The Fe2P type Mn–Fe–P–Si alloys exhibit a giant magneto-elastic first-order transition, but the large hysteresis limits their performance. Crystal structure evolution and magnetocaloric performance were investigated by varying the Mn and Fe contents at a constant V substitution of 0.02 in Fe2P-type (Mn1.17-xFe0.73-yV0.02) (P0.5Si0.5) (where x + y = 0.02). The V substitution of Fe content shows a larger reduction of hysteresis compared with the same substitution amount of Mn content. During magnetoelastic phase transition, V-substitution reduces the volume change and the volumetric stresses, providing a superior mechanical stability. Compound with the V substitution of Fe (y = 0.02) shows the best magnetocaloric effect with a low thermal hysteresis of 0.6 K. Our developed Mn1.17-xFe0.73-yV0.02P0.5Si0.5 alloys are excellent materials for room-temperature magnetic heat-pumping applications by using a permanent magnet.@en

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.@en

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 Mn1.2-xVxFe0.75P0.5Si0.5 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 MnFe0.95P0.595Si0.33B0.075 alloy, illustrating that Mn1.2-xVxFe0.75P0.5Si0.5 alloys are excellent materials for magnetic heat-pumping near room temperature.@en

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 (TC) decreases from 302.0 to 270.5 K in the Mn1.15Fe0.85P0.55Si0.45 alloys and the magnetic-entropy change (ΔSM) increases linearly with annealing temperature. For the Mn1.15Fe0.85P0.52Si0.45B0.03 alloys annealed at 1423 K for different times, TC decreases from 263.8 and 232.8 K with increasing annealing time and ΔSM 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 TC, the thermal hysteresis and the magneto-elastic transition.@en

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 (TC) decreases from 302.0 to 270.5 K in the Mn1.15Fe0.85P0.55Si0.45 alloys and the magnetic-entropy change (ΔSM) increases linearly with annealing temperature. For the Mn1.15Fe0.85P0.52Si0.45B0.03 alloys annealed at 1423 K for different times, TC decreases from 263.8 and 232.8 K with increasing annealing time and ΔSM 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 TC, the thermal hysteresis and the magneto-elastic transition.@en

The lattice dynamics in MnFe0.95Si0.50P0.50 were investigated experimentally using Fe57 nuclear inelastic scattering and inelastic x-ray scattering across the first-order magnetic transition which occurs close to room temperature. The lattice dynamics characterization was supported by a macroscopic magnetic characterization, an x-ray diffraction study, and a hyperfine interactions characterization using Mössbauer spectroscopy. The Fe specific and the x-ray generalized density of phonon states were obtained both in the ferromagnetic and in the paramagnetic state. A prominent shift, 2meV at 20meV, in the x-ray generalized density of phonon states across the first-order magnetic transition, that involves vibrations with essentially Fe character, is revealed corroborated by a change in the local environment quantified in the isomer shift and the quadrupole splitting. Above 35meV the vibrational modes are practically insensitive to the magnetic transition. The entropy change induced by a 1T magnetic field across the magnetic transition, ∼10J/K/kg, is only a fraction of the Fe vibrational entropy change, 62(21)J/K/kg.@en