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Multiferroic bismuth ferrite (BiFeO3) nanopowders have been obtained in room temperature by mechanical synthesis. Depending on the post-synthesis processing the nanopowders have exhibited differences in the mean sizes, presence of amorphous layer and /or secondary phases. Extended magnetic study performed for fresh, annealed and hot-pressed nanopowders have revealed substantial improvement of the magnetic properties in the as-prepared powder.
This study reports on the synthesis of ball-like bismuth ferrite BiFeO3 nanoflowers by means of microwave assisted hydrothermal process and also on their composition and mechanism of growth. It turns out that the petals of the nanoflowers are compose d of the nanocrystals with the size about 35-39 nm whereas their thickness and size depends on the concentration of surfactants. The petals contain BiFeO3 phase and traces of Bi2O3 oxide and metallic Bi and Fe deposited mainly at their surface. Amounts of impurity phases are more pronounced in nanoflowers synthesized during short time, and become almost negligible for longer microwave processing. The nanoflowers contain also mixed Fe valence, with the Fe2+/Fe3+ ratio depending on the time of synthesis. The growth and shape of the nanoflowers result from the process of diffusion in the initial stages of hydrothermal reaction.
Multiferroic (Bi1-xLaxFeO3)0.5(PbTiO3)0.5 ceramics was prepared from mechanical synthesized nanopowders. The XRD studies revealed the tetragonal structure and the tetragonality decreased with La content. Dielectric response of the compounds was found to contain three anomalies: 1) relaxor-like behavior due to lattice disorder (below 300 K); 2) dielectric permittivity maxima at~400 K attributed to the presence of oxygen vacancies; 3) grain boundary effect above 475 K. The Curie point at ~500 K was observed for the compound with x=0.5. The composition near the morphotropic boundary: (Bi0.8La0.2FeO3)0.5(PbTiO3)0.5 shoved the highest remnant magnetization. The irreversible magnetic properties of the (Bi1-xLaxFeO3)0.5(PbTiO3)0.5 compounds can be explained in terms of disorder induced spin-glass behavior due to random substitution of La or Pb ions for Bi sites. A sharp step in magnetization about 250 K is caused by the A-site distortion associated with tilts of FeO6 octahedra leading to modification of Fe-O-Fe angles and of antiferromagnetic coupling between magnetic Fe3+ moments.
The ZFC and FC magnetization dependence on temperature was measured for BiFeO3 ceramics at the applied magnetic field up to H=10T in 2K-1000K range. The antiferromagnetic order was detected from the hysteresis loops below the Neel temperature TN=646K . In the low magnetic field range there is an anomaly in M(H), probably due to the field-induced transition from circular cycloid to the anharmonic cycloid. At high field limit we observe the field-induced transition to the homogeneous spin order. From the M(H) dependence we deduce that above the field Ha the spin cycloid becomes anharmonic which causes nonlinear magnetization, and above the field Hc the cycloid vanishes and the system again exhibits linear magnetization M(H). The anomalies in the electric properties, which are manifested within the 640K-680K range, coincide to the anomaly in the magnetization M(T) dependence, which occurs in the vicinity of TN. We propose to ascribe this coincidence to the critical behaviour of the chemical potential, related to the magnetic phase transition.
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