Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

The Nernst-Ettingshausen coefficient in the normal phase of doped HTSCs of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>y</Subscript> system

The temperature dependence of the Nernst-Ettingshausen coefficient Q(T) in the normal phase of doped HTSCs of the yttrium system was studied. The main features characterizing the behavior of this coefficient were revealed, and the character and mechanism of the effect that various nonisovalent substituents exert on the Q(T) dependence were analyzed. It is shown that the narrow-band model permits one not only to describe all the specific features observed in the Q(T) curves but also to perform a simultaneous quantitative analysis of the temperature dependences of four kinetic coefficients (the electrical resistivity and the Seebeck, Hall, and Nernst-Ettingshausen coefficients) with the use of a common set of model parameters characterizing the band structure and carrier system in the normal phase of an HTSC. This approach was employed to determine the carrier mobilities and the asymmetry of the dispersion curve in the systems studied (YBa₂Cu₃O_y, y = 6.37–6.91; YBa₂Cu_3?xCo_xO_y, x = 0–0.3; Y_1?xCa_xBa₂Cu₃O_y, x = 0–0.25; Y_1?xCa_xBa_2?xLa_xCu₃O_y, x = 0–0.5) and to analyze the effect of the substitutions involved on the variation of these parameters.     

Synthesis,structure, and properties of BIFENBVOX

Solid solutions Bi₄V_2-x Fe _x/2Nb _x/2O_11-δ (х?=?0.05–1.0) and Bi₄V_2-х-y Fe _x Nb _y O_11–δ (with fixed x or y?=?0.2 and variable х or y?=?0.2–0.5 with step 0.1) were synthesized by the standard ceramic technology in the temperature range 773–1113 K and by mechanochemical activation method using Bi₂O₃, V₂O₅ Fe₂O₃, and Nb₂O₅ oxides as initial compounds. The formation of solid solutions was studied. Ranges of stability and temperature values of phase transitions for different polymorphous modifications were defined using dylatometric and thermo gravimetric studies. The morphology and the local chemical composition of the ceramic samples were studied. Samples with concentration of dopants x?>?0.3 contain two phases; both major and impurity phases are solid solutions of the BIFENBVOX type although the dopants atoms distribution between them is random. The thermal expansion coefficients (TEC) were measured. The electrical conductivity of ceramic samples was investigated in a wide range of temperatures. The highest conductivity values among the studied solid solutions are observed for the sample with a small amount of dopants x?=?0.25.     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

Structure,phase composition,and spectral luminescence properties of partially stabilized zirconium dioxide crystals doped with Yb<Superscript>3+</Superscript> ions

Investigation of partially stabilized zirconium dioxide crystals via transmission electron microscopy has revealed a developed twin structure therein. The following compositions of the above crystals have been selected for this study: 97.2 mol % ZrO₂–1.0 mol % Y₂O₃–1.8 mol % Yb₂O₃; 97.2 mol % ZrO₂–2.0 mol % Y₂O₃–0.8 mol % Yb₂O₃; 97.2 mol % ZrO₂–2.5 mol % Y₂O₃–0.3 mol % Yb₂O₃; and 96.3 mol % ZrO₂–3.4 mol % Y₂O₃–0.3 mol % Yb₂O₃. X-ray diffraction analysis of these crystals indicate the presence of transformable (t) and nontransformable (t') tetragonal phases. Optical spectroscopy measurements of ZrO₂–Y₂O₃–Yb₂O₃ crystals with tetragonal and cubic structures have highlighted in Yb³⁺-doped zirconium dioxide samples the formation of the optical centers of the Yb³⁺ ions is observed, whose crystal surrounding is similar to those in cubic zirconium dioxide crystals.     

Electron paramagnetic resonance in mixed crystals (BaF<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript> activated by Ce<Superscript>3+</Superscript> ions

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1?x? y}(LaF₃)_x(CeF₃)_y (y = 0.001 = 0.1%, x = 0–0.02) are investigated in a magnetic field H‖C₄ at a frequency of 9.5 GHz. The angular dependence of the EPR spectrum is measured for the sample with x = 0.02. The lines attributed to Ce³⁺ impurity centers with tetragonal symmetry and g factors (g_‖ = 0.75, g_⊥ = 2.4) close to those measured for the KY₃F₁₀: Ce³⁺ compound are separated in the complex EPR spectrum. The assumption is made that the aforementioned impurity centers are cubooctahedral clusters of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion.     

