Emergence of near-boundary segregation zones in face-centered cubic multiprincipal element alloys

Grain boundaries have been shown to dramatically influence the behavior of relatively simple materials such as monatomic metals and binary alloys. The increased chemical complexity associated with multiprincipal element alloys is hypothesized to lead to unique grain boundary phenomena. To explore the relationship between grain boundary structure and chemistry in these materials, hybrid molecular dynamics/Monte Carlo simulations of a faceted Sigma 11 (110) tilt boundary, chosen to sample both high- and low-energy boundary configurations, are performed in face-centered cubic (fcc) CrFeCoNiCu and CrFeCoNi equiatomic alloys. Unexpected enrichment of Fe is discovered in the fcc regions adjacent to the interface and found to be correlated with a structurally distinct region of reduced atomic volume. Comparison with the boundary of the same type in monatomic Cu demonstrates that altered near-boundary regions exist in simpler systems as well, with the chemical complexity of the multiprincipal element alloys highlighting its existence and importance.