Electronic Origin of α″ to ß Phase Transformation in Ti-Nb-Based Thin Films upon Hf Microalloying.

We present results on thin Ti-Nb-based films containing Hf at various concentrations grown by magnetron sputtering. The films exhibit α" patterns at Hf concentrations up to 11 at.%, while at 16 at.% Hf, the ß-phase emerges as a stable structure. These findings were consolidated by ab initio calculations, according to which the α"-ß transformation is manifested in the calculation of the electronic band energies for Hf contents between 11 and 18 at.%. It turns out that the ß-phase transition originates from the Hf 5d contributions at the Fermi level and the Hf 6s hybridizations at low energies in the electronic density of states. Bonding-anti-bonding first neighbor features existing in the shifted plane destabilize the α″-phase, especially at high Hf concentrations, while the covalent-like features in the first neighborhood stabilize the corresponding plane of the ß-phase. Thin films measurements and bulk total energy calculations agree that the lattice constants of both α″ and ß phases increase upon Hf substitution. These results are important for the understanding of ß-Ti-based alloys formation mechanisms and can be used for the design of suitable biocompatible materials.