Репозиторий Университета

The local crystal/magnetic structures of the SrFe12−xInxO19 solid solutions (x = 0.1; 0.3; 0.6 and 1.2) were investigated using neutron powder diffraction. The measurements of the electric polarization for all investigated samples were carried out as a function of the external electric field. The presence of the ferroelectric and ferromagnetic ordering (dual ferroic ordering) in the SrFe12−xInxO19 hexaferrites at 300 K was found. This appearance contradicts to the conventional opinion describing their crystal structure (centrosymmetric space group P63/mmc (No. 194)). The reason for the existence of a spontaneous polarization (nonzero dipole moment) in the SrFe12−xInxO19 hexaferrites continues controversial. The crystal structure of the hexaferrites was considered both the centrosymmetric P63/mmc and non-centrosymmetric P63mc space groups. This fact made it possible to find a connection between the emerging dipole moment and not equal distortions of the neighbor oxygen polyhedral. The nature description of the nonzero dipole moment formation in a quasi-centrosymmetrical system of the In-substituted SrFe12−xInxO19 hexaferrites was presented based on the neutron diffraction data.

The local crystal/magnetic structures of the SrFe12−xInxO19 solid solutions (x = 0.1; 0.3; 0.6 and 1.2) were investigated using neutron powder diffraction. The measurements of the electric polarization for all investigated samples were carried out as a function of the external electric field. The presence of the ferroelectric and ferromagnetic ordering (dual ferroic ordering) in the SrFe12−xInxO19 hexaferrites at 300 K was found. This appearance contradicts to the conventional opinion describing their crystal structure (centrosymmetric space group P63/mmc (No. 194)). The reason for the existence of a spontaneous polarization (nonzero dipole moment) in the SrFe12−xInxO19 hexaferrites continues controversial. The crystal structure of the hexaferrites was considered both the centrosymmetric P63/mmc and non-centrosymmetric P63mc space groups. This fact made it possible to find a connection between the emerging dipole moment and not equal distortions of the neighbor oxygen polyhedral. The nature description of the nonzero dipole moment formation in a quasi-centrosymmetrical system of the In-substituted SrFe12−xInxO19 hexaferrites was presented based on the neutron diffraction data.

A correlation between the crystal structure and magnetic properties of system (1-x)BiFeO3 – (x)BaTiO3 with compounds across the morphotropic phase boundary was studied using X-ray and neutron diffraction, magnetometry, and Mössbauer spectroscopy measurements. Increase in the dopants content leads to the structural transition from the rhombohedral phase to the cubic phase via a formation of the two-phase region (0.2 < x < 0.33), wherein the magnetic structure changes from the modulated G-type antiferromagnetic to the collinear antiferromagnetic via a stabilization of the non-collinear antiferromagnetic phase with non-zero remanent magnetization. The value of magnetic moment calculated per iron ion based on the Mössbauer and neutron diffraction data decreases from m ≈ 4.4 μB for the compound with x = 0.25 to m = 3.2 μB for the compound with x = 0.35 testifying a dominance of 3 + oxidation state of the iron ions. Increase in the amount of the cubic phase leads to a reduction in the remanent magnetization from 0.02 emu/g for the compounds with the dominant rhombohedral phase (x < 0.27) down to about 0.001 emu/g for the compounds with dominant cubic structure (x ≥ 0.27). Rapid decrease in the remanent magnetization observed in the compounds across the phase coexistence region points at no direct correlation between the type of structural distortion and non-zero remanent magnetization, while the oxygen octahedra tilting is the key factor determining the presence of non-zero remanent magnetization.

© 2020 Elsevier Ltd Neutron diffraction and magnetization measurements of the Bi0.85Ca0.15Fe1-xMnxO3+δ (x = 0.4, 0.5) compounds have been performed at room and low temperatures to disclose the effect of the mixed-valence Mn substitution on the magnetic structure and properties of the Ca-doped bismuth ferrites near the polar/nonpolar phase boundary. It has been confirmed that the Mn substitution results in the filling of anion vacancies produced by the aliovalent replacement of Bi3+ by Ca2+. The Bi0.85Ca0.15Fe0.6Mn0.4O3+δ compound has the acentric structure specific to the pure BiFeO3 (space group R3c) and displays a G-type antiferromagnetic order at room temperature (m300K = 1.35(2) μB). The magnetic moments localized on the Fe/Mn ions are directed along the polar axis. The spin-reorientation transition from the c to a axis takes place with decreasing temperature. An increase in the Mn concentration gives rise to the polar → nonpolar (R3c → Pnma) structural phase transformation. The nonpolar (x = 0.5) compound has a G-type antiferromagnet structure (TN = 210 K) with spins aligned along the orthorhombic b axis. The low-temperature magnetic moments (m5K = 2.67(2) μB and m5K = 1.80(3) μB for the samples with x = 0.4 and x = 0.5, respectively) are considerably smaller than those predicted for complete spin ordering of the interacting ions of Fe3+, Mn3+ and Mn4+ (>4 μB). While the neutron diffraction measurements reveal no contribution associated with a long-range ferromagnetic order at T = 5 K, a significant increase in the magnetization of the samples, suggesting the formation of a glassy phase, is observed with decreasing temperature.

