Phase and magnetic properties of iron oxide clusters in 20CaO·20SiO2·7Fe2O3·6FeO glasses

The annealing of 20CaO·20SiO₂·7Fe₂O₃·6FeO glasses at 973K in vacuo produced clusters of iron oxide, the shape of which was nearly spherical and the diameter distributed in the narrow range 25–115Å. The phase of clusters was identified to be Fe³⁺(Fe³⁺ _{poststagger|1.30}Fe²⁺ _{poststagger|0.55}V_0.15)·O₄ in the inverse spinel structure based upon the Mössbauer spectra and x-ray diffraction profiles. The clusters exhibited superparamagnetism and their effective anisotropy energy constant was inversely proportional to the cluster diameter. The magnetization of the glasses measured by a vibrating sample magnetometer was 7.2 × 10^-6 Wbmkg^-1 at 10 kOe at room temperature and smaller than the value calculated assuming that the whole clusters have superparamagnetism. These results suggest the pinning of spins near the cluster surface.