TiNiSi-type MnCoSi-based alloys show large magnetostriction during the magnetic-field-induced metamagnetic transition. However, the high critical field required to drive the transition directly hinders their potential applications. In this work, we systematically investigate the tricritical behavior and magnetostrictive effect in substituted MnCoSi alloys. Replacing Si with Sb or In, Co with Fe or Cu, and Mn with Co, which can simultaneously reduce the critical field and the temperature of tricritical point, are explored. Among the substituted MnCoSi alloys, Mn_0.983Co_1.017Si displays a temperature of a tricritical point of 250 K and a room-temperature critical field of 0.60 T, which is the lowest up to now. Profited from these optimizations, a large reversible magnetostrictive effect under low field is successfully realized at room temperature. In a field of 1 T, the magnetostriction of Mn_0.983Co_1.017Si alloy is close to 1000 ppm. Besides, a strong relation between critical field and valence electron concentration is revealed in the transition-metal-substituted MnCoSi alloys. Our work greatly enhances the low-field magnetostrictive performance of MnCoSi-based alloys and make them be of interest in potential applications.

We performed neutron-diffraction experiments and density functional theory calculations to study the magnetostructural coupling in MnCoGeBx (x=0, 0.01, and 0.05) alloys. By varying the amount of boron addition, we are able to freely switch the magnetostructural coupling on and off in the MnCoGe alloys. It is found that the boron addition stabilizes the high-temperature hexagonal phase due to the reduced interatomic distances and the enhanced covalent bonding. The hexagonal-orthorhombic structural transition shifts to low temperatures with the boron addition and coincides with the paramagnetic-ferromagnetic (PM-FM) transition in the MnCoGeB0.01 alloy. With a further increase in the boron addition, the structural and magnetic transitions are decoupled again. The hexagonal-orthorhombic structural transition is significantly suppressed in the MnCoGeB0.05 alloy, although subtle distortions in the hexagonal structure are evidenced by a canted spin arrangement below 75 K. The MnCoGe and MnCoGeB0.01 alloys show a collinear FM structure, having a much larger Mn moment than the MnCoGeB0.05 alloy. The relatively small Mn moment in the MnCoGeB0.05 alloy can be attributed to the shortened Mn-Mn distance and the enhanced overlap of the 3d orbitals between the neighboring Mn atoms. The uncovered relationship between the structural evolution and the sizable magnetic moment in the present work offers more insight into the magnetostructural coupling in the MnCoGe-based alloys.

MnMX (M = Co or Ni, X = Si or Ge) alloys with strong magnetostructural coupling exhibit giant magnetic entropy change and are currently extensively studied. However, large thermal hysteresis results in serious irreversibility of the magnetocaloric effect in this well-known system. In this work, we report a low thermal hysteresis and large reversible magnetocaloric effect in a MnNiGe-based system. The introduction of Fe into both Ni and Mn sites can establish stable magnetostructural transitions from paramagnetic hexagonal to ferromagnetic orthorhombic phases. Fascinatingly, a low thermal hysteresis of 5.2 K is achieved in Mn_0.9Fe_0.2Ni_0.9Ge alloy with a large magnetization difference of 62.1 A m²/kg between the two phases. These optimized parameters lead to a partially reversible phase transformation under a magnetic stimulus and bring about a large reversible magnetic entropy change of −18.6 Jkg⁻¹K⁻¹ under the field variation of 0–5 T, which is the largest value reported in MnMX system up to now. Moreover, this low-hysteresis magnetostructural transformation and large reversible magnetocaloric effect can be tuned by doping with Si in a wide temperature range covering room temperature. We also introduce geometrically nonlinear theory to discuss the origin of low hysteresis in MnMX alloys. A strong relation is found between thermal hysteresis and the change of c axis in the orthorhombic structure during the transition. Our work greatly develops the potential of MnMX alloys as magnetocaloric materials and is meaningful to seek or design a MnMX system with low thermal hysteresis.