New magnetocaloric Heusler alloys with larger magnetocaloric effects need to function in relatively low applied magnetic fields ≤ 1 T. Therefore, the emphasis of this Ph.D. thesis was to understand how the first order magnetostructural transformation in Mn-rich Ni-based rare-earth free magnetocaloric Heusler alloys works and to use this understanding for the design of new Mn-rich Ni-based rare-earth free magnetocaloric Heusler alloys. In this context, the rare-earth free, non-toxic, and environmentally friendly Heusler series: Ni2−xMn1+xSn, Mn50Ni50−ySny, and Ni-(Co-)Mn-In were systematically studied. In detail, it pointed out that in the Heusler series Ni2−xMn1+xSn, the structure and the disorder character can be predicted by using simple rules. On the other hand, an isoplethal section of the Heusler series Mn50Ni50−ySny was derived, which is very useful for the design of new magnetocaloric materials. In addition to it, in the Heusler alloy Ni49.9Mn34.5In15.6 a large saturated magnetic moment and a reversible magnetocaloric effect at its purely second order magnetic phase transition was present, which is in reasonable agreement with ab initio calculations. Finally, the effect of post-annealing on the Heusler alloy Ni45.2Co5.1Mn36.7In13 revealed that the magnetocaloric effect could be tuned and improved significantly. Consequently, this work shows that the Heusler alloys are promising candidates for magnetocaloric applications.

New magnetocaloric Heusler alloys with larger magnetocaloric effects need to function in relatively low applied magnetic fields ≤ 1 T. Therefore, the emphasis of this Ph.D. thesis was to understand how the first order magnetostructural transformation in Mn-rich Ni-based rare-earth free magnetocaloric Heusler alloys works and to use this understanding for the design of new Mn-rich Ni-based rare-earth free magnetocaloric Heusler alloys. In this context, the rare-earth free, non-toxic, and environmentally friendly Heusler series: Ni2−xMn1+xSn, Mn50Ni50−ySny, and Ni-(Co-)Mn-In were systematically studied. In detail, it pointed out that in the Heusler series Ni2−xMn1+xSn, the structure and the disorder character can be predicted by using simple rules. On the other hand, an isoplethal section of the Heusler series Mn50Ni50−ySny was derived, which is very useful for the design of new magnetocaloric materials. In addition to it, in the Heusler alloy Ni49.9Mn34.5In15.6 a large saturated magnetic moment and a reversible magnetocaloric effect at its purely second order magnetic phase transition was present, which is in reasonable agreement with ab initio calculations. Finally, the effect of post-annealing on the Heusler alloy Ni45.2Co5.1Mn36.7In13 revealed that the magnetocaloric effect could be tuned and improved significantly. Consequently, this work shows that the Heusler alloys are promising candidates for magnetocaloric applications.