Cross sections of the photoneutron reaction for <Superscript>141</Superscript>Pr and <Superscript>186</Superscript>W nuclei,estimated from physical criteria of data reliability

Using objective physical criteria for data reliability, cross sections of partial photoneutron reactions (γ, 1n), (γ, 2n) and (γ, 3n) that are free of the shortcomings of neutron multiplicity sorting methods used on beams of quasimonoenergetic annihilation photons are obtained for ¹⁴¹Pr and ¹⁸⁶W nuclei. Evaluation is performed using the experimental–theoretical method (ETM), based on the experimental cross section of neutron yield reaction σ^exp(γ, xn) = σ^exp(γ, 1n) + 2 σ^exp(γ, 2ⁿ) + 3 σexp(γ, 3n) + … and ratios F _i ^theor= σ^theor(γ, in)/σ^theor(γ, xn) calculated within the combined model (CM) of photonuclear reactions, which stipulates that σ^eval(γ, in) = F _i ^theor σ^exp(γ, xn). It is found that for ¹⁴¹Pr and ¹⁸⁶W, ratios F ^exp _i do not contradict the data reliability criteria only at energies up to ~21 and ~22 MeV, respectively. At the same time, there are notable discrepancies between F _i ^theor and F ^exp _i, and thus between the evaluated and experimental cross sections of reactions. It is shown that the discrepancies between the evaluated and experimental cross sections are due to the assumed unreliable experimental distribution of neutrons in the channels with multiplicities 1, 2, and 3.     

Atomic and Electronic Structures of Metal-Rich Noncentrosymmetric ZrO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The atomic and electronic structures of metal-rich noncentrosymmetric zirconium oxide synthesized by the ion beam sputtering of a metallic target in an oxygen atmosphere has been studied by X-ray photoelectron spectroscopy, Raman scattering, spectral ellipsometry, and quantum-chemical simulation. It has been established that ZrO_{x < 2} consists of ZrO₂, metallic Zr, and zirconium suboxides ZrO_y. The stoichiometry parameter of ZrO_y has been estimated. It has been shown that the optical properties of ZrO_{x < 2} are determined by metallic Zr. A model of fluctuation of the width of the band gap and a potential for electrons and holes in ZrO_{x < 2} based on spatial fluctuations of the chemical composition has been proposed.     

Correction of the band gap of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Submicron samples of Y₂O₃:Eu³⁺ phosphor with elevated photoluminescence (PL) efficiency and activator concentration of 9 at % obtained by the sol–gel method were investigated by diffuse reflection spectroscopy and PL spectroscopy. It is found that the diffuse reflection spectrum in the vicinity of the fundamental absorption edge (<300 nm) is distorted by the superposition of the PL of Eu³⁺ ions, as a result of which the calculated value of optical band gap E _g of the Y₂O₃ matrix is overestimated. An algorithm for eliminating the PL influence on the absorption edge is proposed, and the correct E _g values are found to be 4.61 ± 0.12 and 4.50 ± 0.12 eV for annealing at 700 and 1300°C, respectively.     

Data on photoneutron reactions from various experiments for <Superscript>133</Superscript>Cs, <Superscript>138</Superscript>Ba and <Superscript>209</Superscript>Bi nuclei

Basic methods for determining cross sections for photoneutron partial reactions are examined. They are obtained directly in experiments with quasimonoeneregetic annihilation photons or from the cross section for the (γ, xn) = (γ, 1n) + 2(γ, 2n) + 3(γ, 3n) +... neutron-yield reaction in experiments with bremsstrahlung photons by introducing corrections based on statistical nuclear-reaction theory. The difference in the conditions of these experiments, which leads to discrepancies between their results because of sizable systematic errors, is analyzed. Physical criteria are used to study the reliability of data on the photodisintegration of ¹³³Cs, ¹³⁸Ba, and ²⁰⁹Bi nuclei. The cross sections for partial and total reactions satisfying the reliability criteria are evaluated within the experimental–theoretical method (σ^eval(γ, in) = F_i^theor × σ^expt(γ, xn)) on the basis of the experimental cross sections σ^expt(γ, xn) and the results of the calculations within the combined model of photonuclear reactions.     

