Occupancies of tetra- and octahedral sites in CoFe2O4 nanoparticles: The effect of the sintering temperature

Abstract

A temperature factor is one of the main parameters in the synthesis of nanoparticles and can affect considerably the arrangement of atoms in the lattice. In the system of magnetically hard CoFe2O4 spinel ferrite, the distribution of cations directly determines the magnetic properties of the sample. It was studied, on products of co-precipitation synthesis followed by a temperature dependent sinterization, by x-ray diffraction (XRD), x-ray absorption (XAS) using synchrotron radiation, vibrating sample magnetometry, and 57Fe Mössbauer spectroscopy (MS). From the Rietveld refinement of XRD patterns, the site occupancies reveal the following trend: with a decrease in the sintering temperature, the inversion degree parameter γ, which is a fraction of Co ions residing in the octahedral sites, decreases. For the highest sintering temperature explored in this work, 1000 °C, γ ≈ 0.83 giving rise to (Co0.17Fe0.83)A[Co0.83Fe1.27]BO4 formulation. For the lowest sintering temperature explored, 500 °C, the inversion degree is approximately 0.69 giving rise to (Co0.31Fe0.69)A[Co0.69Fe1.31]BO4 formulation. The propensity for the cationic arrangement was also confirmed by MS. Qualitative analysis of XAS at Co L32 edges strongly supports the tendency observed by XRD: the lower the sintering temperature, the more Co ions tend to occupy the tetrahedral sites. The magnetic behavior of the samples is consistent with the particle size which was determined by transmission/scanning electron microscopies. The particle size is the product of different sintering temperatures after the primary synthesis.