© 2020 Elsevier B.V. The room- and low-temperature neutron diffraction measurements of the Bi0.9Ca0.1Fe0.6Mn0.4O3+δ compound have been carried out to disclose the influence of Mn substitution on the multiferroic properties of the low-doped Bi1−xCaxFeO3−x/2 perovskites combining ferroelectric and weak ferromagnetic behavior. It has been proven that the material under study retains a polar R3c structure specific to the parent Bi0.9Ca0.1FeO2.95. The Mn doping results in the elimination of oxygen vacancies giving rise to the increase in spontaneous electric polarization. The chemical modification stabilizes the collinear antiferromagnetic structure at room temperature. The reorientation of the antiferromagnetic vector from the c to a axis takes place with decreasing temperature. Reflecting the competitive character of the superexchange interactions between Fe3+, Mn3+ and Mn4+, the coexistence of ferromagnetic glassy and antiferromagnetic long-range-ordered phases is observed at low temperatures.

© 2019 Elsevier B.V. Herein, we report on the crystal structure, magnetic and local ferroelectric properties of the Bi1−xCaxFe1−xTixO3 and Bi1−xCaxFe1−x/2Nbx/2O3 perovskites prepared by a solid state reaction method. It has been found that the Ca2+/Nb5+-containing series is characterized by a narrower concentration range (x ≤ 0.2) over which the acentric R3c structure specific to the pure BiFeO3 can be stabilized. The compositional variation in the critical concentration defining the polar/nonpolar (R3c/Pnma) phase boundary can be understood as related to the chemical modification-induced changes in the lattice spacing diminishing the stability of the a−a−a− tilting in favor of the a−b+a− one. Both the Ca2+/Ti4+ and Ca2+/Nb5+ substitutions ensure the suppression of a cycloidal antiferromagnetic order, thus leading to the formation of a weak ferromagnetic polar state. While this effect is proven to be associated with a composition-driven reduction in polar displacements, lattice defects are supposed to contribute to the instability of the cycloidal spin arrangement.

© 2019 Elsevier B.V. The structural parameters of the Bi0.85AE0.15Fe0.85Ti0.15O3 (AE = Ca and Ba) multiferroics have been determined using variable temperature neutron powder diffraction. The compounds adopt the polar rhombohedral R3c structure near room temperature and undergo phase transitions into either the nonpolar orthorhombic Pnma (AE = Ca) or cubic Pm3-m (AE = Ba) structures on heating. In the ferroelectric phase, a temperature-driven lattice expansion is accompanied by both a diminishing of the off-center ionic displacements (thus resulting in a decrease in the spontaneous electric polarization) and a reduction in the magnitude of the antiphase oxygen octahedra tilting. Being largely different for the materials under study, the latter parameter is supposed to specify the dissimilarity in their magnetic properties.

© 2019 Elsevier B.V. Crystal structure of the Bi1-xBaxFe1-xTixO3 ceramics across the phase boundary region between the polar rhombohedral and pseudo-cubic phases has been investigated by means of X-ray and neutron diffraction, scanning electron microscopy and differential scanning calorimetry techniques. The structural measurements have revealed a decrease in the rhombohedral distortions upon increase in the dopant content followed by the stabilization of the pseudo-cubic phase at x ≥ 0.20. While temperature increase gives rise to the similar pattern of structural changes for the lightly-doped samples, an unpredictable temperature-driven strengthening of the rhombohedral distortions has been found for the compounds belonging to the phase boundary region. The study specifies the peculiarities of the temperature-driven evolution of the crystal structure depending on the structural state of the compounds at room temperature.