Ferroelectric phase transitions in ionic conductors based on bismuth vadanate

Ceramic solid solutions (Bi_{1 ? x} La _x )₄V₂O_{11 ? z} (I), Bi₄(V_{1 ? x} Fe _x )₂O_{11 ? y} (II), and (Bi_{1 ? x} La _x )₄(V_0.96Fe_0.04)₂O_{11 ? y} (III) (x = 0–0.3, step Δx = 0.02) are prepared using solid-phase synthesis. The concentration and temperature ranges of stabilization of different polymorphic modifications, including the ranges of concentrations x corresponding to the stabilization of the ferroelectric phase, are established. It is revealed that an increase in the concentration x in the region of existence of the pseudoorthorhombic phase α of the solid solutions studied leads to a decrease in the transition temperature, smearing of the transition, and an increase in the width of the thermal hysteresis of the ferroelectric phase transition. The effect of compressing of the domain walls by oxygen vacancies was revealed in the samples from the region of existence of the ferroelectric α phase, and the effect of dielectric relaxation was detected in the samples from the region of existence of the orthorhombic phase β.     

Spin-spin interaction and the EPR spectrum of KDy(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The EPR spectrum of a KDy(WO₄)₂ monoclinic crystal is investigated. It is found that the EPR spectrum of magnetically concentrated materials at a low frequency (9.2 GHz) undergoes a substantial transformation in addition to the well-known broadening of the EPR lines. At low Dy³⁺ concentrations (x<10^?2), the EPR spectrum of an isomorphic crystal, namely, KY_(1?x)Dy_x(WO₄)₂, is characterized by the parameters g_x=0, g_y=1.54, and g_z=14.6. For a magnetically concentrated crystal KDy(WO₄)₂, the g values are as follows: g_x=0, g_y=0.82, and g_z=2.52. It is demonstrated that the difference in the parameters is associated with the specific spin-spin interaction between Dy³⁺ ions, including the Dzyaloshinski interaction, which is not observed at high frequencies.     

Reliability of the data on the cross sections of the partial photoneutron reaction for <Superscript>63,65</Superscript>Cu and <Superscript>80</Superscript>Se nuclei

The cross sections of partial photoneutron reactions are evaluated for the ^63,65Cu and ⁸⁰Se isotopes. The cross sections are free of systematic uncertainties from shortcomings of the experimental methods for neutron multiplicity sorting based on measurements of neutron energy used in experiments with quasimonoenergetic annihilation photon beams. An experimental-theoretical method is used to evaluate cross sections σ^eval(γ, in)= F_i^theor σ^exp(γ, xn), where ratios F_i^theor = σ^theor(γ, in)/σ^theor(γ, xn) = σ^theor(γ, in)/σ^theor[(γ, 1n) + 2(γ, 2n) + …] are calculated using a combined model of photonuclear reactions, and σ^exp(γ, xn) is the experimental cross section of the neutron yield reaction free from neutron multiplicity sorting problems. The cross sections are evaluated for reactions (γ, 1n) and (γ, 2n) for the ^63,65Cu and ⁸⁰Se isotopes, and for the total photoneutron reaction σ(γ, Sn) = σ[(γ, 1n) + (γ, 2n) + …]. It is shown that noticeable deviations of the experimental cross sections from the evaluated values result from the unreliable sorting of neutrons between the channels with multiplicities 1 and 2.     

Extreme Electromechanical Characteristics and Microstructural Features of Ferro-Piezoceramics Based on Lead Titanate

Microstructural features and electrophysical parameters of a number of solid solutions based on PbTiO₃ are investigated. Solid solutions (Pb_{1–3/2x + z/2}Nd _x )(Ti_1–y–zMn _y Inz)O₃ and Pb_1–xCa _x Ti_1–y(W_1/2Co_1/2) _y O₃ with extreme values of the mechanical Q-factor and electromechanical anisotropy are chosen as the objects of investigation. The ferro-piezoceramic samples are obtained through conventional sintering and hot pressing. X-ray structural and microstructural studies are performed, and the complex elastic, dielectric, and piezoelectric parameters of experimental samples are measured. The frequency dependences of complex parameters of the experimental samples have been studied at frequencies of up to 40 MHz. It is established that the extreme values of the mechanical Q-factor and piezoelectric anisotropy of the investigated PbTiO₃-based solid solutions are due to microstructural features associated with the technological regimes of ferropiezoceramic fabrication.     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Intrinsic luminescence centers in scandia,yttria, and their solid solutions

