Abstract
Binary ε-Fe3N1.098 and ternary ε-Fe2.322Co0.678N0.888 were synthesized as spherical bulk materials using novel high-pressure solid-state metathesis reactions (HPSSM). The structural and magnetic properties of the two nitrides were investigated using neutron powder diffraction (NPD), a vibrating sample magnetometer (VSM), and first-principle calculations. We found that at high pressure and high temperature (HPHT), nitrogen atoms enter the interstitial 2d sites of the nitrogen-rich ε-Fe3N1.098 structure, space group P6322, which were previously reported to be vacant. The stoichiometry of the nitride (N/Me ratio) and the level of disorder have a significant influence on the site occupancies and local magnetic moments in these iron-based nitrides. The substitution of Fe by Co in ε-Fe2.322Co0.678N0.888 did not reduce the mean magnetic moment (μm) per metal atom at the Wyckoff 6 g site. NPD refinements showed that the magnetic moment per Fe atom in ε-Fe3N1.098 (at 1.8 (4) μB) was slightly higher than that of ε-Fe2.322Co0.678N0.888, where the moment per Fe/Co atom is 1.7(2) μB.
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