Calcium zirconate powders doped with a small amount of CaO were synthesised using the Pechini method. X-ray analysis revealed that solid solution was formed in the concentration up to 51.5% mol CaO. For synthesis of stoichiometric CaZrO3, the highest temperature was required (1150°C), but introduction of excess CaO from 50.5 to 51.5% mol enabled us to lower the synthesis temperature to 800°C. The sintering behaviour of such samples under non-isothermal conditions was studied by dilatometric methods. Deviations were found in stoichiometry; by increasing the CaO concentration in CaZrO3 sinterability improved in comparison to CaZrO3 with stoichiometric composition. The presence of CaO as second phase caused deterioration of the sinterability of the CaZrO3-based samples. Pellets sintered at 1500°C for 2 h reached 96–98% of theoretical density. SEM and TEM observations were used to characterise the microstructure of the prepared samples. The electrical properties of CaZrO3-based samples were investigated by the AC-impedance spectroscopy method. It was found that introduction of excess CaO into the CaZrO3 structure caused an increase in ionic conductivity up to the solubility limit. The possibility of using CaZrO3-based samples for constructing prototype electrochemical oxygen probes to determine activity of oxygen dissolved in molten copper is also demonstrated. <alternatives> [...] </alternatives>
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