Study of Iron oxide nanoparticles using Mössbauer spectroscopy with a high velocity resolution.

Iron oxide (magnetite and maghemite) nanoparticles developed for magnetic fluids were studied using Mössbauer spectroscopy with a high velocity resolution at 295 and 90K. The recorded Mössbauer spectra have demonstrated that usual physical models based on octahedral and tetrahedral sites were not suitable for fitting. Alternatively, the Mössbauer spectra were nicely fitted using a large number of magnetic sextets. The obtained results showed that the Mössbauer spectra and the assessed parameters were different for nanoparticles as-prepared and dispersed in the dispersing fluid at 295K. We claim that this finding is mainly due to the interaction of polar molecules with Iron cations at nanoparticle's surface or due to the surface coating using carboxylic-terminated molecules. It is assumed that the large number of spectral components may be related to complexity of the nanoparticle's characteristics and deviations from stoichiometry, including in the latter the influence of the oxidation of magnetite towards maghemite.

The mechanically induced structural disorder in barium hexaferrite, BaFe12O19, and its impact on magnetism.

The response of the structure of the M-type barium hexaferrite (BaFe12O19) to mechanical action through high-energy milling and its impact on the magnetic behaviour of the ferrite are investigated. Due to the ability of the (57)Fe Mössbauer spectroscopic technique to probe the environment of the Fe nuclei, a valuable insight on a local atomic scale into the mechanically induced changes in the hexagonal structure of the material is obtained. It is revealed that the milling of BaFe12O19 results in the deformation of its constituent polyhedra (FeO6 octahedra, FeO4 tetrahedra and FeO5 triangular bi-pyramids) as well as in the mechanically triggered transition of the Fe(3+) cations from the regular 12k octahedral sites into the interstitial positions provided by the magnetoplumbite structure. The response of the hexaferrite to the mechanical treatment is found to be accompanied by the formation of a non-uniform nanostructure consisting of an ordered crystallite surrounded/separated by a structurally disordered surface shell/interface region. The distorted polyhedra and the non-equilibrium cation distribution are found to be confined to the amorphous near-surface layers of the ferrite nanoparticles with the thickness extending up to about 2 nm. The information on the mechanically induced short-range structural disorder in BaFe12O19 is complemented by an investigation of its magnetic behaviour on a macroscopic scale. It is demonstrated that the milled ferrite nanoparticles exhibit a pure superparamagnetism at room temperature. As a consequence of the far-from-equilibrium structural disorder in the surface shell of the nanoparticles, the mechanically treated BaFe12O19 exhibits a reduced magnetization and an enhanced coercivity.

Comparative study of iron oxide nanoparticles as-prepared and dispersed in Copaiba oil using Mössbauer spectroscopy with low and high velocity resolution.

Iron oxide nanoparticles, probably magnetite, as-prepared and dispersed in Copaiba oil were studied by Mössbauer spectroscopy using two different spectrometers: with a low velocity resolution (512 channels) for measurements at 295 and 21K and with a high velocity resolution (4096 channels) for measurements at 295 and 90K. The fitting of all measured spectra demonstrated that usual models applied to fit Mössbauer spectra of magnetite and maghemite particles were not suitable. Therefore, the recorded spectra were fitted using a large number of spectral components on the basis of better quality of the fit and linearity of differential spectra. The number of components obtained for the better fit appeared to be different for spectra measured with a low and a high velocity resolution. However, these results demonstrated differences of Mössbauer parameters for iron oxide nanoparticles as-prepared and dispersed in Copaiba oil at applied temperatures. The effect of Copaiba oil molecules on Mössbauer parameters may be a result of the interactions of polar molecules such as kaurinic acid with nanoparticles' surface.

Cubic versus spherical magnetic nanoparticles: the role of surface anisotropy.

The magnetic properties of maghemite (gamma-Fe2O3) cubic and spherical nanoparticles of similar sizes have been experimentally and theoretically studied. The blocking temperature, T(B), of the nanoparticles depends on their shape, with the spherical ones exhibiting larger T(B). Other low temperature properties such as saturation magnetization, coercivity, loop shift or spin canting are rather similar. The experimental effective anisotropy and the Monte Carlo simulations indicate that the different random surface anisotropy of the two morphologies combined with the low magnetocrystalline anisotropy of gamma-Fe2O3 is the origin of these effects.