Study of Phase Transformations and Hyperfine Interactions in Fe3O4 and Fe3O4@Au Nanoparticles.

The paper presents the results of a study of iron oxide nanoparticles obtained by chemical coprecipitation, coated (Fe3O4@Au) and not coated (Fe3O4) with gold, which were subjected to thermal annealing. To characterize the nanoparticles under study, scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectroscopy on 57Fe nuclei were used, the combination of which made it possible to establish a sequence of phase transformations, changes in morphological and structural characteristics, as well as parameters of hyperfine interactions. During the studies, it was found that thermal annealing of nanoparticles leads to phase transformation processes in the following sequence: nonstoichiometric magnetite (Fe3-γO4) → maghemite (γ-Fe2O3) → hematite (α-Fe2O3), followed by structural ordering and coarsening of nanoparticles. It is shown that nanoparticles of nonstoichiometric magnetite with and without gold coating are in the superparamagnetic state with a slow relaxation rate. The magnetic anisotropy energy of nonstoichiometric magnetite is determined as a function of the annealing temperature. An estimate was made of the average size of the region of magnetic ordering of Fe atoms in nonstoichiometric magnetite, which is in good agreement with the data on the average sizes of nanoparticles determined by scanning electron microscopy.

Study of Magnetic Properties of Fe100-xNix Nanostructures Using the Mössbauer Spectroscopy Method.

Hyperfine interactions of 57Fe nuclei in Fe100-xNix nanostructures synthesized in polymer ion-track membranes were studied by Mössbauer spectroscopy. The main part of obtained nanostructures was Fe100-xNix nanotubes with bcc structure for 0 ≤ x ≤ 40, and with fcc structure for 50 ≤ x ≤ 90. The length, outside diameter and wall thickness of nanotubes were 12 µm, 400 ± 10 nm and 120 ± 5 nm respectively. For the studied nanotubes a magnetic texture is observedalong their axis. The average value of the angle between the direction of the Fe atom magnetic moment and the nanotubes axis decreases with increasing of Ni concentration for nanotubes with bcc structure from ~50° to ~40°, and with fcc structure from ~55° to ~46°. The concentration dependences of the hyperfine parameters of nanotubes Mössbauer spectra are qualitatively consistent with the data for bulk polycrystalline samples. With Ni concentration increasing the average value of the hyperfine magnetic field increases from ~328 kOe to ~335 kOe for the bcc structure and drops to ~303 kOe in the transition to the fcc structure and then decreases to ~290 kOe at x = 90. Replacing the Fe atom with the Ni atom in the nearest environment of Fe atom within nanotubes with bcc structure lead to an increase in the hyperfine magnetic field by "6-9 kOe", and in tubes with fcc structure-to a decrease in the hyperfine magnetic field by "11-16 kOe". The changes of the quadrupole shift and hyperfine magnetic field are linearly correlated with the coefficient -(15 ± 5)·10-4 mm/s/kOe.