Exploring the negative thermal expansion and magnetocaloric effect in Fe₂(Hf,Ti) Laves phase materials

The transition-metal based Laves phase materials represent an extended family of alloys with rich and fascinating physical properties. In this work, we have investigated the negative thermal expansion and magnetocaloric effect in arc-melted and melt-spun Fe₂Hf_1-xTi_x (x = 0.15, 0.27, 0.30, 0.33, 0.36, 0.40) alloys. For x = 0.30–0.40, two hexagonal phases with different compositions share the same P6₃/mmc lattice symmetry, but have slightly different lattice parameters. The saturation magnetization and Curie temperature both follow a decreasing trend with the average unit-cell volume. For Fe₂Hf_0.6Ti_0.4 melt spinning improves the saturation magnetization from 48.7 to 59.6 Am²/kg and the magnetic entropy change from 0.46 to 0.54 J/kgK at a magnetic field change of 2 T. These enhanced values are attributed to an improved homogeneity caused by a suppression of phase segregation during rapid solidification. We have utilized neutron powder diffraction and Mössbauer spectroscopy to illustrate the correlation between the magnetic order and the negative thermal expansion in single-phase Fe₂Hf_0.85Ti_0.15. The magnetic moments of Fe align below 400 K in the a-b plane and a moment change for the Fe atoms is responsible for the large volumetric coefficient of thermal expansion of −25 × 10⁻⁶ K⁻¹ over a wide temperature range of 300–400 K.