Pulsed cathodoluminescence (PCL) of Y₂O₃ and Sc₂O₃ powders, as well as of ceramic samples of binary (11 mol % Sc₂O₃–ZrO₂ and 10 mol % Y₂O₃–ZrO₂) and ternary (xSc₂O₃–(10–x)Y₂O₃–ZrO₂) (x = 5, 6, 7, 8 mol %) solid solutions are studied in the range of 300–850 nm at room temperature. In Y₂O₃ and Sc₂O₃, series of strong narrow luminescence bands emitted by surface bound radicals _...0^...0>-Y=O and _...0^...0>-Sc=O are found. The PCL spectra of xSc₂O₃–(10–x)Y₂O₃–ZrO₂ ceramic samples showed the same series of narrow bands at 543, 551, 555, 572, 583, 594, 614, and 639 nm as the yttrium oxide spectra. The existence of these luminescence bands, which correspond to the emission of the _...0^...0>-Y=O radical, and the absence of the emission lines of the _...0^...0>-Sc=O radical indicate that yttrium ions, due to their larger radius, are the first that are displaced to the surface of crystallites in these systems, which is accompanied by the formation of the second phase in subsurface layers.     

Sol-gel method and luminescence properties of the ZrO<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> phosphors with different charge compensation

Eu³⁺-doped ZrO₂ phosphors with different charge compensators (Li⁺, Na⁺, K⁺) were prepared by the sol-gel method. The properties of the as-obtained samples are characterized by X-ray diffraction, scanning electron microscope, photoluminescence spectra, and decay curve. The results show that ZrO₂:Eu³⁺ phosphors with different charge compensation are mixed phase of tetragonal and monoclinic phase, and the volume fraction of tetragonal phase of ZrO₂:Eu³⁺/Na⁺ phosphor is bigger than the other phosphors. The phosphors can emit strong red light at 606~616 nm (⁵D₀ → ⁷F₂) excited by ultraviolet light (395 nm). Compared with two charge compensation patterns in the ZrO₂:Eu³⁺, it has been found that ZrO₂:Eu³⁺ phosphors used Na⁺ as charge compensator show greatly enhanced red emission under 395 nm excitation and longer luminescence lifetime.     

Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La_0.3Ln_0.3Sr_0.3Mn_1.1O_3–δ manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, ⁵⁵Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3?c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, or Eu³⁺ when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure, which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T _ms) and ferromagnet–paramagnet (T _C) phase transitions and the increase in electrical resistivity ρ and activation energy E _a with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d ⁴(Mn³⁺)–2p ⁶(O^2–)–3d ³(Mn⁴⁺)–V ^(a)–3d ⁴(Mn³⁺). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric ⁵⁵Mn NMR spectra support the high-frequency electronic double exchange Mn³⁺(3d ⁴) ? O^2–(2p ⁶) ? Mn⁴⁺(3d ³) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the magnetic, magnetotransport, and magnetoresistance properties of rare-earth perovskite manganites.     

Influence of oxidized interlayers on magnetic properties of multilayer films based on amorphous ferromagnet–dielectric nanocomposites

Films of composites (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x, (Co₈₄Nb₁₄Ta₂)_x(SiO₂)_100–x, (Co₄₁Fe₃₉B₂₀)_x(SiO₂)_100–x and multilayer heterogeneous composite–composite structures {[(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x]/[(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x + N₂]}_n, {[(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x]/[(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x + O₂]}_n, {[(Co₄₁Fe₃₉B₂₀)_x(SiO₂)_100–x]/[(Co₄₁Fe₃₉B₂₀)_x(SiO₂)_100–x + O₂]}_n, and {[(Co₈₄Nb₁₄Ta₂)_x(SiO₂)_100–x]/[(Co₈₄Nb₁₄Ta₂)_x(SiO₂)_100–x + O₂]}_n have been deposited using the ionbeam sputtering method with a cyclic supply of reaction gases during deposition. The structure and magnetic properties of the films have been studied. It has been shown that the introduction of an oxidized interlayer makes it possible to suppress the perpendicular magnetic anisotropy in the (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100–x composite with the metallic phase concentration higher than the percolation threshold.     

Stabilizer of a function in the gage group

It is proved that, for the dimension d of the stabilizer of an analytic function z(x, y) in the gage pseudogroup G = {z(x, y) → c(z(a(x), b(y))}, there are precisely four possibilities: (1) d = ∞ and the complexity of z is zero, (2) d = 3 and the complexity of z is equal to one, (3) d = 1 and z is equivalent the function r(x + y) ? x of complexity two, (4) d = 0 in all remaining cases.