An Ab Initio Study of Vacancies in Disordered Magnetic Systems: A Case Study of Fe-Rich Fe-Al Phases

We have performed quantum-mechanical calculations to examine the impact of disorder on thermodynamic, structural and electronic (magnetic) properties of Fe-Al systems with vacancies. A series of supercells was used and their properties were computed employing density-functional theory (DFT) as implemented in the VASP package. Our case study is primarily aimed at a disordered solid solution Fe 81.25 Al 18.75 but we have compared our results also with those obtained for the ordered Fe 3 Al intermetallic compound for which experimental data exist in literature. Both phases are found in Fe-Al-based superalloys. The Fe-18.75at.%Al solid solution was simulated using special quasirandom structures (SQS) in three different disordered states with a different distribution of Al atoms. In particular, we have considered a general disordered case (an A2-like variant), the case without the first nearest neighbor Al-Al pairs (a B2-like distribution of atoms) and also the case without both the first and second nearest neighbor Al-Al pairs (the D0 3 -like variant, in fact, an Fe-rich Fe 3 Al phase). The vacancy formation energies as well as the volumes of (fully relaxed) supercells with vacancies showed a large scatter for the disordered systems. The vacancy formation energies decrease with increasing concentration of Al atoms in the first coordination shell around the vacancy (an anti-correlation) for all disordered cases studied. The computed volumes of vacancies were found significantly lower (by 25-60%) when compared with the equilibrium volume of the missing atoms in their elemental states. Lastly, we have analyzed interactions between the vacancies and the Fe atoms and evaluated vacancy-induced changes in local magnetic moments of Fe atoms.