In view of the interest that (Fe,Co)2(P,Si) compounds have as potential permanent magnets, their structural and magnetic phase diagrams are explored focusing on establishing the range where the hexagonal Fe2P-type structure is observed. In Fe1.93-xCoxP1-ySiy, the highest Si content prior entering a mixed phase domain is y ≈ 0.5. At high Si content but low Co for Fe substitutions, a structural distortion leading to a body-centered orthorhombic structure occurs. At high Co contents, when the Fe2P unit cell reaches a critical volume of about 102.4 Å3, the samples crystallize in a Co2P-type orthorhombic structure. Within the Fe2P-type structural range, the evolution of the unit-cell volume appears to follow the Vegard's law, but this hides strongly anisotropic changes. Simultaneous Co for Fe and Si for P substitutions increase the range where the hexagonal structure is observed in comparison to ternary Fe2(P,Si) and (Fe,Co)2P. The samples are ferromagnetic, but with Curie temperatures showing an unusual evolution, uncorrelated to the c/a ratio of the lattice parameters. At low Si content, TC increases with Co for Fe substitutions. For y = 0.2, the evolution is not significant, while at high Si content TC systematically decreases with the increase in Co. Large Si and Co substitutions lead to a swift weakening of the magnetocrystalline anisotropy until the easy axis anisotropy turns from the c axis toward the a-b plane. This study guides future investigations by restricting the range where desirable properties for permanent magnetic applications can be expected to 0.1 ≲ x ≲ 0.3 and 0.1 ≲ y ≲ 0.3.@en

We explore the crystal structure and magnetic properties of quaternary materials deriving from the hexagonal Fe2P, an iron binary known to present a particularly large magnetocrystalline anisotropy potentially interesting for permanent magnets, but with unfortunately a Curie temperature far too low for applications. Using simultaneous metal and metalloid substitutions in Fe2-zCozP1-xBx and Fe2-zCozP1-ySiy quaternaries, we found it is possible to increase the Curie temperature up to at least 640 K while maintaining a c axis uniaxial magnetocrystalline anisotropy, leading to an appreciable magnetic anisotropy at room temperature. In Fe2-zCozP1-xBx, though boron is appropriate to increase the Curie temperature, its amount is limited as it also favors the formation of secondary phases. Contrary to what could be anticipated from the phase diagrams of Fe2-zCozP or Fe2P1-ySiy ternaries, simultaneous Co for Fe and Si for P substitutions in Fe2-zCozP1-ySiy are found to significantly expand the range of stability of the Fe2P-type crystal structure. X-ray diffraction patterns on powders oriented in magnetic field indicate a c axis uniaxial magnetic anisotropy. Appropriate heat-treatments and slight metal deficiency are found suitable to limit the formation of unwanted secondary phase with 3:1 metal:metalloid ratio. As a result, nearly single-phase Fe1.95-zCozP1-ySiy materials are prepared and exhibit an appreciable magnetic anisotropy with K1 up to approximately 0.93 MJm−3 at room temperature. This study experimentally demonstrates that Fe2P-type transition metal quaternaries can present an interest not only for their first-order magnetic transition, but also for their magnetic anisotropy making them potential candidates for magnetostatic applications.@en

The influence of Nb substitution on the structure, magnetoelastic transition and magnetocaloric properties has been investigated for the Mn1.1Fe0.85-xNbxP0.43Si0.57 alloys. The substitution for Fe by merely 4.7 at.% Nb (i.e. x = 0.04) significantly diminishes the thermal hysteresis from 10 to 1 K due to the reduced structural discontinuity crossing the magnetoelastic transition. This also improves the mechanical stability. The Curie temperature of the magnetoelastic transition is lowered by approximately 11.6 K per at.% of the Nb substitution, originating from the enhanced covalent bonding that favors the paramagnetic state. The giant magnetocaloric effect is still retained in the Nb-substituted alloys.@en

The influence of Nb substitution on the structure, magnetoelastic transition and magnetocaloric properties has been investigated for the Mn1.1Fe0.85-xNbxP0.43Si0.57 alloys. The substitution for Fe by merely 4.7 at.% Nb (i.e. x = 0.04) significantly diminishes the thermal hysteresis from 10 to 1 K due to the reduced structural discontinuity crossing the magnetoelastic transition. This also improves the mechanical stability. The Curie temperature of the magnetoelastic transition is lowered by approximately 11.6 K per at.% of the Nb substitution, originating from the enhanced covalent bonding that favors the paramagnetic state. The giant magnetocaloric effect is still retained in the Nb-substituted alloys.@en