MnFeP(As, Ge, Si) series compounds are three kinds of MnFe-based magnetocaloric materials, which have giant magnetocaloric effect. In this work, the experimental characteristic curves of new style Mn-Fe-P-Si materials, numbered as 1: Mn_1.32Fe_0.67P_0.52Si_0.49, 2: Mn_1.37Fe_0.63P_0.5Si_0.5, and 3: Mn_1.35Fe_0.66P_0.5Si_0.5 are presented. Based on the experimental data of these component materials and thermodynamic analysis method, a novel composite material is put forward. The optimal molar mass ratios of the composite material are obtained and they are 0.22, 0.33, 0.45, respectively. A regenerative Brayton refrigeration cycle employing the optimal composite material with thermal hysteresis as the working medium is built. By numerical calculation, the influences of thermal hysteresis on the main thermodynamic quantities are evaluated. The results show that the thermal hysteresis of the working medium results in a decrease of 13.6%, 14.6%, 18.8%, and 16.1% of the cooling quantity, net cooling quantity, optimally working temperature range, and coefficient of performance, respectively. These conclusions are beneficial to the optimal parameter design and performance improvement of active magnetic refrigerators.

The giant magnetocaloric effect is widely achieved in hexagonal MnMX-based (M = Co or Ni, X = Si or Ge) ferromagnets at their first-order magnetostructural transition. However, the thermal hysteresis and low sensitivity of the magnetostructural transition to the magnetic field inevitably lead to a sizeable irreversibility of the low-field magnetocaloric effect. Here, we show an alternative way to realize a reversible low-field magnetocaloric effect in MnMX-based alloys by taking advantage of the second-order phase transition. With introducing Cu into Co in stoichiometric MnCoGe alloy, the martensitic transition is stabilized at high temperature, while the Curie temperature of the orthorhombic phase is reduced to room temperature. As a result, a second-order magnetic transition with a negligible thermal hysteresis and a large magnetization change can be observed, enabling a reversible magnetocaloric effect. By both calorimetric and direct measurements, a reversible adiabatic temperature change of about 1 K is obtained under a field change of 0-1 T at 304 K, which is larger than that obtained in a first-order magnetostructural transition. To gain a better insight into the origin of these experimental results, first-principles calculations are carried out to characterize the chemical bonds and the magnetic exchange interaction. Our work provides an understanding of the MnCoGe alloy and indicates a feasible route to improve the reversibility of the low-field magnetocaloric effect in the MnMX system.

The first-order magneto-elastic transition in the Mn–Fe–P–Si alloys can be tailored by vanadium substitution. Alloys with a suitable V substitution provide an excellent magnetocaloric effect with minor hysteresis in low magnetic fields up to 1.2 T. Mössbauer measurements show that the hyperfine field is reduced by V substitution. Neutron diffraction reveals that Fe is substituted by V on the 3f site and the magnetic moment on the 3f site is enhanced by the V substitution. The modified magnetic exchange field around the 3f and 3g positions in the lattice can be utilized to design suitable magnetocaloric materials that operate in low magnetic fields.

Approaching the border of the first order transition and second order transition is significant to optimize the giant magnetocaloric materials performance. The influence of vanadium substitution in the Mn_1.2-xV_xFe_0.75P_0.5Si_0.5 alloys is investigated for annealing temperatures of 1323, 1373 and 1423 K. By tuning both the annealing temperature and the V substitution simultaneously, the magnetocaloric effect can be enhanced without enlarging the thermal hysteresis near the border of the first to second order transition. Neutron diffraction measurements reveal the changes of site occupation and interatomic distances caused by varying the annealing temperature and V substitution. The properties of the alloy with x = 0.02 annealed at 1323 K is comparable to those found for the MnFe_0.95P_0.595Si_0.33B_0.075 alloy, illustrating that Mn_1.2-xV_xFe_0.75P_0.5Si_0.5 alloys are excellent materials for magnetic heat-pumping near room temperature.

A rotary active magnetic regeneration refrigerator prototype named FAME Cooler was developed for studying the performance of different magnetocaloric materials in a realistic practical environment. The rotary magnetic field source generates an average magnetic field of 0.875 T within a volume of 0.71 l The regenerator is designed asymmetrically and holds in total 1.18 kg of gadolinium spheres for a first performance test. Combined with a real-time controlled programmable solenoid-valves system, different working parameters or thermodynamic cycles can be applied. In the performance test, while the temperature of system hot side was fixed at 295 K, under a utilization condition of 0.25, this prototype achieved a maximum zero-span cooling power of 162.4 W, and a zero-power temperature span of 11.6 K. Under a utilization condition of 0.15, a maximum COP of 1.85 was reached. These performance metrics are comparable with existing magnetic heat pump devices of the same scale.

The relation between the microstructure and the magnetic properties of Fe₂P-type (Mn,Fe)₂(P,Si,B) based materials has been systematically investigated by changing the annealing temperature and time. X-ray diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy measurements show that the alloys contain the main Fe₂P-type phase and two impurity phases of (Fe,Mn)₅Si₃-type and Fe₂MnSi-type. Boron appears to facilitate the formation of the Fe₂P-type phase during the arc-melting progress. Upon increasing the annealing temperatures from 1123 to 1423 K, the Curie temperature (T_C) decreases from 302.0 to 270.5 K in the Mn_1.15Fe_0.85P_0.55Si_0.45 alloys and the magnetic-entropy change (ΔS_M) increases linearly with annealing temperature. For the Mn_1.15Fe_0.85P_0.52Si_0.45B_0.03 alloys annealed at 1423 K for different times, T_C decreases from 263.8 and 232.8 K with increasing annealing time and ΔS_M reaches a maximum value after annealing for 48 h. The differences in the annealing temperature and time influence the Si content in the Fe₂P-type phase of the alloys and determine T_C, the thermal hysteresis and the magneto-elastic transition.