V. Chlan

Bentonite/Iron Oxide Composites: Preparation and Characterization by Hyperfine Methods

Bentonite/iron oxide system is prepared by isothermal calcination of powder composed of bentonite clay and precursor containing ferric acetate. This preparation technique enables one to get the composite material directly, that is, iron oxide particles embedded in a bentonite matrix. Calcination temperature is varied from 320°C to 700°C. The resulting series of samples is characterized by local methods based on hyperfine interactions: 57Fe nuclear magnetic resonance (NMR) and the Mössbauer spectroscopy. The results show that the phase composition changes significantly in dependence on calcination temperature. The amount of maghemite phase rapidly increases up to °C and decreases abruptly for higher than 460°C.

Magnetically induced structural reorientation in magnetite studied by nuclear magnetic resonance

Phenomenon related to low symmetry phase of magnetite Fe3O4 below the Verwey transition is the switching of magnetic easy axis by external magnetic field connected with a structural transition. Results of nuclear magnetic resonance (NMR) studies of axis switching are presented, preceded by careful characterization by magnetic measurements. We detect changes in the F57e NMR spectra that evidence the structural transition interrelated with the axis switching. We also observe the switching process in time and analyze the dynamics of the phenomenon. Phenomenological approach according to Kolmogorov–Johnson–Mehl–Avrami is employed to find a link between the experimental data from magnetization measurements and NMR, showing that the effect observed by these two methods has the same origin. Additionally, NMR identifies separately the unswitched and switched phase during the switching process.

Cluster Superconductivity in the Magnetoelectric Pb(Fe_{1/2}Sb_{1/2})O₃ Ceramics

We report the observation of cluster (local) superconductivity in the magnetoelectric Pb(Fe1/2Sb1/2)O3 ceramics prepared at a hydrostatic pressure of 6 GPa and temperatures 1200-1800 K to stabilize the perovskite phase. The superconductivity is manifested by an abrupt drop of the magnetic susceptibility at the critical temperature TC 7 K. Both the magnitude of this drop and TC decrease with magnetic field increase. Similarly, the low-field paramagnetic absorption measured by EPR spectrometer drops significantly below TC as well. The observed effects and their critical magnetic field dependence are interpreted as manifestation of the superconductivity and Meissner effect in metallic Pb nanoclusters existing in the ceramics. Their volume fraction and average size were estimated as 0.1-0.2% and 140-150 nm, respectively. The superconductivity related effects disappear after oxidizing annealing of the ceramics.

Crystal structure transformations induced by surface stresses in BaTiO3 and BaTiO3@SiO2 nanoparticles and ceramics

Lattice structure transformations in nanopowders of ferroelectric BaTiO3 and BaTiO3@SiO2 core-shell nanostructured ceramics were studied by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) at the temperatures 120–450 K and particle size of 300 and 500 nm. NMR spectra of all studied samples in the paraelectric phase are identical to the spectra in bulk material indicating their perfect perovskite structure without visible influence of particle surface. However, we have found that surface of particles essentially influence the ferroelectric phase transitions detected by both NMR and EPR techniques. The strongest changes as compared to bulk material were observed in BaTiO3@SiO2 core-shell ceramics. Thorough analysis of NMR spectra suggests that the orthorhombic-like symmetry phase coexists here with other polar phases up to the Curie temperature. Depending on temperature, its relative volume varies from 25% to 100%. We assume that the orthorhombic-like symmetry phase is stabilized by anisotropic components of surface stresses which increase also global stability of polar state in nanoceramics to the temperature in bulk material. We summarize our results in a phase diagram.

Easy axis switching in magnetite

The easy magnetic axis switching in magnetite is investigated. Magnetization data confirmed activation character of the process with activation energy of the same order as that of the Verwey transition, suggesting common origin. On the other hand this activation energy rises with pressure (up to 1.2GPa), unlike TV. The axis switching is clearly reflected in field dependence of resistivity and the direct structural data showed that it is simultaneous with the reorganization of structure. Thus, control of the structure can be possible with the application of magnetic field, as in shape memory materials. Finally, NMR showed that all, possibly decoupled entities: lattice distortion and charge and orbital orderings, change simultaneously while the axis switching occurs.

Electric field gradient in FeTiO3 by nuclear magnetic resonance and ab initio calculations

Temperature dependence of nuclear magnetic resonance (NMR) spectra of (47)Ti and (49)Ti in polycrystalline ilmenite FeTiO(3) was measured in the range from 5 to 300 K under an external magnetic field of 9.401 T. NMR spectra collected between 300 and 77 K exhibit a resolved quadrupole splitting. The electric field gradient (EFG) tensor was evaluated for Ti nuclei and the ratio of (47)Ti and (49)Ti nuclear quadrupole moments was refined during the fitting procedure. Below 77 K, the fine structure of quadrupole splitting disappears due to the enormous increase of anisotropy. As a counterpart, ab initio calculations were performed using full potential augmented plane waves + local orbitals. The calculated EFG tensors for Ti and Fe were compared to the experimental ones evaluated from NMR and the Mössbauer spectroscopy experiments.

Analysis of Cationic Impurity Impact on Hyperfine Interactions in Magnetite

The Al, Ga, Ti and Zn impurities were studied in high quality single crystal samples of magnetite (Fe3O4). The cases when the valence of the substitution ion differs from that of the original iron ion are of a particular interest. The measurement of nuclear magnetic resonance (NMR) of 57Fe was chosen as the experimental method for its sensitivity to Fe magnetic and electronic structure and to local ordering in the neighborhood of resonating nuclei. Local electronic structure and hence also the hyperfine interactions are affected by the presence of the substitution and thus resonance frequencies of nuclei in the vicinity of the substitution are shifted due to the modified hyperfine field, therefore satellite signals are observed in the NMR spectra. Temperature dependences of spectra above the Verwey transition were measured in a zero external magnetic field. Subsequently, the dependences of frequencies of main lines and satellite signals in the spectra on temperature were fitted with spin-wave model dependences and compared for different types of the substitution. Furthermore, a mean-field model was applied on the substituted magnetite system and calculated temperature dependences were confronted with the experimental data. The agreement of mean field model with the experimental temperature dependences of satellite resonances is better for those induced by the cationic substitutions at octahedral sites.

Anisotropy of hyperfine interactions as a tool for interpretation of NMR spectra in magnetic materials

Approach for interpretation of nuclear magnetic resonance (NMR) spectra in magnetic materials is presented, consisting in employing the anisotropy of hyperfine interaction. The anisotropic parts of hyperfine magnetic fields on (57)Fe nuclei are calculated ab initio for a model example of lithium ferrite and utilized to assign the experimental NMR spectral lines to iron sites in the crystal structure.

Hyperfine interactions in lutetium iron garnet

Nuclear Magnetic Resonance/Near Quadupole Resonace specra of Lu175 in lutetium iron garnet (LuIG) were measured in the range of 10–500MHz in zero external magnetic field at a temperature of 4.2K. Experimentally observed spectra had complicated structure and a theory was needed to interpret them. To this end we calculated the electronic structure of LuIG and from it the values of magnetic hyperfine fields and the components of electric-field-gradient tensor at the lutetium nuclei were determined. These parameters were used to simulate the theoretical spectra of Lu175 in LuIG. Simulated spectral lines of Lu175 at dodecahedral sublattice correspond reasonably well with the system of measured lines in the range of 10–200MHz. Several spectral lines in the range of 300–500MHz can be interpreted as the resonance of Lu175 at the octahedral sites that are nominally occupied by the ferric cations.