Formation of Solid Solutions and Physicochemical Properties of the High-Entropy Ln_1−xSr_x(Co,Cr,Fe,Mn,Ni)O_3−δ (Ln = La, Pr, Nd, Sm or Gd) Perovskites

• Main Authors: Juliusz Dąbrowa, Klaudia Zielińska, Anna Stępień, Marek Zajusz, Margarita Nowakowska, Maciej Moździerz, Katarzyna Berent, Maria Szymczak, Konrad Świerczek
• Format: Article
• Language: English
• Published: MDPI AG 2021-09-01
• Series: Materials
• Subjects: high entropy oxides; perovskites; structural properties; electrical properties
• Online Access: https://www.mdpi.com/1996-1944/14/18/5264

Phase composition, crystal structure, and selected physicochemical properties of the high entropy Ln(Co,Cr,Fe,Mn,Ni)O_3−δ (Ln = La, Pr, Gd, Nd, Sm) perovskites, as well as the possibility of Sr doping in Ln_1<i>−x</i>Sr<i>_x</i>(Co,Cr,Fe,Mn,Ni)O_3−δ series, are reported is this work. With the use of the Pechini method, all undoped compositions are successfully synthesized. The samples exhibit distorted, orthorhombic or rhombohedral crystal structure, and a linear correlation is observed between the ionic radius of Ln and the value of the quasi-cubic perovskite lattice constant. The oxides show moderate thermal expansion, with a lack of visible contribution from the chemical expansion effect. Temperature-dependent values of the total electrical conductivity are reported, and the observed behavior appears distinctive from that of non-high entropy transition metal-based perovskites, beyond the expectations based on the rule-of-mixtures. In terms of formation of solid solutions in Sr-doped Ln_1−<i>x</i>Sr<i>_x</i>(Co,Cr,Fe,Mn,Ni)O_3−δ materials, the results indicate a strong influence of the Ln radius, and while for La-based series the Sr solubility limit is at the level of x_max = 0.3, for the smaller Pr it is equal to just 0.1. In the case of Nd-, Sm- and Gd-based materials, even for the x_Sr = 0.1, the formation of secondary phases is observed on the SEM + EDS images.