Effect of high pressure synthesis conditions on the formation of high entropy oxides

TL;DR

This study investigates how high-pressure synthesis influences the stabilization and formation of high entropy oxides, revealing new phases and transformation pathways not accessible at ambient conditions.

Contribution

It demonstrates that high-pressure conditions can stabilize unique high entropy oxide phases and induce phase transformations, expanding the synthesis possibilities beyond traditional methods.

Findings

High-pressure synthesis leads to new high entropy oxide phases.

Transformation of spinel HEO into a metastable ludwigite-type structure at 15 GPa.

High-pressure conditions enable formation of phases not achievable at ambient pressure.

Abstract

High entropy materials are often entropy stabilized, meaning that the configurational entropy from multiple elements sharing a single lattice site stabilizes the structure. In this work, we study how high-pressure synthesis conditions can stabilize or destabilize a high entropy oxide (HEO). We study the high-pressure and high-temperature phase equilibria of two well-known families of HEOs: the rock-salt structured compound (Mg,Co,Ni,Cu,Zn)O including some cation substitutions and the spinel structured (Cr,Mn,Fe,Co,Ni)$_3$O$_4$. Syntheses were performed at various temperatures, pressures, and oxygen activity levels resulting in dramatically different synthesis outcomes. In particular, in the rock salt HEO we observe the competing tenorite and wurtzite phases and the possible formation of a layered rock salt phase, while the spinel HEO is highly susceptible to decomposition into a mixture of rock-salt and corundum phases. At the highest tested pressures, 15 GPa, we discover the transformation of the spinel HEO into a metastable modified ludwigite-type structure with nominal formula (Cr,Mn,Fe,Co,Ni)$_4$O$_5$. The relationship between the synthesis conditions and the final reaction product is not straightforward. Nonetheless, we conclude that high-pressure conditions provide an important opportunity to synthesize high entropy phases that cannot be formed any other way.