Temperature-Driven Transformation of the Crystal and Magnetic Structures of BiFe0.7Mn0.3O3 Ceramics.

The compound BiFe0.7Mn0.3O3 consisting at room temperature of coexistent anti-polar orthorhombic and polar rhombohedral phases has a metastable structural state, which has been studied by laboratory X-ray, synchrotron and neutron diffraction, magnetometry, differential thermal analysis, and differential scanning calorimetry. Thermal annealing of the sample at temperatures above the temperature-driven phase transition into the single phase rhombohedral structure (~700 K) causes an increase of the volume fraction of the rhombohedral phase at room temperature from ~10% up to ~30%, which is accompanied by the modification of the magnetic state, leading to strengthening of a ferromagnetic component. A strong external magnetic field (~5 T) applied to the sample notably changes its magnetic properties, as well as provides a reinforcement of the ferromagnetic component, thus leading to an interaction between two magnetic subsystems formed by the antiferromagnetic matrix with non-collinear alignment of magnetic moments and the nanoscale ferromagnetic clusters coexisting within it. The modification of the structural state and magnetic properties of the compounds and a correlation between different structural and magnetic phases are discussed focusing on the effect of thermal annealing and the impact of an external magnetic field.

Structural and Magnetic Phase Transitions in BiFe1 - xMnxO3 Solid Solution Driven by Temperature.

The crystal structure and magnetic state of the (1 − x)BiFeO3-(x)BiMnO3 solid solution has been analyzed by X-ray diffraction using lab-based and synchrotron radiation facilities, magnetization measurements, differential thermal analysis, and differential scanning calorimetry. Dopant concentration increases lead to the room-temperature structural transitions from the polar-active rhombohedral phase to the antipolar orthorhombic phase, and then to the monoclinic phase accompanied by the formation of two-phase regions consisting of the adjacent structural phases in the concentration ranges 0.25 < x1 < 0.30 and 0.50 ≤ x2 < 0.65, respectively. The accompanied changes in the magnetic structure refer to the magnetic transitions from the modulated antiferromagnetic structure to the non-colinear antiferromagnetic structure, and then to the orbitally ordered ferromagnetic structure. The compounds with a two-phase structural state at room temperature are characterized by irreversible temperature-driven structural transitions, which favor the stabilization of high-temperature structural phases. The magnetic structure of the compounds also exhibits an irreversible temperature-induced transition, resulting in an increase of the contribution from the magnetic phase associated with the high-temperature structural phase. The relationship between the structural parameters and the magnetic state of the compounds with a metastable structure is studied and discussed depending on the chemical composition and heating prehistory.

Creation and Magnetic Study of Ferrites with Magnetoplumbite Structure Multisubstituted by Al3+, Cr3+, Ga3+, and In3+ Cations.

Multisubstituted barium ferrites with a magnetoplumbite structure were obtained by the method of solid-phase reactions with ferritization and pre-firing. Three-charged, mainly diamagnetic cations Al3+, Cr3+, Ga3+, and In3+ were chosen as substituents for the Fe3+ iron cations, the proportion of which in solid solutions did not exceed 50%. The values of the configurational mixing entropy were calculated for all the compositions. A slight deviation of the chemical composition of the obtained solid solutions from the nominal value was established by the energy-dispersive X-ray spectroscopy method. The phase purity and values of the unit cell parameters were refined from X-ray scattering data using full-profile analysis in the Rietveld method. A non-monotonic behavior of the unit cell parameters as a function of the B-sub-lattice average ionic radius of the magnetoplumbite structure was found. A minimum unit cell volume of ~667.15 Å3 was found for the composition BaFe6.11Al1.56Cr2.17Ga2.16O19 with a B-sub-lattice average ionic radius of ~7.449 Å. The average crystallite size varied within 5.5-6.5 µm. The temperature and field dependencies of the magnetization have been measured. The values of the saturation magnetization, residual magnetization, hysteresis loop squareness, and coercivity at 50 K and 300 K were extracted from the experimental data. Using the Law of Approach to Saturation, the magnetic crystallographic anisotropy coefficient and anisotropy field were calculated. Multisubstitution leads to a significant decrease in such magnetic parameters as the magnetic ordering temperature and spontaneous magnetization at both temperatures. The maximum magnetic ordering temperature of ~297.7 K was found for the composition BaFe5.84Ga6.19O19 with a B-sub-lattice average ionic radius of ~7.586 Å in a field of 500 Oe. A maximum saturation magnetization of ~24.7 emu/g was found for the composition BaFe5.84Ga6.19O19 with a B-sub-lattice average ionic radius of ~7.586 Å at 50 K. A maximum hysteresis loop squareness of ~0.72 was found for the composition BaFe6.11Al1.56Cr2.17Ga2.16O19 with an average ionic radius of ~7.449 Å at 50 K. A maximum magnetic crystallographic anisotropy coefficient of ~2.09 × 105 Erg/g was found for the composition BaFe6.19Al1.25Cr1.57Ga1.74In1.26O19 with a B-sub-lattice average ionic radius of ~7.706 Å at 50 K. The frustrated magnetic state including the nano-sized clusters with an average diameter in the range of 50-200 nm was established from the results of measuring the ZFC and FC temperature magnetizations. The interpretation of the obtained experimental data is carried out taking into account the increased stability of high-entropy phases and regular changes in the intensity of the Fe3+(Al3+, Cr3+, Ga3+, In3+)-O2--Fe3+(Al3+, Cr3+, Ga3+, In3+) indirect superexchange interactions as a result of magnetic dilution of the iron sub-lattice in the magnetoplumbite structure.

Crystal and Magnetic Structure Transitions in BiMnO3+δ Ceramics Driven by Cation Vacancies and Temperature.

The crystal structure of BiMnO3+δ ceramics has been studied as a function of nominal oxygen excess and temperature using synchrotron and neutron powder diffraction, magnetometry and differential scanning calorimetry. Increase in oxygen excess leads to the structural transformations from the monoclinic structure (C2/c) to another monoclinic (P21/c), and then to the orthorhombic (Pnma) structure through the two-phase regions. The sequence of the structural transformations is accompanied by a modification of the orbital ordering followed by its disruption. Modification of the orbital order leads to a rearrangement of the magnetic structure of the compounds from the long-range ferromagnetic to a mixed magnetic state with antiferromagnetic clusters coexistent in a ferromagnetic matrix followed by a frustration of the long-range magnetic order. Temperature increase causes the structural transition to the nonpolar orthorhombic phase regardless of the structural state at room temperature; the orbital order is destroyed in compounds BiMnO3+δ (δ ≤ 0.14) at temperatures above 470 °C.

Peculiarities of the Crystal Structure Evolution of BiFeO3-BaTiO3 Ceramics across Structural Phase Transitions.

Evolution of the crystal structure of ceramics BiFeO3-BaTiO3 across the morphotropic phase boundary was analyzed using the results of macroscopic measuring techniques such as X-ray diffraction, differential scanning calorimetry, and differential thermal analysis, as well as the data obtained by local scale methods of scanning probe microscopy. The obtained results allowed to specify the concentration and temperature regions of the single phase and phase coexistent regions as well as to clarify a modification of the structural parameters across the rhombohedral-cubic phase boundary. The structural data show unexpected strengthening of structural distortion specific for the rhombohedral phase, which occurs upon dopant concentration and temperature-driven phase transitions to the cubic phase. The obtained results point to the non-monotonous character of the phase evolution, which is specific for metastable phases. The compounds with metastable structural state are characterized by enhanced sensitivity to external stimuli, which significantly expands the perspectives of their particular use.