Mass spectrometric study of ceramics in the Sm₂O₃‐ZrO₂‐HfO₂ system at high temperatures

Abstract

Rationale Systems containing zirconia, hafnia, and rare earth oxides are indispensable in various areas of high‐temperature technologies as a basis of ultra‐high refractory ceramics. Exposure of these materials to high temperatures may result in unexpected selective vaporization of components or phase transitions in the condensed phase leading to changes in physicochemical properties. Consequently, reliable application of the ceramics based on systems such as Sm2O3‐ZrO2‐HfO2 is impossible without data on its vaporization processes and thermodynamic properties, which may be used to predict the physicochemical characteristics of the ultra‐high refractory ceramics. Methods Ceramics based on the Sm2O3‐ZrO2‐HfO2 system were obtained by solid‐state synthesis and characterized by X‐ray fluorescence and X‐ray phase analyses. The vaporization and thermodynamics of the system considered were examined by the high‐temperature mass spectrometric method using a MS‐1301 magnetic sector mass spectrometer with a tungsten twin effusion cell. Vapor species effusing from the cell were ionized by electrons with an energy of 25 eV. Results The main vapor species over the Sm2O3‐ZrO2‐HfO2 system were shown to be SmO, Sm, and O at a temperature of 2373 K, indicating selective vaporization of Sm2O3 from the samples. The partial pressures of these vapor species and the Sm2O3 activities were determined in the Sm2O3‐ZrO2‐HfO2 system and allowed the excess Gibbs energies to be evaluated. These excess Gibbs energy values were compared with the results obtained by the semi‐empirical and statistical thermodynamic approaches. Conclusions The data obtained in this study showed negative deviations from the ideal behavior in the Sm2O3‐ZrO2‐HfO2 system at 2373 K. The results calculated according to the semi‐empirical methods and statistical thermodynamic Generalized Lattice Theory of Associated Solutions were in agreement with each other. Thus, this evidenced the desirability of further experimental investigation of the Sm2O3‐ZrO2‐HfO2 system by the high‐temperature mass spectrometric method.

Knudsen effusion mass spectrometry: Current and future approaches

“…KEMS studies on the following relevant systems have recently been reported: Sm 2 O 3 ‐ZrO 2, 67,305 UO 2 ‐ZrO 2, 306 and Sm 2 O 3 ‐ZrO 2 ‐HfO 2. 244,307 …”