Temperature-dependent lattice dynamics study on phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2-type Ni–Mn–Ti Heusler alloy

The all-d-metal Ni–Mn–Ti Heusler alloy with its good mechanical properties and colossal caloric effects has attracted significant attention for mechanocaloric refrigeration. However, the phase stability of the B2-type disordered structure at finite temperatures and the physical origin of large phase transformation entropy change in theoretical calculation remain unclear. In view of thermal and strongly anharmonic effects, we combined the first-principles and temperature dependent effective potential calculations to systematically study the phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2 partial disordered structures for Ni8Mn5Ti3 and Ni8Mn6Ti2. Our results showed the austenitic structures of Ni8Mn5Ti3 and Ni8Mn6Ti2 both exhibit antiferromagnetic interaction behaviors at targeted temperatures, resolving the contradiction between previous calculations and experiments. By the analysis of phonon dispersion relations and Helmholtz free energies at low and high temperatures, we provided a deeper explanation for the underlying mechanism of martensitic transformation. Meanwhile, the phase transformation temperatures and vibrational entropy changes were accurately predicted compared with the experiment results. Specifically, we demonstrated that the large vibrational entropy change of Ni–Mn–Ti material originates from the contributions of both the tetragonal distortion ratio and volume change, which provides important theoretical guidance and has great practical significance for designing the solid-state material with large vibrational entropy change in the application of solid-state refrigeration.