Ion-electron transfer in solid solutions Rb2 ? 2xFe2 ? xPxO4

The rubidium monoferrite RbFeO₂-based solid solutions with the composition Rb_{2 − 2x} Fe_{2 − x} P _x O₄ have been synthesized, and their crystal structure and the temperature and concentration dependences of the total and electron conductivities have been studied. The introduction of P⁵⁺ ions has been found to sharply decrease the electron conductivity that prevails in pure rubidium monoferrite and, at the same time, to increase the ionic conductivity. The latter becomes dominant as the phosphorus concentration increases. The maximum rubidium-cation conductivity of the materials under study is ∼3 × 10⁻² S/cm at 300°C and ∼3 × 10⁻¹ S/cm at 700°C. The results have been compared with the previously obtained data for similar solid solutions based on rubidium monogallate and monoaluminate.     

M?ssbauer study of compounds of Cu3 ? xFexSnS4 and Cu2Fe1 ?xZnxSnS4 systems

A M?ssbauer study of the structural and charge states of ⁵⁷Fe and ¹¹⁹Sn atoms in the compounds of Cu_{3 −x} Fe _x SnS₄ and Cu₂Fe_{1 − x} Zn _x SnS₄ systems was performed. It was shown that the iron atoms in the compounds of both systems were in the divalent and trivalent states occupying the tetrahedral positions of the structure. The character of the changes of the degree of covalency of the Fe²⁺-S, Fe³⁺-S and Sn⁴⁺-S bonds during the isomorphic substitution in the systems was established.     

Thermal expansion of (Ba1 ? xLax)Ti1 ? x/4O3 solid solutions

Deformation and the thermal expansion coefficient of ceramic samples of (Ba_{1 − x} La _x )Ti_{1 − x/4}O₃ solid solutions (x = 0, 0.026, 0.036, 0.054) were studied in the temperature range 120–700 K. Based on an analysis of the data obtained, the temperature-composition phase diagram is refined, and the temperature dependence of the polarization is calculated. The results are discussed in combination with the dielectric measurement data. Original Russian Text ? M.V. Gorev, I.N. Flerov, Ph. Sciau, S. Guillemet-Fritsch, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 4, pp. 746–752.     

Novel synthesis of NixZn1?xFe2O4 (0?≤?x?≤?1) nanoparticles and their dielectric properties

Nanocrystalline Ni _x Zn_1−x Fe₂O₄ (0 ≤ x ≤ 1) ferrite powders with average particle size 15–20 nm have been successfully prepared at a very low temperature (180 °C) by a novel auto combustion process using citric acid and ethylenediamine as a coordinating agent and bridging ligand, respectively. Phase purity of the solid solutions has been confirmed by X-ray diffraction. Morphological characterizations of the prepared samples were performed by high resolution transmission electron and field emission scanning electron microscopy. Extensive Fourier transformed infrared spectroscopic characterization has been carried out to identify the plausible mechanism of the synthesis process. Composition-dependent electrical properties (resistivity and dielectric constant) of the synthesized solid solution have been investigated. Interestingly, a non-linear variation of dielectric permittivity with respect to composition has been observed. The room temperature electrical resistivity as well as the dielectric permittivity of Ni_0.5Zn_0.5Fe₂O₄ was found to decrease with the decrease of particle size.     

Optical characterization in Pb(Zr1?xTix)1?yNbyO3 ferroelectric ceramic system

In this work, visible photoluminescence was observed at room temperature in a sintered Pb(Zr_1-xTi_x)_1-y Nb_yO₃\mathrm{Pb}(\mathrm{Zr}_{1-x}\mathrm{Ti}_{x})_{1-y} \mathrm{Nb}_{y}\mathrm{O}_{3} perovskite-type structure system, doped with Nb using the next excitation bands 325, 373 and 457 nm. The intensity and energy of such emissions have been studied by changing the Nb concentration (0<y<0.01) and the Ti content (x), with x=0.20,0.40,0.53,0.60 and 0.80, on both sides of the morphotropic phase boundary (MPB) zone. The principal bands become visible at energies of 1.73, 2.56 and 3.35 eV. The results reveal the role of the Nb⁵⁺ ion substitutions by Zr⁴⁺ or Ti⁴⁺ ions and the symmetry presented in the rhombohedral or tetragonal side of the MPB. Raman spectra which are similar for compositions: 20/80, 40/60 and 53/47 (tetragonal phases) show nine bands, centered around 137, 194, 269, 331, 434, 550, 612, 712 and 750 cm⁻¹. The spectra for samples 60/40 and 80/20, rhombohedral phase, show significant differences, only six bands appear, centered around 124, 209, 234, 330, 549 and 682 cm⁻¹. In addition, optical absorption spectroscopy, structural and micro-structural measurements were carried out by using Uv-vis spectroscopy, X-ray diffraction and scanning electron microscopy techniques, respectively. The experimental results of band gap energy, e.g., in our samples are in accordance with the findings by J. Baedi et al. in the calculations of band structure, energy gap and density of states for different phases of Pb(Zr_1−x Ti _x )O₃ using density functional theory (DFT).     

