The influence of off-stoichiometry and of doping with the 5d transition metal Ta has been studied in the quaternary (Mn,Fe)₂(P,Si)-based compound, which is one of the most promising materials systems for magnetic refrigeration. It is found that Ta substitution can decrease the transition temperature T_tr, while the thermal hysteresis ∆T_hys remains about constant. A low Ta doping enhances the magnetocaloric effect (MCE). For Mn_0.6Fe_1.27-yTa_yP_0.64Si_0.36 with y = 0.01 the magnetic entropy change ∆S_m shows and enhancement of 30.7% compared to the undoped material for a low magnetic field change of 1 T. The occupancy of substitutional Ta atoms is determined by XRD and DFT calculations. The T_tr shift and enhanced MCE upon Ta doping are ascribed to the competition between a weakening of the magnetic exchange interactions and a strengthening of the hybridization. Our studies provide a good strategy to further optimize the MCE of this material family.

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In this work, the magnetocaloric effect and negative thermal expansion in melt-spun Fe₂Hf_0.83Ta_0.17 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 Fe₂Hf_0.83Ta_0.17 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 (dT_t/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.

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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.

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Magnetic refrigeration (MR) is a cutting-edge technology that promises high energy efficiency and eco-friendliness, making it an exciting alternative to traditional refrigeration systems. However, the main challenge to its widespread adoption is cost competitiveness. In this context, the use of liquid metals as heat transfer liquids in the MR has been proposed as a game-changing solution. Unfortunately, the toxicity and flammability of these liquid metals have raised serious concerns, limiting their practical use. In this study, we investigate the compatibility of a nontoxic and nonflammable GaInSn-based liquid metal with a magnetocaloric material, La(Fe,Mn,Si)₁₃H_z, over a 1.5 year period. Our findings reveal nearly a 14% reduction in specific cooling energy and peak-specific isothermal magnetic entropy change for the considered magnetocaloric material. Our study provides valuable insights into the long-term stability of magnetocaloric materials and their compatibility with liquid metals, facilitating the development of more cost-effective and sustainable MR systems.

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The effect of Co and Ni doping on the structure, magnetic and magnetocaloric properties of Fe-rich (Mn,Fe)₂(P,Si) compounds was studied. With increasing Co and Ni content, both the Curie temperature (T_c) and the thermal hysteresis (ΔT_hys) decreased, whereas the hexagonal P-62 m crystal structure was maintained. A pronounced reduction in hysteresis was observed upon Co doping, while a significant reduction in Curie temperature was found upon Ni doping. Mössbauer spectroscopy measurements and DFT calculations indicated the substitution of Fe at the 3f site for both Co and Ni doping. Rietveld refinement of the X-ray diffraction data showed that Co substitute atoms in the main phase and the impurity phase, while Ni exhibits an affinity to the main phase. Magnetization measurements on the Co doped samples revealed an increase in magnetization for 2 at.% of Co, followed by a decrease for higher concentrations. DFT calculations showed that the magnetic moment on the 3f site is enhanced by Co substitution, whereas an opposite trend was observed for Ni substitution.

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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 ∆S_m of 2.3 Jkg⁻¹K⁻¹ for a magnetic field change of 0–5 T, has been identified. The T_C and saturation magnetization M_S can be controlled by adjusting the Ni/Co concentration and doping non-magnetic Cu atoms. The compositional maps of T_C and M_S 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.

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Solid‐state caloric effects as intrinsic responses from different physical external stimuli (magnetic‐, uniaxial stress‐, pressure‐ and electronic‐ fields) have been evaluated near magnetic phase transformations. In the last decades the magnetically driven caloric changes in various magnetocaloric materials (MCMs) have been exploited extensively for magnetic refrigeration and magnetic heat pumping scenarios near room temperature. This thesis systematically investigates the magnetocaloric effect (MCE) for the representative magnetoelastic (Mn,Fe)2(P,Si) system. Special emphasis has been directed towards the giant MCE in nanoscale particles and the influence of doping with elements that show a strong electronegativity on the magnetic properties of this metal‐metalloid system. Meanwhile, two optimization strategies (decoupling and light element B doping) are successfully introduced to regulate the thermal hysteresis ΔThys, the ferromagnetic phase transition TC and improve the reversibility of the MCE for magnetostructural transition in the all‐d‐metal NiCoMnTi Heusler alloys.@en

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.

