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 (Ms) is mainly attributed to the increased concentration of an atomically disordered shell, and with a decreased particle size, both the thermal hysteresis and Tc 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 Ms from 120 to 148 Am2kg−1 and the magnetic entropy change (ΔSm) 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.@en

The magnetocaloric properties of Mn5Si1-xPxB2 (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 TC 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. Mn5Si1-xPxB2 compounds exhibit a magnetization difference of 28.1 - 31.3 Am2kg−1 for a temperature span of 30 K around TC in an applied magnetic field of 1 T. The considerable change in magnetization, the tunable TC near and above room temperature and the absence of thermal hysteresis make these compounds promising candidates for magnetocaloric energy harvesting materials.@en

The influence of doping with the 5d transition metal W has been studied in the quaternary (Mn,Fe)2(P,Si) based giant magnetocaloric compounds, which is one of the most promising systems for magnetic refrigeration. It is found that W substitution can separately decrease the Curie temperature TC and retain the thermal hysteresis ∆Thys at an almost constant level (∼5 K) for Mn0.6Fe1.27-xWxP0.64Si0.36 (x ≤ 0.02). Low-content W doping conserves the good magnetocaloric effect (MCE) without an obvious degradation. For x ≤ 0.02 the average magnetic entropy change |∆Sm| amounts to 11.4 Jkg−1K−1 for an applied magnetic field change of 2 T and the adiabatic temperature change ∆Tad amounts to 3.9 K for an applied magnetic field change of 1.5 T. The occupancy of substitutional W atoms is determined by XRD experiments and DFT calculations. Our studies provide a good strategy to further optimize the MCE of this material family.@en

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 Fe2Hf1-xTix (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 Fe2Hf0.6Ti0.4 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 Fe2Hf0.85Ti0.15. 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.@en

The influence of partial substitution of Bi for Sb on the structure, magnetic properties and magnetocaloric effect of Mn2Sb1-xBix (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 Mn2Sb0.93Bi0.07. As large lattice parameters are found for Bi substituted Mn2Sb, the origin of the AFM-FIM transition in Mn2Sb(1-x)Bix 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 dTt/dµ0H = −5.4 K/T in Mn2Sb0.95Bi0.05 indicate that this alloy is a promising candidate material for magnetocaloric applications.@en

In this work, the magnetocaloric effect and negative thermal expansion in melt-spun Fe2Hf0.83Ta0.17 Laves phase alloys were studied. Compared to arc-melted alloys, which undergo a first-order magnetoelastic transition from the ferromagnetic to the antiferromagnetic phase, melt-spun alloys exhibit a second-order transition. For Fe2Hf0.83Ta0.17 ribbons, we observed a large volumetric coefficient of negative thermal expansion of −19 × 10−6 K−1 over a wide temperature range of 197 – 297 K and a moderate adiabatic temperature change of 0.7 K at 290 K for a magnetic field change of 1.5 T. The magnetic field dependence of the transition temperature (dTt/dµ0H = 4.4 K/T) for the melt-spun alloy is about half that of the arc-melted alloy (8.6 K/T). The origin of second-order phase transition of the melt-spun alloy is attributed to the partially suppressed frustration effect, which is due to the atomic disorder introduced by the rapid solidification.@en

The novel all-d-metal Ni(Co)MnTi based magnetic Heusler alloys provide an adjustable giant magnetocaloric effect and good mechanical properties. We report that the second-order magnetic phase transition can be tailored in this all-d-metal NiCoMnTi based Heusler system by optimizing the Mn/Ti ratio, resulting in a reversible ferromagnetic-to-paramagnetic magnetic transition. A candidate material Ni33Co17Mn30Ti20 with a magnetic entropy change ∆Sm of 2.3 Jkg−1K−1 for a magnetic field change of 0–5 T, has been identified. The TC and saturation magnetization MS can be controlled by adjusting the Ni/Co concentration and doping non-magnetic Cu atoms. The compositional maps of TC and MS have been established. Density functional theory (DFT) calculations reveal a direct correlation between the magnetic moments and the Co content. By combining XRD, SQUID, SEM and DFT calculations, the (micro)structural and magnetocaloric properties have been investigated systematically. This study provides a detailed insight in the magnetic phase transition for this all-d-metal Ni(Co)MnTi-based Heusler alloy system.@en

Magnetic refrigeration is based on the magnetocaloric effect (MCE) and has attracted considerable attention due to its potentially higher energy efficiency, environmental friendliness and quietness compared to conventional vapour compression refrigeration. Boosting giant MCE materials with a magnetoelastic transition into commercial applications requires not only insights into the coupling between its magnetism and the lattice, but also the correlation between macroscopic performance and microstructure. In this thesis, the fundamental physical properties, including crystal structure, microstructure, magnetic structure, negative thermal expansion behaviour and the magnetocaloric effect, are studied in Mn2Sb-based intermetallic compounds with an antiferromagnetic-to-ferrimagnetic transition and Fe2Hf-based Laves phase compounds with a ferromagnetic-to-antiferromagnetic transition...@en

The influence of excess Mn on the magnetoelastic ferromagnetic-to-antiferromagnetic transition Tt 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 Tt with increasing excess Mn at a fixed nominal Cr content. However, we observed that Tt 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.@en

The quarternary (Mn,Fe)2(P,Si)-based materials with a giant magnetocaloric effect (GMCE) at the ferromagnetic transition TC are promising bulk materials for solid-state magnetic refrigeration. In the present study we demonstrate that doping with the light elements fluorine and sulfur can be used to adjust TC near room temperature and tune the magnetocaloric properties. For F doping the first-order magnetic transition (FOMT) of Mn0.60Fe1.30P0.64Si0.36Fx (x = 0.00, 0.01, 0.02, 0.03) is enhanced, which is explained by an enhanced magnetoelastic coupling. The magnetic entropy change |ΔSm| at a field change (Δμ0H) of 2 T markedly improved by 30% from 14.2 Jkg−1K−1 (x = 0.00) at 335 K to 20.2 Jkg−1K−1 (x = 0.03) at 297 K. For the F doped material the value of |ΔSm| for Δμ0H = 1 T reaches 11.6 Jkg−1K−1 at 294 K, which is consistent with the calorimetric data (12.4 Jkg−1K−1). Neutron diffraction experiments reveal enhanced magnetic moments by F doping in agreement with the prediction of DFT calculation. For S doping in Mn0.60Fe1.25P0.66-ySi0.34Sy (y = 0.00, 0.01, 0.02, 0.03, 0.04) three impurity phases have been found from microstructural analysis, which reduce the stability of the FOMT in the main phase and decrease TC, e.g. the |ΔSm| reduces from 7.9(12.6) Jkg-1K-1 (332 K) for the undoped sample to 3.4(6.2) Jkg-1K-1 (313 K) for the maximum doped sample for Δμ0H = 1(2) T. Neutron diffraction experiments combined with first-principles theoretical calculation, distinguish the occupation of F/S dopants and the tuning mechanism for light element doping, corresponding to subtle structural changes and a strengthening of the covalent bonding between metal and metalloid atoms. It is found that the light elements F and S can effectively regulate the magnetocaloric properties and provide fundamental understanding of (Mn,Fe)2(P,Si)-based intermetallic compounds.@en