Up to now, the crystallographic structure of the magnetoelectric perovskite EuTiO3 has been considered to remain cubic down to low temperature. Here we present high-resolution synchrotron x-ray powder-diffraction data showing the existence of a structural phase transition, from cubic Pm-3m to tetragonal I4/mcm, involving TiO6 octahedra tilting, in analogy to the case of SrTiO3. The temperature evolution of the tilting angle and of the full width at half maximum of the (200) cubic reflection family indicate a critical temperature Tc = 235 K. This critical temperature is well below the recent anomaly reported by specific-heat measurement at TA $\sim${} 282 K. By performing atomic pair distribution function analysis on diffraction data, we provide evidence of a mismatch between the local (short-range) and the average crystallographic structures in this material. Below the estimated Tc, the average model symmetry is fully compatible with the local environment distortion, but the former is characterized by a reduced value of the tilting angle compared to the latter. At T = 240 K, data show the presence of local octahedra tilting identical to the low-temperature one, while the average crystallographic structure remains cubic. On this basis, we propose that intrinsic lattice disorder is of fundamental importance in the understanding of EuTiO3 properties.

Here we report on the impact of reducing the crystalline size on the structural and magnetic properties of γ-Fe₂O₃ maghemite nanoparticles. A set of polycrystalline specimens with crystallite size ranging from ~2 to ~50 nm was obtained combining microwave plasma synthesis and commercial samples. Crystallite size was derived by electron microscopy and synchrotron powder diffraction, which was used also to investigate the crystallographic structure. The local atomic structure was inquired combining pair distribution function (PDF) and X-ray absorption spectroscopy (XAS). PDF revealed that reducing the crystal dimension induces the depletion of the amount of Fe tetrahedral sites. XAS confirmed significant bond distance expansion and a loose Fe-Fe connectivity between octahedral and tetrahedral sites. Molecular dynamics revealed important surface effects, whose implementation in PDF reproduces the first shells of experimental curves. The structural disorder affects the magnetic properties more and more with decreasing the nanoparticle size. In particular, the saturation magnetization reduces, revealing a spin canting effect. Moreover, a large effective magnetic anisotropy is measured at low temperature together with an exchange bias effect, a behavior that we related to the existence of a highly disordered glassy magnetic phase.