Extracting free energies from local composition fluctuations in solids: A frequency distribution analysis of simulated atom probe data obtained by TAPSim

Abstract

The present work proposes a novel methodology to extract direct thermodynamic information, i.e. Gibbs free energies, from local composition fluctuations found in atom probe data based on statistical mechanics. The proof-of-concept is demonstrated with an exemplary simulated Cu–Ni alloy, which has first been equilibrated using Monte Carlo techniques with an embedded-atom method potential and subsequently field evaporated by TAPSim. It is shown that the variance of the frequency distribution of the local composition on the reconstructed data reveals a systematic dependence on the size of the chosen spherical (sub-) volume used for the evaluation, but nevertheless the extrapolation to an infinitely large volume unveils a unique link to the curvature of the Gibbs free energy. Given the composition range is explored at several points, the Gibbs excess free energy of mixing could be recovered in a CALPHAD-style parametrization. This methodology promises to improve the accuracy of thermodynamic information (e.g. miscibility gap, mixing/demixing tendencies, critical solution temperature) from direct atom probe measurements.