Optimizing the synthesis of ZnFe₂O₄ through chemical and physical methods: effects of the synthesis route on the phase purity, inversion, and magnetic properties of spinel zinc ferrite

Abstract

In this work, ZnFe2O4 ferrites were prepared by chemical (coprecipitation) and ceramic (ball-milling) methods. The effects of the synthesis route on the phase purity, crystallinity, particle size distribution, and magnetic properties were investigated to identify the most appropriate conditions for the syhnthesis of high quality ferrites. The samples were exmined by X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and Mössbauer spectroscopy. The XRD patterns revealed that a high-purity spinel phase was obtained by coprecipitation at pH ≥ 7 by calcining the pristine powder at T ≥ 900 °C, whereas a single spinel phase was obtained at T ≥ 700 °C in the ball-milling method. The crystallite size of the spinel phase exhibited general increasing trends with the increase of the pH value under the same heat-treatment conditions, and with the increase of the calcination temperature. Additionally, the mean physical particle size exhibited an increasing trend with the increase of the calcination temperature. The VSM measurements revealed a noticeable degree of inversion in the spinel ferrites prepared by coprecipitation (exhibiting the highest degree at pH = 10), and an insignificant degree of inversion in the spinel ferrites prepared by the ceramic method. However, calcining the powder exhibiting the highest degree of inversion (prepared by coprecipitation at pH = 10) at 1100 °C resulted in ordering the zinc ions at tetrahedral sites of the spinel structure. Mössbauer spectra for representative zinc ferrite samples prepared by the two methods revealed a major central doublet (with a small magnetic sextet corresponding to the α-Fe2O3 phase in the sample at pH = 7). The hyperfine parameters of the doublet observed in the Mössbauer spectra of the samples, and the corresponding magnetization behavior revealed a higher degree of ionic disorder in the spinel ferrite prepared by coprecipitation.