The crystal and magnetic structures of orthorhombic ε-Fe2O3 have been studied by simultaneous Rietveld refinement of X-ray and neutron powder-diffraction data in combination with Mössbauer spectroscopy, as well as magnetization and heat-capacity measurements. It has been found that above 150 K, the ε-Fe2O3 polymorph is a collinear ferrimagnet with magnetic moments directed along the a axis, whereas the magnetic ordering below 80 K is characterized by a square-wave incommensurate structure. The transformation between these two states is a second-order phase transition and involves subtle structural changes mostly affecting the coordination of the tetrahedral and one of the octahedral Fe sites. The temperature dependence of the ε-Fe2O3 magnetic properties is discussed in light of these results.

The magnetic properties of maghemite (gamma-Fe2O3) cubic and spherical nanoparticles of similar sizes have been experimentally and theoretically studied. The blocking temperature, T(B), of the nanoparticles depends on their shape, with the spherical ones exhibiting larger T(B). Other low temperature properties such as saturation magnetization, coercivity, loop shift or spin canting are rather similar. The experimental effective anisotropy and the Monte Carlo simulations indicate that the different random surface anisotropy of the two morphologies combined with the low magnetocrystalline anisotropy of gamma-Fe2O3 is the origin of these effects.

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The intimate relationship between stoichiometry and physicochemical properties in transition-metal oxides makes them appealing as tunable materials. These features become exacerbated when dealing with nanostructures. However, due to the complexity of nanoscale materials, establishing a distinct relationship between structure-morphology and functionalities is often complicated. In this regard, in the FexO/Fe3O4 system a largely unexplained broad dispersion of magnetic properties has been observed. Here we show, thanks to a comprehensive multi-technique approach, a clear correlation between the magneto-structural properties in large (45 nm) and small (9 nm) FexO/Fe3O4 core/shell nanoparticles that can explain the spread of magnetic behaviors. The results reveal that while the FexO core in the large nanoparticles is antiferromagnetic and has bulk-like stoichiometry and unit-cell parameters, the FexO core in the small particles is highly non-stoichiometric and strained, displaying no significant antiferromagnetism. These results highlight the importance of ample characterization to fully understand the properties of nanostructured metal oxides.

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