Since the discovery of giant magnetocaloric effect in MnFeP1-x As x compounds,much valuable work has been performed to develop and improve Fe2P-type transition-metal-based magnetic refrigerants.In this article,the recent progress of our studies on fundamental aspects of theoretical considerations and experimental techniques,effects of atomic substitution on the magnetism and magnetocalorics of Fe2P-type intermetallic compounds MnFeX（X=P,As,Ge,Si） is reviewed.Substituting Si（or Ge） for As leads to an As-free new magnetic material MnFeP1-xSi（Ge）x.These new materials show large magnetocaloric effects resembling MnFe（P,As） near room temperature.Some new physical phenomena,such as huge thermal hysteresis and ＇virgin＇ effect,were found in new materials.On the basis of Landau theory,a theoretical model was developed for studying the mechanism of phase transition in these materials.Our studies reveal that MnFe（P,Si） compound is a very promising material for room-temperature magnetic refrigeration and thermo-magnetic power generation.
The Mn Fe P0.56Si0.44 compound is investigated by x-ray diffraction, magnetic measurements, and x-ray absorption fine structure spectroscopy. It crystallizes in Fe2P-type structure with the lattice parameters a = b = 5.9823(0) and c = 3.4551(1) and undergoes a first-order phase transition at the Curie temperature of 255 K. The Fe K edge and Mn K edge x-ray absorption fine structure spectra show that Mn atoms mainly reside at 3g sites, while 3f sites are occupied by Fe atoms. The distances between the absorbing Fe atom and the first and second nearest neighbor Fe atoms in a 3f-layer shift from 2.65 and 4.01 in the ferromagnetic state to 2.61 and 3.96 in the paramagnetic phase. On the other hand, the distance between the 3g-layer and 3f-layer changes a little as 2.66 –2.73 below the Curie temperature and2.68 –2.75 above it.
