Synchrotron X-ray absorption spectroscopy study of disordered cation distribution of nanosized zinc ferrite powders

Abstract

The zinc ferrite (ZnFe2O4) powders of various nanoparticle sizes were synthesised at different milling times (0 to 24 h) of the as-combusted powders. The non-equilibrium site occupancy of zinc (Zn2+) and ferric (Fe3+) ions was investigated through Zn and Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra. The XRD and SEM strongly confirm the particle size of these ferrites decreasing with the increasing milling time. Compared with the bulk specimen of zinc ferrite, both XANES and EXAFS spectra of zinc ferrite powders clearly exhibit the large translocation of Zn2+ ions from the tetrahedral (A) sites to the octahedral (B) sites and the opposite translocation of some of Fe3+ ions without affecting the long-range structural order. Moreover, the curve-fitting analysis of Zn and Fe K-edge EXAFS spectra indicates that the degree of inversion increases as the particle size decreases resulting in significant differences in the magnetic behaviours.