The effect of process parameters on the amorphous citrate sol-gel synthesis of Cu-doped Ca12Al14O33

Abstract

Ca12Al14O33 (C12A7) is a highly functional material due to its ability to act as an anionic source and its conversion from a wide band-gap insulator to a conductive oxide material as a function of processing. Cationic doping, on the order of 1 mol%, of C12A7 has been shown to have profound effects on the physical properties of the material. One such cation, Cu, increases the catalytic efficiency and drastically alters the electronic landscape. The amorphous citrate sol-gel synthesis technique is widely used to synthesize doped C12A7 materials as it promises homogeneous cationic dispersion and a fine and controlled grain size. This promise relies on the formation of a homogeneous citrate resin of cationic citrate species, homogeneous decomposition of cation citrate species, and homogeneous crystallization of the desired phase. In this report, theoretical complex diagrams are calculated to determine the optimal pH for citrate resin formation in the Cu-C12A7 system. The resin decomposition and crystallization kinetics are characterized through high-temperature X-ray diffraction and thermogravimetric analysis. The optimal pH range for the citrate resin homogeneity was theoretically determined to be a range from 3 to 6, and experimental characterization shows that raising the pH from < 1 to 4 leads to Cu-C12A7 phase purity, reduces grain size by 30%, and inhibits CaCO3 formation to lower the synthesis temperature from ∼900 °C to 840 °C. This report highlights the importance of sol-gel solution chemistry and the corroboration of XRD analysis with microstructural analysis