematite powders dedicated to akae is strongly desired by various porcelain producers. Inspired by Fukiya bengala, a high-quality old red pigment produced in Japan in the early 18th century, we produced Al-substituted hematite powder through wet-process in a large scale. In this study, we investigated the effect of dispersion and aggregation of hematite particles on the color tone of the resultant powder, and developed a technique to produce high-quality akae using the hematite powder. The prepared powder is primarily composed of hematite nanoparticles ³10 nm in diameter that contains 5 mol % of Al 3+ in the structure, and these primary particles are aggregated to form secondary particles 3070 nm in diameter. The powder showed dark brown color regardless of its nanometric character because the secondary particles form large aggregated particles with high volume fraction of hematite, leading to prevent transmission of visible light. Applying ultrasonic and silica-coating treatments that realize low volume fraction of hematite, we obtained the hematite powder exhibiting yellowish red color. In addition, high-quality akae test pieces having highly dispersive hematite particles in a glass layer were successfully prepared using ballmilling technique and subsequent combination process with the submicron-sized lead-free frit.

Inspired by a bacteriogenic, iron-based oxide material and a traditional Japanese red pigment, a bright yellowish-red pigment was prepared by heating an Al-containing iron oxyhydroxide precursor. The obtained red pigment had a unique porous disk-like structure, comprising Alsubstituted hematite particles and crystalline alumina nanoparticles. Although these disk-like structures loosely gathered to form an aggregate in powder, they can be easily dispersed into a single, disk-like structure by simple ultrasonic irradiation. The powder exhibited a bright yellowish-red color and high thermostability, making it attractive as a coloring material for various industrial products needing a bright-red color, high weather resistance, and durability. Quantitative color measurements revealed extremely high L*, a*, and b* values that are much greater than those of commercially available hematite. The thermostability test showed that even after exposure to high temperatures, the pigment retained the red color, indicating its high thermostability. The unique microstructure should be strongly related to the bright yellowish-red color and the high thermostability of the developed red pigment.

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 °C. The sample powder prepared at 90 °C was almost monophasic α-Fe 2 O 3 (hematite) and exhibited the brightest red color (highest L *, a *, and b * values). This powder featured primary particles of ∼15 nm in diameter that aggregated to form secondary spherical particles of ∼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.