This study investigated the effect of the secondary phases on multi-step phase transitions and the magnetocaloric properties depending on the Ge content in the MnFeCoPSiGe alloys. Two-step phase transitions were observed by the variations of the Fe2P-type hexagonal structure (first-order) and secondary phases (second-order). The Curie temperature alters with non-linear behavior consistent with change of the lattice parameters. In addition, the magnetic entropy change decreased with the increase of the Ge content and, subsequently, fractions of the secondary phases. However, the morphological variation of microstructure, distributed as a circular-type shape of the Fe2P-type hexagonal structure in the Ge-rich matrix, increased the magnetic entropy change. Therefore, the addition of Ge enables the control of the Curie temperature to be applicable for high temperature operating devices. The control of the secondary phases and morphology of the microstructure are crucial to improve the phase transition and magnetic entropy change.

This study investigated the improvement in magnetocaloric properties with magnetocrystalline anisotropy by Ge doping in MnFeHfPSi alloys. The maximum magnetic entropy change gets larger in alloys with higher magnetocrystalline anisotropy. This result is induced by the fractions of easy and hard magnetization planes. In addition, the magnetocaloric properties indicate large differences based on the direction between the easy magnetization plane and the applied magnetic field. Especially, the difference in magnetic entropy change under a low magnetic field is higher than that under a strong magnetic field. Besides, when magnetic transition occurs from a ferromagnetic to a paramagnetic state, the fraction of the easy magnetization plane decreases. Therefore, orientations with an easy magnetization plane play an important role in the enhancement of magnetocaloric properties.

Abstract With the discovery of bulk metallic glasses (BMGs), there has been considerable interest in understanding their mechanical behavior. In spite of these previous observations on the relation between plastic deformation of metallic glasses and their diffusion behavior, a detailed understanding on the diffusion of BMGs is still unexplored. We evaluated the contribution of deformation-induced structural transformations (elastic, anelastic, viscoplastic or viscoelastic responsive and plastic strain) on the diffusion of Zr-based bulk metallic glasses in as-cast, elastostatically stressed and plastically deformed states. Experimental investigations of the diffusion process and the elemental distributions in the glassy alloy were performed following plastic deformation by multiple cold rolling and elastostatic cyclic compression, respectively. We compared the vacancy model and the transition state model to verify the diffusion mechanism in the deformed bulk metallic glass. The diffusion of tracer atoms, i.e., Fe, in the bulk metallic glass is affected by viscoelastic responsive strain governing the transition-state model. In contrast, the diffusion of constituent atoms, i.e., Ti, Zr, in the bulk metallic glass is dominantly affected by plastic strain governing the vacancy model. The results reveal that the diffusion behavior of bulk glassy alloys can be changed by variation of the constituent elements and applying different strain modes upon deformation.