Multivariate pressure effects on an electron hopping process in ferroelectric KTa<Subscript>1−x</Subscript>Nb<Subscript>x</Subscript>O<Subscript>3</Subscript>

The effect induced by the presence of a polaron related relaxation process on the dielectric properties of a ferroelectric KTa_1?x Nb _x O₃ (KTN) crystal was investigated (10^-2?10⁶ Hz, at 300?375 K) using broadband dielectric spectroscopy. Characterization of the process using just the standard frequency domain dielectric parameters can nonetheless provide penetrating insight into its nature and origins. The three parameters, namely: relaxation time (τ), Cole-Cole loss broadening (α), and dielectric strength (Δ?) provide each one in its own way, much useful and often overlooked information. The Activation Energy along with the Meyer-Neldel dependance, both extracted from τ serve to illuminate the dynamic properties. At the same time, α and especially the combined α(lnτ) relationship, expose the fractal structure of the underlying landscape. Finally, the static parameter Δ?, enables quantification of the dipolar correlations. Hydrostatic pressure (up to 7.5 kbar) was applied to gently perturb the system and observe the outcome on all of the various parameters. This additional degree of freedom allows for a much more comprehensive exploration of the phase space behavior of the system.     

Soft polar modes and phase states of Ca<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>x</Subscript>TiO<Subscript>3</Subscript> solid solutions

Dielectric spectra ?′(ν) and ?″(ν) of Ca_1?xPb_xTiO₃ ceramic samples (x=0, 0.15, 0.2, 0.4) have been studied in the frequency range ν=7–1000 cm^?1 at temperatures from 5 to 300 K using IR Fourier spectroscopy and submillimeter-range techniques. In the low-frequency range, polar phonons were established to undergo temperature-induced evolution. The results obtained are discussed in terms of the Landau theory of second-order phase transitions for coupled soft modes. The existence of one (or several) phase state(s) in the intermediate concentration region of Ca_1?xPb_xTiO₃ solid solutions is tentatively assumed.     

Heat capacity of the Pb<Subscript>5</Subscript>(Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>x</Subscript>)<Subscript>3</Subscript>O<Subscript>11</Subscript> ferroelectric system

The temperature dependences of the molar heat capacity at constant pressure, C_p, of Pb₅(Ge_1?xSi_x)₃O₁₁ crystals with x=0, 0.39, and 0.45 in the range 5–300 K, as well as of their permittivity, dielectric losses, and the pyroelectric effect, have been measured. Experimental data on the temperature behavior of the heat capacity are presented in the form of a sum of two Debye and one Einstein terms, C_p(T)=0.405C_D1(Θ_D1=160 K, T)+0.53C_D2(Θ_D2=750 K, T)+0.046C_E(Θ_E=47 K, T). Besides a peak in the region of the ferroelectric Curie point T_c=450 K for crystals with x=0, the temperature dependences of the heat capacity did not reveal any other pronounced anomalies.     

Rotatable anisotropy of epitaxial Fe<Subscript>1−x</Subscript>Ga<Subscript>x</Subscript> thin films

We show by a combined magnetic force microscopy and synchrotron radiation spectroscopy study that stripe-like patterned magnetic domains are present in Fe_1?x Ga _x thin films. These stripes, whose origin is attributed to an out-of-plane magnetic component, can be rotated by an external magnetic field.     

Transformation of dielectric properties and appearance of relaxation behavior in Pb<Subscript>5</Subscript>(Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>x</Subscript>)<Subscript>3</Subscript>O<Subscript>11</Subscript> crystals

The special features of the dielectric properties and conduction of ferroelectric crystals of Pb₅(Ge_1?xSi_x)₃O₁₁ (0 ≤ x ≤ 0.67) solid solutions were studied. Permittivity anomalies close to the temperatures T₁ ≈ 260 K and T₂ ≈ 130 K, the appearance of relaxator behavior at x > 0.35, and critical behavior of the concentration dependences of dielectric and pyroelectric characteristics at x₁ = 0.35 and x₂ = 0.60 were observed and studied. These phenomena were found to be related to the dynamics of charge localization on defects with activation energies of U_a1 ≈ 0.6 eV and U_a2 ≈ 0.23 eV. Relaxator behavior appears when the Curie point lies in the temperature region of thermal charge localization. The concentration dependence features at x₁ and x₂ are explained by the coincidence of the Curie point and the centers of the temperature regions of charge localization on the U_a1 and U_a2 defect levels, respectively.     

