Preparation of TiO2–SiO2–CaCO3 composite opacifier by hydrophobic agglomeration and mechanism of inhibiting glaze yellowing

Abstract

This study investigates the preparation of TiO2–SiO2–CaCO3 composite opacifier (Ti–Si–Ca) and its application in sanitary ceramic glazes. This approach involved hydrophobic agglomeration through surface-induced hydrophobic modification of TiO2, SiO2 and CaCO3 particles, along with the interactions between the hydrophobic carbon chains of modifiers. The Ti–Si–Ca formed a uniform coating with well-dispersed TiO2 and SiO2 particles on the CaCO3 surface and strong bonds formed among TiO2, SiO2 and CaCO3 through interpenetration of the organic carbon chains on the surface. The Ti–Si–Ca was added to the basic glazes of sanitary ceramics at a proportion of 15.5 % and fired at 1125 °C for 4 h. The resulting white ceramic glazes had chromaticity values of L*, a*, and b* at 93.76, −0.73, and 3.89, respectively, demonstrating superior glaze opacity and whiteness compared to glazes made with a ZrSiO4 opacifier (L* 90.30, b* 4.50). Glass and titanite phase make up the majority of the Ti–Si–Ca ceramic glazing layer of, with titanite serving as the opacified phase. Elimination of organic groups in Ti–Si–Ca during glaze firing formed interfacial chemical bonds among TiO2, SiO2 and CaCO3, which facilitated the synthesis of titanite from the three components at high temperatures. The Ti–Si–Ca was a highly opaque glaze without yellowing because the organic groups of Ti–Si–Ca were removed and interfacial chemical bonds formed among the TiO2, SiO2 and CaCO3 in the low-temperature stage of glaze firing. This transformed the three phases into titanite at high temperature and eliminated free TiO2. The formation of rutile TiO2, which has a yellow hue, at high temperatures was inhibited. This study provides a novel approach for low-energy preparation of TiO2–SiO2–CaCO3 composite opacifiers and addresses the challenge of replacing ZrSiO4 with TiO2 in ceramic opacifiers.