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Magnetocaloric materials undergoing reversible phase transitions are highly desirable for magnetic refrigeration applications. (Mn,Fe)₂(P,Si) alloys exhibit a giant magnetocaloric effect accompanied by a magnetoelastic transition, while the noticeable irreversibility causes drastic degradation of the magnetocaloric properties during consecutive cooling cycles. In the present work, we performed a comprehensive study on the magnetoelastic transition of the (Mn,Fe)₂(P,Si) alloys by high-resolution transmission electron microscopy, in situ field- and temperature-dependent neutron powder diffraction as well as density functional theory calculations (DFT). We found a generalized relationship between the thermal hysteresis and the transition-induced elastic strain energy for the (Mn,Fe)₂(P,Si) family. The thermal hysteresis was greatly reduced from 11 to 1 K by a mere 4 at.% substitution of Fe by Mo in the Mn_1.15Fe_0.80P_0.45Si_0.55 alloy. This reduction is found to be due to a strong reduction in the transition-induced elastic strain energy. The significantly enhanced reversibility of the magnetoelastic transition leads to a remarkable improvement of the reversible magnetocaloric properties, compared to the parent alloy. Based on the DFT calculations and the neutron diffraction experiments, we also elucidated the underlying mechanism of the tunable transition temperature for the (Mn,Fe)₂(P,Si) family, which can essentially be attributed to the strong competition between the covalent bonding and the ferromagnetic exchange coupling. The present work provides not only a new strategy to improve the reversibility of a first-order magnetic transition but also essential insight into the electron-spin-lattice coupling in giant magnetocaloric materials.

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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.

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The all-d-metal Ni-(Co)-Mn-Ti-based Heusler alloys are found to show a giant magnetocaloric effect near room temperature and are thereby potential materials for solid-state refrigeration. However, the relative large thermal hysteresis and the moderate ferromagnetic magnetization provides limitations for real applications. In the present study, we demonstrate that introducing interstitial B atoms within Ni36.5Co13.5Mn35Ti15 alloys can effectively decrease the thermal hysteresis ΔThys (down to 4.4 K), and simultaneously improve the saturation magnetization (maximum 40% enhancement) for low concentrations of B doping (up to 0.4 at. %). In comparison to the undoped reference material, the maximum magnetic entropy change (ΔSm) for the Ni36.5Co13.5Mn35Ti15B0.4 alloy shows a remarkable improvement from 9.7 to 24.3 J kg-1K-1 for an applied magnetic field change (Δμ0H) of 5 T (30.2 J kg-1K-1 for Δμ0H = 7 T). Additionally, due to the obtained low thermal hysteresis ΔThys, the maximum reversible ΔSmrev amounts to 18.9 J kg-1K-1 at 283 K for Δμ0H = 5 T (22.0 J kg-1K-1 at 281 K for Δμ0H = 7 T), which is competitive to the traditional Ni-Mn-X-based Heusler alloys (X = Ga, In, Sn, Sb). The enhancement of the magnetic moments by B doping is also observed in first-principles calculations. These calculations clarify the atomic occupancy of B and the changes in the electronic configuration. Our current study indicates that interstitial doping with a light element (boron) is an effective method to improve the magnetocaloric effect in these all-d-metal Ni-Co-Mn-Ti-based magnetic Heusler compounds.

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The quarternary (Mn,Fe)₂(P,Si)-based materials with a giant magnetocaloric effect (GMCE) at the ferromagnetic transition T_C 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 T_C near room temperature and tune the magnetocaloric properties. For F doping the first-order magnetic transition (FOMT) of Mn_0.60Fe_1.30P_0.64Si_0.36F_x (x = 0.00, 0.01, 0.02, 0.03) is enhanced, which is explained by an enhanced magnetoelastic coupling. The magnetic entropy change |ΔS_m| 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 |ΔS_m| 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 Mn_0.60Fe_1.25P_0.66-ySi_0.34S_y (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 T_C, e.g. the |ΔS_m| 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.

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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.

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