Ab initio study of phosphorus effect on vacancy-mediated process in nickel alloys - an insight into Ni2Cr ordering

TL;DR

This study combines computational and experimental methods to reveal how phosphorus accelerates the ordering process in Ni-Cr alloys by enhancing vacancy diffusion, which impacts alloy strength and ductility.

Contribution

It provides new insights into vacancy-mediated diffusion mechanisms influenced by phosphorus in nickel alloys, supported by first-principles calculations and experimental validation.

Findings

Phosphorus significantly lowers vacancy migration energy barriers.

Enhanced vacancy diffusion by two orders of magnitude at 400-500°C.

Phosphorus addition accelerates Ni2Cr ordering, affecting alloy properties.

Abstract

The development of long range order in nickel-chromium alloys is of great technological interest but the kinetics and mechanisms of the transformation are poorly understood. The present research utilizes a combined computational and experimental approach to elucidate the mechanism by which phosphorus accelerates the ordering rate of stoichiometric Ni_2Cr in Ni-Cr alloys. A series of Ni-33%Cr-x%P samples (in atomic percent) were fabricated with phosphorus concentrations, x = <0.005-0.1 at.% and aged between 373 and 470{\deg}C for times up to 3000 h. The first-principles modeling considers fcc Ni with dilute P as a reasonable approximation for the complex Ni-Cr-P alloy system. Calculation results show a pronounced enhancement of vacancy transport by vacancy-solute pair diffusion via consecutive exchange and rotation jumps of vacancies associated with the phosphorus atom. The energy barriers of these two migration paths are at least 0.35 eV lower than that of vacancy-atom exchange in pure Ni solvent. The analytical diffusion model predicts enhanced solvent diffusion by 2 orders of magnitude for 0.1 at.% P at 400-500{\deg}C. The model prediction is in good agreement with the evolution of micro-hardness. We characterize the micro-hardness result by a kinetic ordering model, showing a significant decrease of the activation energy of ordering transformation. These results help gauge the risk of industrial alloys developing long range order which increases strength but degrades ductility and toughness. Specifically, minor alloying additions that bind with excess vacancies and lower the vacancy migration barrier can greatly accelerate hardening via Ni_2Cr precipitation.