Phase formation in near-morphotropic region of the PbZr1 ? xTixO3 system, structural defects, and electromechanical properties of the solid solutions

Ceramics of PbZr_{1 − x} Ti _x O₃ solid solutions were systematically studied in the range 0.37 ≤ x ≤ 0.57. The x-T phase diagram (T = 25°C) is constructed containing in single-phase regions isosymmetric states characterized by different concentration dependences of the structural and electrophysical parameters. There are also regions where these states coexist, with their unit cell volume remaining unchanged. The existence of these states is interpreted in terms of the real (defect) structure of the ceramics. Several reasons are indicated that are responsible for the appearance of the phase states and related to the crystallochemical peculiarities of the solid solutions: the alternate valence of titanium ions; the infinitely adaptive structure of titanium dioxide; and the formation, ordering, and rotation of the planes of crystallographic shear. It is shown that the transition from the rhombohedral to tetragonal phase occurs indirectly, through two intermediate phases with lower symmetry whose appearance is favored by the defects in the solid solutions. Original Russian Text ? L.A. Reznichenko, L.A. Shilkina, O.N. Razumovskaya, E.A. Yaroslavtseva, S.I. Dudkina, O.A. Demchenko, Yu.I. Yurasov, A.A. Esis, I.N. Andryushina, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 5, pp. 958–965.     

Thermal conductivity of single crystals of Ca1 ? xErxF2 + x and Ca1 ? xTmxF2 + x solid solutions

The thermal conductivity of single crystals of Ca_{1 − x} Er _x F_{2 + x} (x = 0.01, 0.05, 0.07, and 0.10) and Ca_{1 − x} Tm _x F_{2 + x} (x = 0.02, 0.04, and 0.06) solid solutions is studied in the temperature ranges 50–300 and 298–673 K. With increasing content of rare-earth elements, the behavior of thermal conductivity in these solid solutions changes from the characteristic of defect single crystals to glasslike. The concentration dependences of thermal conductivity for the two systems differ insignificantly.     

Low-field magnetization of ludwigites Co3O2BO3 and Co3 ? xFexO2BO3 (x ≈ 0.14)

Ludwigite single crystals of compositions Co₃O₂BO₃ and Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) have been synthesized. The crystal structure is investigated at room temperature, and the magnetization is studied in the temperature range T = 4.2–100 K in magnetic fields of up to 600 Oe. The orthorhombic symmetry is revealed, and the unit cell parameters are determined. A number of features are established for the temperature dependence of the magnetization. In unsubstituted Co₃O₂BO₃, two magnetic transitions are found at T _C1 = 43 K and T _C2 = 15 K. At temperatures below 40 K, spin-glass state is revealed. Substitution of iron ions for cobalt ions leads to a noticeable shift in the magnetic transitions toward the high-temperature range: T _C1 = 83 K and T _C2 = 74 K. A ferromagnetic ordering of the P type is found in the Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) compound. Original Russian Text ? N.V. Kazak, N.B. Ivanova, V.V. Rudenko, A.D. Vasil’ev, D.A. Velikanov, S.G. Ovchinnikov, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 5, pp. 916–919.     

Studying the local structural features of Zn2 ? 2xCd2xV2O7 by NMR and IR spectroscopy

The local structure of pyroanion groups in the incommensurate phase X-Zn_{2 − 2x} Cd_2x V₂O₇ (0.11 ≤ x ≤ 0.48) with a zero volumetric expansion coefficient is studied. Comparative analysis of IR and NMR spectra of samples in the X-phase and of ZnCdV₂O₇ revealed that vanadium atoms have a similar structural and an identical charge environment. Additional bands in the IR spectra of the X-phase in the range of end vibrations are due to the influence of the cation sublattice.     

