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Ni–Mn–Ga Heusler alloys are multifunctional materials that demonstrate macroscopic strain under an externally applied magnetic field through the motion of martensite twin boundaries within the microstructure. This study sought to comprehensively characterize the microstructural, mechanical, thermal, and magnetic properties near the solidus in binder-jet 3D printed 14M Ni50Mn30Ga20. Neutron diffraction data were analyzed to identify the martensite modulation and observe the grain size evolution in samples sintered at temperatures of 1080 °C and 1090 °C. Large clusters of high neutron-count pixels in samples sintered at 1090 °C were identified, suggesting Bragg diffraction of large grains (near doubling in size) compared to 1080 °C sintered samples. The grain size was confirmed through quantitative stereology of polished surfaces for differently sintered and heat-treated samples. Nanoindentation testing revealed a greater resistance to plasticity and a larger elastic modulus in 1090 °C sintered samples (relative density ~95%) compared to the samples sintered at 1080 °C (relative density ~80%). Martensitic transformation temperatures were lower for samples sintered at 1090 °C than 1080 °C, though a further heat treatment step could be added to tailor the transformation temperature. Microstructurally, twin variants ≤10 μm in width were observed and the presence of magnetic anisotropy was confirmed through magnetic force microscopy. This study indicates that a 10 °C sintering temperature difference can largely affect the microstructure and mechanical properties (including elastic modulus and hardness) while still allowing for the presence of magnetic twin variants in the resulting modulated martensite. 

Abstract Transitioning current cooling and refrigeration technologies to solid-state cooling leveraging the magnetocaloric effect would improve efficiency and eliminate a harmful influence on the environment. Employing additive manufacturing as a production method would increase geometrical freedom and allow designed channels and porosity in heat exchangers made from magnetocaloric materials, to increase surface area for heat transfer via a fluid. This study is the first to demonstrate a successful deposition of the Ni43Co7Mn39Sn11 magnetocaloric material by direct laser deposition. Samples were defined as either properly- or overbuilt, and representative ones were characterized for microstructural features before and after homogenization heat treatment, as well as magnetic behavior and constituent phases. As-built microstructures consisted of dendrites, columnar grains, and elongated cells, with a mix of both austenite and 7M martensite phases. Homogenization increased the fraction of 7M martensite, and encouraged distinct equiaxed and columnar grains, eliminating dendrites and cellular structures. The increased fraction of the weak magnetic martensitic phase also resulted in a strong reduction of the saturation magnetization. Some differences in structure and performance may be related to an energy density difference causing higher Mn loss in the properly built sample, with a lower powder-to-energy input ratio. As a whole, it is found that direct laser deposition (DLD) additive manufacturing of Ni-Mn-based magnetocaloric material is very promising, since representative transformation, phase state, and magnetic properties have been achieved in this study.