Universal Characterization of Hierarchical Ordering Tendency in High-Entropy Alloys from Configurational Geometry

TL;DR

This study uses first-principles calculations and a new theoretical approach to characterize the hierarchical ordering tendencies in high-entropy alloys, revealing limitations of conventional atomic radius measures and proposing a normalized atomic radius ratio for better comparison.

Contribution

It introduces a systematic method to characterize ordering tendencies in high-entropy alloys using atomic radius ratios derived from fluctuated configurations, improving upon traditional measures.

Findings

Hierarchical ordering in HEAs cannot be captured by conventional atomic radii.

Atomic radius ratios from fluctuated configurations effectively characterize ordering.

Normalized atomic radius ratios enable comparison across different alloy compositions.

Abstract

Microscopic structures for fcc-based quaternary high-entropy alloys (HEA) in thermodynamically equilibrium state is examined based on first-principles (FP) calculation combined with our recently-developed theoretical approach. We find that (i) hierarchical ordering tendency for whole quaternary, and ternary and binary subsystems for the present five HEAs cannot be reasonably characterized by conventional Goldschmidt atomic radius or by those obtained from unary system for FP calculation, but can be systematically characterized by atomic radius from specially fluctuated configuration. (ii) ordering tendency for whole- and sub-systems can be simultaneously treated with individual definition of atomic radius ratio, and that linear correlation between ordering tendency and atomic radius ratio naturally decreases with decrease of number of constituents for whole (or sub-) system due to the counterbalance breaking of like- and unlike-atom neighboring pair. We also find that by introducing appropriate normalization, ordering tendency for systems with different number of constituents (here, quaternary and ternary) can also be simultaneously treated by the atomic radius ratio.