On the Effect of Standard Deviation of Cationic Radii on the Transition Temperature in Fluorite-Structured Entropy-Stabilized Oxides (F-ESO)

: It is confirmed that Fluorite-structured Entropy-Stabilized Oxides (F-ESO) can be obtained with multicomponent (5) equimolar systems based on cerium, zirconium, and other rare earth elements, selected according to the predictor already proposed by the authors. Indeed, in the present study, three different samples owning a standard deviation (SD in the following) of their cationic radii greater than the threshold value (i.e., SD > 0.095 with cationic radii measured in Å) needed to ensure the formation of the single-phase fluorite structure, were prepared via co-precipitation method. After a calcination step at 1500 °C for 1 h, the entropy-driven transition from multiple phases to single-phase fluorite-like structure has been actually confirmed. Thus, with the aim of defining the temperature at which such entropy-driven transition occurred, and identifying possible relation between such temperature and the actual value of SD, the phase evolution of all the prepared samples as a function of temperature (ranging from 800 °C to 1300 °C) was analyzed by in situ High Temperature X-ray Diffraction. An apparent inverse correlation between the standard deviation and the entropy-driven transition temperature has been identified, i.e., the higher the former, the lower the latter. These results, based on the conducted basic structural analysis, provide further support to the SD-based empirical predictor developed by the authors, suggesting that high values of SD could bring additional contribution to the overall entropy of the system, other than the configurational one. Thus, this SD-driven entropy contribution directly increases with the increasing of the standard deviation of the cationic radii of a given F-ESO.