Electronic and thermodynamic properties of α-Pu2O3

Based on density functional theory+U$\text{density functional theory}+U$ calculations and the quasi-annealing simulation method, we obtain the ground electronic state for α-Pu₂O₃ and present its phonon dispersion curves as well as various thermodynamic properties, which have seldom been theoretically studied because of the huge unit cell. We find that the Pu–O chemical bonding is weaker in α-Pu₂O₃ than in fluorite PuO₂, and subsequently a frequency gap appears between oxygen and plutonium vibration density of states. Based on the calculated Helmholtz free energies at different temperatures, we further study the reaction energies for Pu oxidation, PuO₂ reduction, and transformation between PuO₂ and α-Pu₂O₃. Our reaction energy results are in agreements with available experiment. And it is revealed that high temperature and insufficient oxygen environment are in favor of the formation of α-Pu₂O₃.     

Electrical and magnetic properties of [(CoFeZr)x(Al2O3)1 ? x/(α-SiH)]n multilayer structures

The concentration dependences of the electrical resistivity and complex permeability of [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n multilayer structures and (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites have been studied. It has been established that introduction of a semiconductor interlayer into the (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites substantially decreases the electrical resistivity of [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n multilayer structures. The concentration dependences of the real and imaginary parts of the complex permeability of the [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n nanomultilayer structures substantially differ from those of the (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} composites. The real part of the complex permeability of the [“(Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} ”/“α-Si: H”] _n nanomultilayer structures follows the curve with a minimum near the percolation threshold of the composite, and the imaginary part smoothly decreases as the ferromagnetic phase concentration increases. The results obtained are explained by the increase in the bifurcation temperature due to the conduction electrons of the semiconductor interlayer, which favor magnetic ordering of ferromagnetic grains.     

Thermoelectric properties of p-Bi2 ? xSbxTe3 solid solutions under pressure

This paper reports on a study of the Seebeck coefficient and power factor κ of p-Bi_{2 − x} Sb _x Te₃ solid solutions with different contents of antimony atoms in the bismuth sublattice for x = 0, 1.4, 1.5, and 1.6 under variation of pressure of up to 15 GPa. The magnitude of κ has been found to grow nonmonotonically within the pressure region of 2–4 GPa. The effective mass of the density of states m/m ₀ and the mobility μ₀ have been calculated with due account of degeneracy within the parabolic model of the energy spectrum assuming isotropic charge carrier scattering. It has been shown that application of pressure brings about a decrease of the effective mass m/m ₀ and an increase of carrier mobility. The power factor κ of the p-Bi_0.6Sb_1.4Te₃ composition exhibits at the pressure P ≈ 4 GPa the largest increase of the power factor κ as a result of a weak decrease of the effective mass m/m ₀ and an increase of carrier mobility as compared to the other solid solution compositions. The specific feature of the variation of the power factor κ with a change of the pressure in bismuth telluride near P ≈ 3 GPa, which is accompanied by formation of a knee in the m/m ₀ vs. P dependence, can be assigned to an electronic topological transition.     

Electronic excitations in ZnWO4 and ZnxNi1?xWO4 (x = 0.1 ? 0.9) using VUV synchrotron radiation

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO₄ as well as the Zn _x Ni_1−x WO₄ solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO₆]⁶⁻ anions, becomes modulated by the optical absorption of Ni²⁺ ions in the Zn _x Ni_1−x WO₄ solid solutions; and (ii) no significant change in the excitation spectra of Zn_0.9Ni_0.1WO₄ is observed compared to pure ZnWO₄. At the same time, a shift of the excitonic bands to smaller energies and a set of peaks, attributed to the one-electron transitions from the top of the valence band to quasi-localized states, were observed in the excitation spectrum of nano-sized ZnWO₄.     

Mechanism of NdSr2 ? xCaxMn2O7 (0 ≤ x ≤ 2.0) solid solution formation

The mechanisms of formation of NdSr_{2− x} Ca _x Mn₂O₇ (0 ≤ x ≤ 2.0) solid solution have been studied. The dependence of its volume magnetic susceptibility on the calcium concentration is obtained. The stability of this solid solution is compared with that of similar solid solutions in lanthanum-containing systems.     