Specifics of the Electrical Properties of Composite Solid Oxide Membranes Based on SrTi<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3–δ</Subscript>

The electrical properties of dual-phase fluorite-pervoskite oxide systems based on strontium titanate- ferrite (SrTi_0.5Fe_0.5O_3–δ) are studied. We find that the oxygen ionic and ambipolar conductivities of strontium titanate-ferrite can be considerably improved by introducing the fluorite phase Ce_0.8(Sm_0.8Sr_0.2)_0.2O_2–δ. This is advantageous considering the prospects of applying these types of composite materials in different electrochemical devices, e.g., as membrane materials in electrochemical converters for the production of hydrogen and syngas and anode materials in solid oxide fuel cells.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Orbital phase transition in Pr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript>

The phenomenological theory of phase transition in Pr_0.6 Ca_0.4 MnO₃ manganite is developed. It is shown that this is the orbital phase transition and that the two electronic states of the manganese ion, which are discussed in the literature, result from two different types of condensation of the same orbital order parameter. Thus, the manganese ions in Pr_1?xCa_x MnO₃ manganites with 0.3≤_x≤0.5 may be in either of the two electronic states, depending on the thermodynamic parameters.     

AC and DC properties of M-type SrCo<Subscript>x</Subscript>Ti<Subscript>x</Subscript>Fe<Subscript>(12−2x)</Subscript>O<Subscript>19</Subscript> hexagonal ferrite

Microwave characterization of SrCo _x Ti _x Fe_(12?2x)O₁₉ (x = 0.0, 0.2, 0.3, 0.5, 0.6, 0.7, 1.0) ferrites has been studied as a function of frequency, substitution and thickness, and static electrical current density-electric field characteristics have been investigated as a function of substitution. Microwave characteristics have been measured using power meter in the rectangular slotted waveguide and current density is measured using electrometer. The microwave absorption is evaluated using the standard available model. The results depict ?11.57 dB reflection loss at 10.38 GHz in composition x = 0.6. The electrical current density decreases at lower substitution and increases at higher substitution. The substitution of Co²⁺ and Ti⁴⁺ ions causes enhancement of electromagnetic and static electrical properties.     

Thermal expansion of (Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript>x</Subscript>)<Subscript>3</Subscript>Ru<Subscript>2</Subscript>O<Subscript>7</Subscript> single crystals at low temperatures

For single-crystal samples of the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates, the temperature dependence of the thermal expansion coefficient α(T)) is measured in the range 4.2–80 K. The effect of magnetic fields H ≤ 3.5 T on thermal expansion is analyzed. It is found that the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates exhibit an anomalous (negative) thermal expansion coefficient in the temperature range T ≤ 18 K. The position and width of the anomaly revealed in the temperature dependence of the thermal expansion coefficient α(T)) depend substantially on the magnetic field. The origin of the thermal expansion anomaly in ruthenates, the correlation of this anomaly with the stability of the crystal lattice, and the common nature of the anomalies in the thermal properties of ruthenates and high-temperature superconductors are discussed.     

Mössbauer studies of stoichiometry of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: characterization of nanoparticles for biomedical applications

The iron oxide Fe₃O₄, the mineral magnetite sometimes called ferrosoferric oxide, is notoriousy non-stoichiometric even in bulk form so its formula may be written Fe_3?δO₄. In nanoparticle form, where it has applications in medicine and information technology, it is even more susceptible to oxidation. In this paper we report synthesis and studies of superparamagnetic Fe₃O₄ nanoparticles with controlled diameters of 5.3, 10.6 and 11.9 nm. In room temperature spectra, departures from stoichiometry δ of up to 0.02 were estimated from the relative amounts of Fe ³⁺/ Fe ²⁺ and from their isomer shifts. This cannot be used for very small particles of diameter 10.6 nm and less as they are superparamagnetic at room temperature and do not show hyperfine splitting owing to fast relaxation. Such particles have promise for use in enhancing MRI signals. The magnetic spectrum is restored by the application of a relatively small magnetic field (10 kG). As the temperature is lowered the relaxation slows down and 6-line magnetic hyperfine patterns appear below a blocking temperature T_B. The values of T_B obtained are lower than those of many other researchers reported in the literature, suggesting that our particles are less affected by magnetic interactions between them. At low temperatures all the spectra are similar and closely resemble that of bulk Fe₃O₄ confirming that departures from stoichiometry are small.     

Magnetorefractive effect in (Co<Subscript>50</Subscript>Fe<Subscript>50</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> granular films

The reflectivity spectra and the magnetorefractive effect (MRE) of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x metal-dielectric granular films (0.07<x<0.52) are analyzed in the IR spectral range λ=2.5–25 µm. It is revealed that the specific features observed in the spectra at λ≈8.5 and 20 µm are associated with the excitation of phonon modes in the dielectric matrix. The magnetorefractive effect in the films is observed below the percolation thresh-old only in p-polarized light and above the percolation threshold for both the p and s polarizations. It is demonstrated that the optical properties of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x films in the IR spectral range, to a first approximation, can be interpreted in the framework of the effective-medium theory and the magnetorefractive effect can be explained in terms of the modified Hagen-Rubens relation.     

