Ab initio phase stabilities of Ce-based hard magnetic materials and comparison with experimental phase diagrams

Recent developments in electrical transportation and renewable energies have significantly increased the demand of hard magnetic materials with a reduced critical rare-earth content, but with properties comparable to (Nd,Dy)-Fe-B permanent magnets. Though promising alternative compositions have been identified in high-throughput screenings, the thermodynamic stability of these phases against decomposition into structures with much less favorable magnetic properties is often unclear. In the case of Ce-Fe-Ti alloys, we have used finite temperature ab initio methods to provide this missing information. Employing state-of-the-art approaches for vibrational, electronic, and magnetic entropy contributions, the Helmholtz free energy, F(T,V), is calculated for the desired hard magnetic CeFe11Ti phase and all relevant competing phases. The latter have been confirmed experimentally by employing reactive crucible melting (RCM) and energy-dispersive x-ray spectroscopy (EDS). Our ab initio based free energy calculations reveal that the presence of the CeFe2 Laves phase suppresses the formation of CeFe11Ti up to 700 K. The result is in agreement with RCM, in which CeFe11Ti is only observed above 1000 K, while the CeFe2 and Ce2Fe17 phases are stable at lower temperatures.