Combining DFT and CALPHAD for the development of on-lattice interaction models: The case of Fe-Ni system

Abstract

We present a model of pair interactions on rigid lattice to study the thermodynamic properties of iron-nickel alloys. The pair interactions are fitted at 0 K on ab initio calculations of formation enthalpies of ordered and disordered (special quasirandom) structures. They are also systematically fitted on the Gibbs free energy of the $\ensuremath{\gamma}$ Fe-Ni solid solution as described in a CALPHAD (CALculation of PHAse Diagrams) study by Cacciamani et al. This allows the effects of finite temperature, especially those of magnetic transitions, to be accurately described. We show that the ab initio and CALPHAD data for the $\ensuremath{\gamma}$ solid solution and for the $\mathrm{Fe}{\mathrm{Ni}}_{3}\text{\ensuremath{-}}\mathrm{L}{1}_{2}$ ordered phase can be well reproduced, in a large domain of composition and temperature, using first and second neighbor pair interactions which depend on temperature and local alloy composition. The procedure makes it possible to distinguish and separately compare magnetic, chemical, and configuration enthalpies and entropies. We discuss the remaining differences between the pair interaction model and CALPHAD, which are mainly due to the treatment of the short-range order and configurational entropy of the solid solution. The FCC phase diagram of the Fe-Ni system is determined by Monte Carlo simulations in the semigrand canonical ensemble and is compared with experimental studies and other models. We especially discuss the stability of the $\mathrm{Fe}\mathrm{Ni}\text{\ensuremath{-}}\mathrm{L}{1}_{0}$ phase at low temperature.