We investigate the effect of Co2+ ion doping in magnetite (Fe3O4) on its crystal structure, magnetic properties, and phase stability during air and vacuum annealing. The nanoparticles are prepared by co-precipitation method and the particles are characterized by XRD, small angle x-ray scattering (SAXS), themogravimetric and differential scanning calorimetry (DSC), and vibrating sample magnetometer. The SAXS analysis on the doped samples show the most probable size, shape, and the polydispersity of particles, synthesized with different fractions (0–0.6) of Co2+ ion doping remains almost the same. On increasing cobalt content ferrimagnetic to the antiferromagnetic hematite (α-Fe2O3) phase transformation temperature is found to increase dramatically. For 0.1 fraction of Co2+ metal ion doping, an enhancement of 100 °C in the γ-Fe2O3 to α-Fe2O3 phase transition temperature is observed in the air annealed samples, whereas magnetic nature remains stable up to 1000 °C in vacuum annealed samples. On increasing the cobalt fractions beyond 0.2, air annealed samples show no change in the phase transition temperature. The observed enhancement in the phase transition temperature is attributed to the increased activation energy for phase transformation in presence of Co2+. Further, the DSC results corroborate the finding of an increase in the maghemite to hematite phase transition temperature with increase in cobalt fraction (x). The decrease in enthalpy from 89.86 to 17.62 J g−1 with an increase in cobalt content indicates that the degree of conversion of maghemite to hematite decreases with the cobalt content, which is in good agreement with the Rietveld analysis. The decrease in the Ms value in air annealed sample is attributed to the re-distribution of cations in the tetrahedral and octahedral sites, as the Fe3+A-Fe3+B super-exchange interaction is different from the Co2+A-Fe3+B interaction. These results suggest that a very small percentage of Co2+ metal ion doping can dramatically enhance the thermal stability of magnetic nanoparticles, which will have important consequences on the phase stability of ferrite nanocrystals.

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Magnetite nanoparticles of size ranging from 7-10 nm are prepared from aqueous solutions of Fe2+ and Fe3+ by microwave irradiation at different reaction temperatures ranging from 50 to 200 °C. The effect of reaction temperature on the structural and magnetic properties of nanoparticles is studied using X-ray diffraction (XRD), Transmission electron microscopy (TEM), Small angle X-ray scattering (SAXS), Thermo gravimetry (TGA), Differential scanning calorimetry (DSC), Vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR) techniques. The average size of the prepared particles, obtained from SAXS, is found to vary from 11 to 15±1 nm as the reaction temperature is increased from 50 to 200 °C. The weight gain curves under an external magnetic field show slope changes at 300 and 596 °C because of the magnetite to maghemite phase transition and ferri to paramagnetic phase transitions, respectively. The ferromagnetic γ-Fe2O3 to antiferromagnetic α-Fe2O3 phase transition temperature is found to be enhanced by 154 °C for the nanoparticles prepared at 200 °C, due to an enhanced activation energy for the cubic to a more compact hexagonal transition. The increase in the phase stability of nanoparticles prepared at elevated temperature is attributed to the diffusion of Na+ in the spinel structure. These results are useful to tailor magnetic particles with enhanced thermal stability for practical applications.

We study the effect of Zn2+ doping on crystal structure, magnetic properties, blocking and Curie temperatures, and the high temperature phase stability of magnetite nanoparticles under air and vacuum annealing. The Zn2+ doped nanoparticles (ZnxFe3−xO4 with x = 0, 0.2, 0.4, and 0.6) are prepared by simple co-precipitation technique and are characterized by high temperature X-ray powder diffraction (HTXRD), vibrating sample magnetometer, small angle X-ray scattering, thermogravimetry, differential scanning calorimetry (DSC), and transmission electron microscopy. Our HTXRD studies show that the decomposition temperature of pure magnetite (Fe3O4) in vacuum is increased by 300 °C (from 700 to 1000 °C), with 0.2 fraction of Zn2+ doping. The DSC studies under air environment also show that the γ-Fe2O3 to α-Fe2O3 phase transition temperature increases with the zinc fraction. The increase in transition temperature is attributed to the increase in the activation energy of the maghemite to hematite phase transition after the replacement of Fe3+ with larger diameter Zn2+ in the A site. Interestingly, the saturation magnetization increases from 61 to 69 emu/g upon 0.2 fraction of Zn2+, which augments the utility of the doped compound for practical applications. While the Curie temperature is found to increase with doping concentration, the blocking temperature shows an opposite trend. The blocking temperature values were found to be 262, 196, 144, and 153 K for 0, 0.2, 0.4, and 0.6 fraction of zinc, respectively. The reduction in TB is attributed to weak dipole–dipole interactions and local exchange coupling between nanoparticles. All the Zn2+ doped samples show superparamagnetic nature. These findings are extremely useful in producing superparamagnetic nanoparticles with enhanced magnetic properties for high temperature applications.

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