Effect of cation trapping on thermal stability of magnetite nanoparticles

We investigate the effect of sodium trapping on thermal stability of magnetite (Fe3O4) nanoparticles. The pure magnetite nanoparticles incubated in sodium hydroxide solutions and subsequently washed with water to remove the excess sodium. The amount of sodium in magnetite is measured using atomic absorption spectroscopy. The size distribution obtained from Small angle X-ray scattering measurements show that particles are fairly monodisperse. The FTIR spectra of nanoparticles show transmission bands at 441 and 611 cm(-1) are due to the symmetric stretching vibrations (v) of Fe-O in octahedral and tetrahedral sites respectively. With 500 ppm of sodium ions (Na+) in magnetite, the cubic ferrite structure of maghemite (gamma-Fe2O3) to hexagonal hematite (alpha-Fe2O3) phase transition is enhanced by -150 degrees C in air. The Rietveld analysis of sodium doped magnetite nanoparticles show that above 99% of metastable gamma-Fe2O3 is converted to a thermodynamically stable alpha-Fe2O3 after air annealing at 700 degrees C. A decrease in enthalpy observed in doped magnetite unambiguously confirms that the activation energy for maghemite to hematite transition is increased due to the presence of trapped sodium ions. These results suggest that the trapped cations in ferrite nanoparticles can stabilize them by increasing the activation energy.