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Abstract: Japanese traditional red overglaze enamel decorations on porcelain known as akae are produced using lead‐containing frits, leading to a problem of lead release. Although many lead‐free frits have been developed, a well‐colored akae has not yet been realized, mainly because of no information on the reaction between lead‐free frits and hematite during the heating process in akae production. To reveal the effect of such interaction between the frits and hematite in akae on the color tone, various akae test pieces were prepared and investigated. On using low‐melting‐point lead‐free alkali borosilicate glass system, which contain zinc oxide, the formation of zinc ferrite proceeds simultaneously with the dissolution and particle growth of hematite in the frit melt. The particle growth rate due to dissolution and precipitation in the frit melt is faster than that due to sintering of particles caused by heat treatment of hematite powder in dry process. The dissolving capacity and promoting effect of particle growth depended on frit compositions. We also showed that the composition of akae glass layer varies because of ions diffusing from the glaze layer. Compositional changes in the akae glass could strongly affect the reactivity between the frits and hematite, resulting in variation in the color tone, the crystal phases formed, and their segregated states. [ABSTRACT FROM AUTHOR]

Inspired by the ion diffusion at the interface between the red glaze and glaze layers, which was confirmed by the study of overglaze painting on porcelain test pieces, we developed frits with compositions in which a lime glaze was systematically added to a lead-free multicomponent alkali borosilicate glass frit. When the mixed powder of the frit and hematite was heat-treated, the excessive reaction with hematite was suppressed as the lime glaze content increased, due to the increase of the frit viscosity. The dissolution of hematite was suppressed in the sample with the same viscosity at a higher heat treatment temperature, i.e., with a higher lime glaze content, confirming that the composition of the frit strongly affects the dissolution of hematite. We attempted to improve the chroma of lime-glaze-added samples, and the highest chroma in this system was achieved by adjusting the amount of initial hematite and heat treatment temperature. • Frits with compositions in which a lime glaze was systematically added to an alkali borosilicate glass frit were developed. • Reaction between the lead-free frit and hematite was investigated. • Viscosity and chemical composition of the frit affected the reaction. • Red color was successfully controlled by adjusting initial experimental conditions. [ABSTRACT FROM AUTHOR]

• Crystal growth mechanism of hematite in high-temperature lead-free glass frit was investigated. • Hematite particles slightly grew due to sintering up to near softening point of the frit. • Hematite crystal growth occurs through Ostwald ripening above softening point. • Resultant hematite crystal was surrounded by low index crystal planes having low surface free energy. To elucidate the crystal growth process of hematite in high-temperature lead-free multicomponent alkali borosilicate glass, which is essentially important to control the color of red overglaze enamels, frit and hematite mixture is heat-treated and subjected to microscopic observations. Hematite particles slightly grew due to sintering at low temperature. Once the glass matrix formed near the softening point of frit, hematite dissolved into glass fluid. Hematite crystal growth concomitantly ensued with decrease in the number of hematite particles via Ostwald ripening as the temperature increased. The grown particles exhibited an anisotropic morphology with straight outlines reflecting crystal planes, the morphology of which is completely different from those grown by sintering and particles prior to heating. These results suggest that comprehensive understanding of frit and hematite from the perspectives of glass science and chemistry as well as powder technology are important to truly control the color of red overglaze enamels. [ABSTRACT FROM AUTHOR]

A mixture of a lead-free multicomponent alkali borosilicate glass frit containing zinc ions and hematite was heat-treated under various conditions to elucidate the reaction between the two components, which is essentially important for controlling the color of red overglaze enamels. Above the glass transition temperature, the interaction between the frit fluid and hematite was evident, as the viscosity of the frit decreased. Moreover, hematite dissolved, the iron ions diffused into the glass matrix and they precipitated on residual hematite, resulting in enhanced crystal growth through Ostwald ripening. Concurrently, the iron and zinc ions reacted to form zinc ferrite. During cooling, the supersaturated iron ions were consumed for precipitation of hematite and zinc ferrite. Because frit and hematite dramatically react during heat treatment, conventional modification of hematite alone is insufficient. Development of the frit exhibiting low reactivity toward hematite through precise control of physical properties is a future challenging issue. [ABSTRACT FROM AUTHOR]