Calorimetry of (1 − <Emphasis Type="Italic">x</Emphasis>)BaTiO<Subscript>3</Subscript>-<Emphasis Type="Italic">x</Emphasis>Ba(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> solid solutions

Phase transitions in ceramic samples of (1 ? x)BaTiO₃-xBa(Mg_1/3Nb_2/3)O₃ solid solutions were studied by differential scanning calorimetry for x = 0, 0.01, 0.02, and 0.03 in the temperature ranges 255–290 K and 310–410 K. The experimental data obtained were used to derive the thermodynamic parameters of the phase transitions occurring at T _c ≈ 400?300 K and T ₁ ≈ 290?300 K and construct the concentration phase diagram.     

Structure and magnetic properties of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3+δ</Subscript> compounds

The structural and magnetic properties of La_1?x Ca_xMnO_3+δ (x = 0.01–0.10) compounds with a high superstoichiometric oxygen content (0.01 < δ < 0.07) are investigated. It is demonstrated that all the studied compounds are characterized by a magnetically inhomogeneous state at temperatures below 280 K. It is found that the compound with the calcium content x = 0.05 differs substantially in structure and superstoichiometric oxygen content from the other compounds in the system under investigation. The revealed difference in properties of the compounds can be associated with the fact that a specific state or a specific phase is formed in this system at the calcium content x = 0.05.     

Spectroscopic study of magnetic phase transitions in Nd<Subscript>x</Subscript>Gd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Magnetic ordering and spin reorientation in iron borates Nd_xGd_1?xFe₃(BO₃)₄ (x = 0.01, 0.04, 0.25, 1.0) are studied using a rare-earth spectroscopic probe.     

Structural phase transition in (1−<Emphasis Type="Italic">x</Emphasis>)SrTiO<Subscript>3</Subscript>+<Emphasis Type="Italic">x</Emphasis>SrMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> solid solutions

The temperature dependences of the shear modulus and internal friction in ceramic samples of (1?x)SrTiO₃+xSrMg_1/3Nb_2/3O₃ solid solutions were studied by the torsional vibration method in the range 80–300 K. It was established that the temperature T _a of the O _h ¹ -D _4h ¹⁸ structural phase transition in these solid solutions increases with increasing x, although the lattice constant also increases. A discussion is presented of the contributions to the T _a (x) dependence due to a change in the volume and changes caused by the presence of a second solid-solution component (the impurity contribution). It is also shown that the defect-induced relaxation revealed earlier in a study of the dielectric properties of these materials manifests itself in internal friction peaks.     

Heat capacity study of double perovskite-like compounds BaTi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript>x</Subscript>O<Subscript>3</Subscript>

The temperature dependence of the heat capacity of two compositions in the solid solution system BaTi_1?xZr_xO₃ (x = 0.25, 0.35) was measured using adiabatic calorimetry. In the T-x phase diagram, these compounds occupy positions near the crossover from conventional ferroelectric behavior to the relaxor state. Both compounds reveal diffuse heat capacity anomalies: two anomalies in the temperature ranges 250–350 and 150–200 K at x = 0.35 and one anomaly within the range ～150–320 K at x = 0.25. The results obtained are discussed together with structural and dielectric measurements.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

Phase transitions and magnetoelectric coupling in BiFe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> multiferroics

Multiferroic BiFe_1?xZn _x O₃ ceramics were prepared by solution combustion method. Their structure, magnetoelectric, dielectric, magnetic, thermal characteristics were studied. The magnetic M(T) and heat capacity C _p (T) measurements demonstrate an antiferromagnetic to paramagnetic phase transition (T _N ) around 635 K. The anomaly on the temperature dependence of the dielectric constant near T _N was observed, which could be induced by the magnetoelectric coupling between electric and magnetic ordering. The magnetoelectric behavior was also confirmed by the linear relation between Δε and M², which is in the agreement of the Ginzburg-Landau theory for the second-order phase transition.     

Preparation and investigation of weakly ferromagnetic Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>x</Subscript>BO<Subscript>3</Subscript> single crystals

Single crystals of iron borate FeBO₃, with part of the iron ions substituted for by Ga diamagnetic ions, were grown through spontaneous crystallization from a melt solution. The chemical composition of the crystals thus prepared, Fe_1?xGa_xBO₃ (x=0, 0.15, 0.25, 0.3), was derived from x-ray microprobe analysis data. Mössbauer spectroscopy and magnetometry were employed to determine the hyperfine interaction parameters (effective magnetic fields at the iron nucleus sites, quadrupole splittings, isomer chemical shifts) and Néel temperatures for these crystals and to derive their temperature behavior.