Abstract

Fe L2,3-edge XAS and XMCD studies have been used to unravel structural trends in the MgAl2O4–Fe3O4 solid solution where thermodynamic modeling has presented a challenge due to the complex ordering arrangements of the end-members. Partitioning of Fe3+ and Fe2+ between tetrahedral (Td) and octahedral (Oh) sites has been established. In the most Fe-rich samples, despite rapid quenching from a disordered state, FeTd2+ is not present, which matches the ordered, inverse spinel nature of end-member magnetite (Mgt) at room temperature. However, in intermediate compositions Al and Mg substantially replace Fe and small amounts of FeTd2+ are found, stabilized, or trapped by decreasing occurrence of the continuous nearest neighbor Fe–Fe interactions that facilitate charge redistribution by electron transfer. Furthermore, in the composition range ~Mgt0.4–0.9, XAS and XMCD bonding and site occupancy data suggest that nanoscale, magnetite-like Fe clusters are present. By contrast, at the spinel-rich end of the series, Mgt0.17 and Mgt0.23 have a homogeneous long-range distribution of Fe, Mg, and Al. These relationships are consistent with the intermediate and Fe-rich samples falling within a wide solvus in this system such that the Fe-clusters occur as proto-nuclei for phases that would exsolve following development of long-range crystalline order during slow cooling.

Unit-cell edges calculated from the spectroscopy-derived site occupancies show excellent agreement with those measured by X-ray powder diffraction on the bulk samples. Calculated saturation magnetic moments (Ms) for the Fe-rich samples also show excellent agreement with measured values but for the most Mg-rich samples are displaced to slightly higher values; this displacement is due to the presence of abundant Mg and Al disrupting the anti-parallel alignment of electron spins for Fe atoms.

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