Anomalous behavior of the coercive force of dilute nickel ferrites NiGaxAlxFe2 ? 2 xO4 with a frustrated magnetic structure

The behavior of the spontaneous magnetization σ _s (T) and coercive force H _c (T) of dilute nickel ferrites NiGa _x Al _x Fe_{2 − 2x} O₄ (x = 0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) has been studied. Above the transition temperature T _t , the coercive force H _c is found to reveal an anomalous behavior for compositions with x ≥ 0.4, namely, the temperature dependence of the coercive force H _c (T) exhibits a maximum in the range from T _t to T _C. For the reduced temperature θ₂ = 0.8 T _C, at which ferrites with the substitution x ≥ 0.4 reside in the spin glass state, the coercive force H _c is observed to increase sharply with x. The assumption is made that the clusters prevailing in the spin glass state are no larger than 3 nm in size. Original Russian Text ? L.G. Antoshina, A.B. Korshak, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 5, pp. 900–903.     

Phase transformations and magnetotransport properties of the Pr0.5Sr0.5Co1 ? xMnxO3 system

The structural, magnetic, and magnetotransport properties of Pr_0.5Sr_0.5Co_{1 − x} Mn _x O₃ (x < 0.65) perovskites are studied by magnetization and electrical conductivity measurements in magnetic fields up to 14 T and by neutron diffraction. In the manganese concentration range x < 0.5 and T = 300 K, the crystal structure is described by monoclinic space group I2/a; at x > 0.5, it is described by orthorhombic space group Imma. When the temperature decreases, a structural transformation without changing the symmetry takes place in all compounds. This transformation is caused by an active role of the inner shells of the praseodymium ion in chemical bond formation. The substitution of manganese for cobalt breaks a long-range ferromagnetic order near x ≈ 0.25, and a metal-dielectric transition occurs at x ≈ 0.15. The negative magnetoresistance is found to be maximal near a critical manganese concentration, where a long-range magnetic order is broken; it reaches 95% in a field of 14 T at T = 10 K for x = 0.2. An unusual dielectric magnetic state with a small spontaneous magnetic moment and a sharp transition into a paramagnetic state at T > 200 K is revealed in the concentration range 0.30 ≤ x ≤ 0.65 in spite of the absence of coherent magnetic neutron scattering. A model is proposed to explain the behavior of the magnetic properties in this phase.     

Magnetic anisotropy and magnetoelectric properties of Tb1 ? xErxFe3(BO3)4 ferroborates

Magnetic and magnetoelectric properties of ferroborate single crystals with complex composition (Tb_{1 − x} Er _x Fe₃(BO₃)₄, x = 0, 0.75) and with competing exchange Tb-Fe and Er-Fe interactions are investigated. Jumps in electric polarization, magnetostriction, and magnetization are observed as a result of spin-flop transitions, as well as a considerable decrease in the critical field upon an increase in the Er concentration, in a field H _c parallel to the c axis. The observed behavior of phase-transition fields is analyzed and explained using a simple model taking into account anisotropy in g factors and exchange splitting of funda-mental doublets of the easy-axis Tb³⁺ ion and easy-plane Er³⁺ ion. It is established that magnetoelectric and magnetostriction anomalies under spin-flop transitions are mainly controlled by the Tb subsystem. The Tb subsystem makes a nonmonotonic contribution ΔP _a (H _a , T) to polarization along the a axis: the value of ΔP _a reverses its sign and increases with temperature due to the contribution from the excited states of the Tb³⁺ ion. Original Russian Text ? A.K. Zvezdin, A.M. Kadomtseva, Yu.F. Popov, G.P. Vorob’ev, A.P. Pyatakov, V.Yu. Ivanov, A.M. Kuz’menko, A.A. Mukhin, L.N. Bezmaternykh, I.A. Gudim, 2009, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 136, No. 1, pp. 80–86.     

Yb:Y2－2xLa2xO3激光透明陶瓷的光谱性能

对一种低温易烧结的Yb:Y_2-2xLa_2xO₃激光透明陶瓷的光谱性能进行了初步研究，Yb:Y_2-2xLa_2xO₃激光透明陶瓷具有宽的吸收带和大的吸收截面，在最强的吸收峰977nm处吸收截面达4.0×10^-20cm²；其荧光发射寿命为1.1ms，发射截面在1033nm处为1.0×10^-20cm²，在1077nm处为0.7×10^-20cm².Yb:Y_2-2xLa_2xO₃陶瓷的各项光学性能指标接近或达到单晶的指标. 关键词： 氧化镧钇 激光陶瓷 低温烧结 光谱性能