Atomistic mechanisms of binary alloy surface segregation from nanoseconds to seconds using accelerated dynamics

TL;DR

This study uses multiscale atomistic simulations to investigate the transient and equilibrium surface segregation processes in CuNi alloys over timescales from nanoseconds to seconds, revealing rare events and vacancy dynamics.

Contribution

It introduces a multiscale computational approach combining MD, ParSplice, AKMC, and KMC to observe rare segregation events over extended timescales, bridging the gap between simulations and experiments.

Findings

Vacancy diffusion occurs within tens of nanoseconds.

Rare vacancy re-entry into subsurface occurs on microsecond timescale.

Equilibrium segregation profile develops over seconds, matching experimental observations.

Abstract

Although the equilibrium composition of many alloy surfaces is well understood, the rate of transient surface segregation during annealing is not known, despite its crucial effect on alloy corrosion and catalytic reactions occurring on overlapping timescales. In this work, CuNi bimetallic alloys representing (100) surface facets are annealed in vacuum using atomistic simulations to observe the effect of vacancy diffusion on surface separation. We employ multi-timescale methods to sample the early transient, intermediate, and equilibrium states of slab surfaces during the separation process, including standard MD as well as three methods to perform atomistic, long-time dynamics: parallel trajectory splicing (ParSplice), adaptive kinetic Monte Carlo (AKMC), and kinetic Monte Carlo (KMC). From nanosecond (ns) to second timescales, our multiscale computational methodology can observe rare stochastic events not typically seen with standard MD, closing the gap between computational and experimental timescales for surface segregation. Rapid diffusion of a vacancy to the slab is resolved by all four methods in tens of ns. Stochastic re-entry of vacancies into the subsurface, however, is only seen on the microsecond timescale in the two KMC methods. Kinetic vacancy trapping on the surface and its effect on the segregation rate are discussed. The equilibrium composition profile of CuNi after segregation during annealing is estimated to occur on a timescale of seconds as determined by KMC, a result directly comparable to nanoscale experiments.