The magnetocaloric properties of Mn₅Si_1-xP_xB₂ (0 ≤ x ≤ 1) compounds were studied for energy harvesting applications. The crystal structure and the magnetic structure were characterized by powder X-Ray Diffraction and powder Neutron Diffraction. The results indicate that these magnetocaloric materials crystallize in the tetragonal Cr₅B₃-type crystal structure. The introduction of P causes a stretching of the c axis and compression of the a-b plane, leading to a decrease in the unit-cell volume V. In the ferromagnetic state the magnetic moments align within the a-b plane, and the magnetic moment of the Mn1 atom on the 16 l site is larger than that of the Mn2 atom on the 4c site. The Curie temperature T_C can be adjusted continuously from 305 K (x = 1) to 406 K (x = 0) by replacing Si with P. The corresponding magnetic entropy change varies from 1.90 Jkg⁻¹K⁻¹ (x = 0) to 1.35 Jkg⁻¹K⁻¹ (x = 1) for a magnetic field change of 1 T. The PM-FM transition in these compounds corresponds to a second-order phase transition. Mn₅Si_1-xP_xB₂ compounds exhibit a magnetization difference of 28.1 - 31.3 Am²kg⁻¹ for a temperature span of 30 K around T_C in an applied magnetic field of 1 T. The considerable change in magnetization, the tunable T_C near and above room temperature and the absence of thermal hysteresis make these compounds promising candidates for magnetocaloric energy harvesting 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.

Structural, magnetic and magnetocaloric properties of Mn₃Sn_1-xZn_xC antiperovskite carbides have been studied. With increasing Zn content the first-order magnetic transition (FOMT) is weakened. The Curie temperature (T_C) reduces first from 273 to 197 K and when x > 0.3, T_C increases, reaching its maximum of 430 K for x = 1.0. An increase in T_C is accompanied by pronounced changes in magnetic behaviour and a significant rise in magnetization from 21.82(4) to 76.2(2) Am²kg⁻¹ for x = 0.8 in the maximum applied magnetic field of 5 T. Neutron powder diffraction (NPD) was employed to study the magnetic structure of Mn₃Sn_1-xZn_xC compounds. The refinement of the NPD data for x = 0.3 revealed a magnetic structure with propagation vector k = (½,½,0) with a decrease in the canted antiferromagnetic (AFM) moment, which results in a reduction of the negative volume change at the magnetic transition and a decrease in the magnetocaloric effect (MCE). For x = 0.4, the magnetic structure is described by a propagation vector k = (½,½,½) for the AFM moment which dominates at low temperature, with the presence of a minor ferromagnetic (FM) component with a k = (0, 0, 0) propagation vector, which confirms the presence of the ferrimagnetic (FiM) state. For a higher Zn content (x = 0.6), the magnetic moment originates mainly from the FM component found on three independent Mn positions and an additional AFM moment oriented in the a-b plane. The results presented confirm the presence of competing AFM-FM interactions in Mn₃Sn_1-xZn_xC antiperovskite carbides.

The influence of excess Mn on the magnetoelastic ferromagnetic-to-antiferromagnetic transition T_t in the magnetocaloric compound (Mn,Cr)₂Sb has been studied. With increasing excess Mn the magnetoelastic transition temperature for (Mn,Cr)₂Sb initially increases and then decreases. This trend is accompanied by a strong reduction of the (Mn,Cr)Sb secondary phase. With increasing excess Mn a higher Cr content was found in the (Mn,Cr)Sb secondary phase in comparison to the matrix phase. This competition for Cr leads to a nonlinear dependence of T_t with increasing excess Mn at a fixed nominal Cr content. However, we observed that T_t depends linear on the c/a ratio for a wide range of temperatures from 170 to 350 K. A compositional diagram of the c/a ratio was constructed to assist the selection of (Mn,Cr)₂Sb alloys with a desired transition temperature.

In the field of nanoscale magnetocaloric materials, novel concepts like micro-refrigerators, thermal switches, microfluidic pumps, energy harvesting devices and biomedical applications have been proposed. However, reports on nanoscale (Mn,Fe)₂(P,Si)-based materials, which are one of the most promising bulk materials for solid-state magnetic refrigeration, are rare. In this study we have synthesized (Mn,Fe)₂(P,Si)-based nanoparticles, and systematically investigated the influence of crystallite size and microstructure on the giant magnetocaloric effect. The results show that the decreased saturation magnetization (M_s) is mainly attributed to the increased concentration of an atomically disordered shell, and with a decreased particle size, both the thermal hysteresis and T_c are reduced. In addition, we determined an optimal temperature window for annealing after synthesis of 300–600 °C and found that gaseous nitriding can enhance M_s from 120 to 148 Am²kg⁻¹ and the magnetic entropy change (ΔS_m) from 0.8 to 1.2 Jkg⁻¹K⁻¹ in a field change of Δμ₀H = 1 T. This improvement can be attributed to the synergetic effect of annealing and nitration, which effectively removes part of the defects inside the particles. The produced superparamagnetic particles have been probed by high-resolution transmission electron microscopy, Mössbauer spectra and magnetic measurements. Our results provide important insight into the performance of giant magnetocaloric materials at the nanoscale.

The influence of partial substitution of Bi for Sb on the structure, magnetic properties and magnetocaloric effect of Mn₂Sb_1-xBi_x (x = 0, 0.02, 0.04, 0.05, 0.07, 0.09, 0.15, 0.20) compounds has been investigated. The transition temperature of the antiferro-to-ferrimagnetic (AFM-FIM) transition initially increases with increasing Bi and decreases above 9%. Density functional theory calculations indicate that the Bi atoms prefer to occupy only the Sb site, which accounts for the large magnetization jump in Mn₂Sb_0.93Bi_0.07. As large lattice parameters are found for Bi substituted Mn₂Sb, the origin of the AFM-FIM transition in Mn₂Sb_(1-x)Bi_x compounds is ascribed to an enhanced coefficient of thermal expansion along the c axis, resulting from the Bi substitution. The moderate entropy change of 1.17 J/kg K under 2 T originating from the inverse magnetocaloric effect and the strong magnetic field dependence of the transition temperature of dT_t/dµ₀H = −5.4 K/T in Mn₂Sb_0.95Bi_0.05 indicate that this alloy is a promising candidate material for magnetocaloric applications.