Dielectric properties of perovskite ceramics of (1–x)BiFeO3 ? x(KBi)1/2TiO3 (0.40 < x < 0.85) solid solutions from impedance spectroscopy data

The dielectric properties of the ceramics of (1 − x)BiFeO₃ − x(KBi)_1/2TiO₃ (0.40 < x < 0.85) solid solutions with an orthorhombic structure have been studied using impedance spectroscopy in the frequency range 25–10⁶ Hz at different temperatures. It has been shown that these solid solutions undergo a diffuse ferroelectric phase transition. The Curie temperature is found to be in the range 620–640 K. The activation energies of dielectric polarization relaxation (δE _M ) and dc charge carriers (ΔE _dc) are determined. It has been established that, in the vicinity of 460 K, ΔE _dc increases jumpwise as the temperature increases.     

Mössbauer spectroscopy studies of the preparation steps of unsupported Fe- and FeMo-sulfide hydrotreating catalysts

Both the gas atmosphere (Ar, 15% H₂S−H₂, H₂) and the temperature of treatment strongly affect the distribution of iron atoms among different phases (FeS₂-pyrite, Fe_1−x S-pyrrhotite, FeS-troilite, mixed Fe−Mo−S structure) in Fe- and FeMo sulfide catalysts. In FeMo sulfide catalysts FeS₂ (pyrite) and the Fe−Mo−S structure are stabilized by MoS₂.     

Superconductivity and possible overdoping in Lu1−x Ca x Ba2Cu3O7−δ

Structural and superconducting properties of the system Lu_1−x Ca _x Ba₂ Cu₃O_7−δ, both in bulk as well as thin film form, have been investigated. Presence of large Ca-ions at the Lu-sites is responsible for phase stability (in 1–2–3 phase) in bulk. In argon annealed tetragonal samples (δ:1) superconductivity is reinstated as in these samples, presence of Ca-ions lead to the generation of holes in the Cu−O planes. In oxygen annealed bulk samples and thin films, there is a large depression ofT _c due to divalent Ca-ions present in concentrationx<0.2. Our data indicate that this depression ofT _c is likely due to overdoping effect.     

Near-ordering structural transitions in amorphous metal alloys

The temperature variations in the modulus of elasticity (Young’s modulus) E and internal friction Q ⁻¹ of the amorphous metal alloys Ti₅₀Cu_50−x Ni_x (5⩽x⩽20) are studied at temperatures of 300–800 K. There is an anomalous increase in E(T) at temperatures above T _x (which varies from 440 to 525 K, depending on the composition). When the amount of nickel in the alloy is high (x>12 at. %), a small peak shows up in Q ⁻¹(T). These effects are related to structural transitions in near-ordering regions (clusters). A model for structural relaxation of near ordering in amorphous alloys is proposed on the basis of these experiments. Fiz. Tverd. Tela (St. Petersburg) 40, 389–392 (March 1998)     

Far-infrared spectral studies of magnesium and aluminum co-substituted lithium ferrites

Polycrystalline Mg_xAl_2xLi_0.5(1−x)Fe_2.5(1−x) O₄ (x = 0.0, 0.2, 0.5, 0.6 and 0.7) ferrites were prepared by standard ceramic method, and characterized by X-ray diffraction and infrared absorption spectroscopy. The spectra show two significant absorption bands in the wave number range of 400–1000 cm⁻¹ arising from interatomic vibrations in the tetrahedral and octahedral coordination compounds. The decrease in intensity and increase in broadness of bands with concentration (x) are explained on the basis of cation distribution. The force constants and bulk modulus are found to decrease with Mg-Al content (x) which suggested weakening of interatomic bonding. An alternate method for the determination of bulk modulus, longitudinal and transverse velocities is suggested. The magnetic and electrical properties of these compounds are explained in the light of structural and optical properties.     

Study of the amorphous Fe100−x B x and (Fe70Co30)100−x B x powder prepared by borohydride reduction

The amorphous fine particles of Fe_100−x B _x (20.7≤x≤36.5) and (Fe₇₀Co₃₀)_100−x B _x (26.9≤x≤40.2) were prepared by borohydride reduction. The amorphous state of the samples was identified with both X-ray and electron diffraction measurements. With increasing boron content, the average hyperfine magnetic fields decrease. Comparing the hyperfine parameters of the glassy powder with those of the ribbons having the same compositions, the average hyperfine fields and the isomer shifts are different. The differences may be due to the amorphous polymorphism which is produced by the different preparation methods. Project is partly supported by the National Natural Science Foundation of China.     

