Comparison of magnetic properties and high-temperature phase stability of phosphate- and oleic acid-capped iron oxide nanoparticles

Abstract

We study the influence of dynamic capping of Fe3O4 nanoparticles with phosphate and oleic acid, on their structure, magnetic properties and thermal stability of magnetic nanoparticles. It is observed that the phosphate coating on iron oxide lowers the dipole–dipole interaction significantly, as compared to oleic acid capping. The Mossbauer results show that the spin canting order of oxidized shell and the mean hyperfine field values follow the order Fe0 (uncoated) > FeOA (oleic acid capped) > FP1 (phosphate capped). The uncoated Fe3O4 nanoparticle is non-stoichiometric in nature due to oxidation, whereas FP1 and FeOA are of the correct stoichiometry. Mossbauer and photoacoustic spectroscopic studies on air-annealed phosphate-coated magnetite nanoparticles confirm that the magnetic iron oxide phase is preserved up to 833 K and a complete conversion of Fe3O4 into the non-magnetic hematite phase occurs at 1173 K. The iron oxide air annealed at 833 K is found to have a shell of orthorhombic α-Fe2O3 over the magnetite core. However, in oleic acid-coated nanoparticles, the magnetic to non-magnetic phase transformation commences at 623 K and the conversion was complete at 823 K. The photoacoustic spectra of the air-annealed phosphate-coated Fe3O4 particles showed a flipping of the absorption intensity between 500−700 nm and 800−1000 nm, due to the conversion of Fe3O4 to γ-Fe2O3 at 923 and γ-Fe2O3 to α-Fe2O3 at 1173 K, respectively. The γ-Fe2O3 showed an intense absorption peak above 750 nm, whereas the α-Fe2O3 showed a peak broadening in the wavelength range of 600–700 nm, in addition to the strong peaks at a wavelength above 750 nm. This study suggests that the photoacoustic spectroscopy can distinguish clearly the three polymorphs of iron oxide i.e., Fe3O4, γ-Fe2O3 and α-Fe2O3. Our results confirm the ability of phosphate-capped iron oxide particles to retard the oxidation of Fe2+ contents during the crystal growth process.