Effect of Heating Modes on Reactive Sintering of Ca₃Co₄O₉ Ceramics

The traditional solid-state reaction method was employed to synthesize bulk calcium cobaltite (Ca349/Ca₃Co₄O₉) ceramics via ball milling the precursor mixture. The samples were compacted using conventional sintering (CS) and spark plasma sintering (SPS) at 850, 900, and 950 °C. The X-ray diffraction (XRD) pattern indicates the presence of the Ca349 phase for samples sintered at 850 and 900 °C. In addition, SPS fosters higher densification (81.18%) than conventional sintering (50.76%) at elevated sintering temperatures. The thermo-gravimetric analysis (TGA) and differential thermal analysis (DTA) performed on the precursor mixture reported a weight loss of ~25.23% at a temperature range of 600-820 °C. This current work aims to analyze the electrical properties (Seebeck coefficient (s), electrical resistivity (ρ), and power factor) of sintered samples as a function of temperature (35-500 °C). It demonstrates that the change in sintering temperature (conventional sintering) did not evince any significant change in the Seebeck coefficient (113-142 μV/K). However, it reported a low resistivity of 153-132 μΩ-m and a better power factor (82-146.4 μW/mK²) at 900 °C. On the contrary, the SPS sintered samples recorded a higher Seebeck coefficient of 121-181 μV/K at 900 °C. Correspondingly, the samples sintered at 950 °C delineated a low resistivity of 145-158 μΩ-m and a better power factor (97-152 μW/mK²).