Advances in single crystal growth and annealing treatment of electron-doped HTSC

High quality electron-doped HTSC single crystals of Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ have been successfully grown by the container-free traveling solvent floating zone technique. The optimally doped Pr_2−xCe_xCuO_4+δ and Nd_2−xCe_xCuO_4+δ crystals have transition temperatures T _c of 25 K and 23.5 K, respectively, with a transition width of less than 1 K. We found a strong dependence of the optimal growth parameters on the Ce content x. We discuss the optimization of the post-growth annealing treatment of the samples, the doping extension of the superconducting dome for both compounds as well as the role of excess oxygen. The absolute oxygen content of the as-grown crystals is determined from thermogravimetric experiments and is found to be ≥ 4.0. This oxygen surplus is nearly completely removed by a post-growth annealing treatment. The reduction process is reversible as demonstrated by magnetization measurements. In as-grown samples the excess oxygen resides on the apical site O(3). This apical oxygen has nearly no doping effect, but rather influences the evolution of superconductivity by inducing additional disorder in the CuO₂ layers. The very high crystal quality of Nd_2−xCe_xCuO_4+δ is particularly manifest in magnetic quantum oscillations observed on several samples at different doping levels. They provide a unique opportunity of studying the Fermi surface and its dependence on the carrier concentration in the bulk of the crystals.     

Crystallization kinetics of the Fe−Co−B amorphous alloys

A series of amorphous ribbons Fe_85−x Co _x B₁₅ was subjected to the isothermal crystallization annealing. The alloys forx=12, 15, 17, 19, 21, 23, and 25 at.% Co were measured at room temperature by standard transmission technique during interrupted annealing. The samples with 12 and 21 at.% Co were used for direct scanning at constant velocity of the outermost metallic peak. In both cases gradually increasing content of the metallic Fe−Co phase was observed in at least two stages. Several scanning temperatures applied with the 12 and 21 at.% Co samples made it possible to draw the Arrhenius plots and to estimate the activation enthalpies of the processes. By analysing the Avrami exponents and activation enthalpies, the first process is attributed to a comparatively fast primary Fe−Co crystallization followed by the transformations of the amorphous rest.     

Size of the interpolated cation and hole carrier density: two key parameters for the optimisation of colossal magnetoresistive properties of Pr-based manganites

The exploration of the magnetic and transport properties of four series of manganese perovskites, Pr_0.7Ca_0.34−xA_xMnO_3−δ (A=Sr, Ba), Pr_0.7−xLa_xCa_0.3 MnO_3−δ and Pr_0.66Ca_0.34−x Sr_xMnO_3−δ has allowed four phases with colossal magnetoresistive (CMR) properties to be isolated: Pr_0.7Ca_0.25Sr_0.025MnO_3−δ and Pr_0.66Ca_0.26Sr_0.08MnO_3−δ that exhibit a variation of resistance of 2.5. 10⁷% and 10⁹% at μ₀ H=5 T for T=88 K and 50 K respectively, Pr_0.58La_0.12Ca_0.3 MnO_3−δ that exhibits a variation of 6.10⁶% for μ₀ H=5 T at T=80 K and Pr_0.7Ba_0.025Ca_0.275MnO_3−δ for which a resistance variation of 5.10⁹%, at T=50 K, for μ₀ H=5 T is evidenced. for each compound of this series except the barium phase, one observes that the temperature T_max, which corresponds to the resistance maximum on the R(T) curves in zero magnetic field, increases dramatically as the mean size of the interpolated cations increases, and that the CMR effect correlatively decreases dramatically. The comparison of the two series Pr_0.7Ca_0.3−xSr_xMnO_3−δ and Pr_0.66Ca_0.34−xSr_xMnO_3−δ shows also the crucial role of the hole carrier density: for a same mean ionic radius of the interpolated cation T_max is decreased of about 50 K by introducing 0.034 hole per Mn mole.     

AC Conductivity,XRD and transport properties of melt quenched PbI<Subscript>2</Subscript>–Ag<Subscript>2</Subscript>O–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Composite materials used for electrode and electrolyte materials have been intensely studied in view of their advantages such as higher conductivity and better operational performance compared to their single-phase counterparts. The present work aims at studying the electrical and structural characteristics of a new composite electrolyte namely, (PbI₂) _x  − (Ag₂O–Cr₂O₃)_100−x where x = 5, 10, 15, 20, and 25 mol%, respectively, prepared by the melt quenching technique. The room temperature X-ray diffraction spectra revealed certain crystalline phases in the samples. AC conductivity analysis for all the prepared samples was carried out over the frequency range 1 MHz–20 Hz and in the temperature window 297–468 K. The room temperature conductivity values were calculated to be in the order of 10⁻⁵–10⁻³ Scm⁻¹. An Arrhenius dependence of temperature with conductivity was observed, and the activation energies calculated were found to be in the range 0.27–0.31 eV. Furthermore, the total ionic transport number (t _i) values obtained for all these indicated the ionic nature of this system. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Bound state solutions of the two-electron Dirac-Coulomb equation

We present a variational method for solving the two-electron Dirac-Coulomb equation. When the expectation value of the Dirac-Coulomb Hamiltonian is made stationary for all possible variations of the different components of a well-behaved trial function one obtains solutions representative of the physical bound state wave functions. The ground state wave function is derived from the application of a minimax principle. Since the trial function remains well-behaved, the method remains safe from the twin demons of variational collapse and continuum dissolution. The ground state wave function thus derived can be interpreted as a linear combination of different configurations. In particular, the admixing of intermediate states having one (two) electron(s) deexcited to a negative-energy orbital (orbitals) contributes a second-order level shiftE ₀₋ ⁽²⁾ which can be identified with the second-order shift due to the Pauli blocking of the production of one (or two) virtual electron-positron pair(s). Thus the minimax solution corresponds to the renormalized ground state in quantum electrodynamics, with deexcitations to negative-energy orbitals taking the place of the avoidance of virtual pairs. If one extends the relativistic configuration interaction (RCI) treatment by additionally including negative-energy and mixed-energyeigenvectors of the Dirac-Hartree-Fock hamiltonian matrix in the two-electron basis, the calculated energy will be shifted from the conventional RCI value by an amount that is much smaller thanE ₀₋ ⁽²⁾ . For two-electron atoms, we have derived expressions for the all-spinor limit (δE) and thes-spinor limit (δE _s) of this shift in leading orders. The all-spinor limit (δE) is of orderα ⁴ Z ^{4 1/3} whereas thes-spinor limit (δE _s) is of orderα ⁴ Z ^{3 2/3}. leading components are related to the 1-pair component ofE ₀₋ ⁽²⁾ in a simple way, and the relationships offer the possibility of computing energy due to virtual pairs. Numerical results are discussed.     

Depth distribution of point defects in Si bombarded by high-energy N5+ and Si5+ ions

Electron spin resonance has been used to study the depth distribution of point defects in Si samples bombarded by N⁵⁺ (E=16 MeV) and Si⁵⁺ (E=26.8 MeV) ions at 175 and 300 K in the dose range (4–8)×10¹⁵ cm⁻². It was established that unlike the implantation of moderate-energy Si ions (E ∼ 100 keV), the depth distributions of planar tetravacancies in samples bombarded by ions at 300 K under these conditions have two maxima. The experimental results indicate that the tetravacancy density maximum closer to the surface is formed as a result of secondary defect formation processes. No continuous amorphous layer was observed in the bulk of any of the Si samples. This experimental observation is evidence of defect annealing which takes place when high-energy ions are implanted in Si. Fiz. Tverd. Tela (St. Petersburg) 40, 217–222 (February 1998)     

Dielectric properties of epitaxial Pb1−x Sn x Te layers at microwave frequencies

The dielectric properties of epitaxial Pb_1−x Sn _x Te layers are investigated at 9 GHz in a composition range betweenx=0 and 0.225. The samples are characterized by fairly low carrier concentrations between 1.4×10¹⁶ and 32×10¹⁶ cm⁻³. Data of the static dielectric constant (ε ^s ) are obtained at temperatures of 77 and 300 K. The results of ε ^s are 25% to 100% higher compared to previous measurements in bulk material from other authors. The observed higher values of ε ^s in the investigated samples may be due to the reduced number of point defects in epitaxially grown Pb_1−x Sn _x Te layers. The model of Kawamura which predicts a dependence of ε ^s on the effective band gap cannot be verified.     

Unusual vortex dynamics in the quantum-liquid phase of a-MoxSi1−x films

We find the unusual vortex dynamics in the low-temperature liquid phase of amorphous Mo_xSi_1−x films by measuring the fluctuating component of the flux-flow voltage δV(t) about the average voltage. For the thick film, in which the quantum vortex liquid (QVL) phase has been well-determined in the field-temperature plane, δV(t) originating from the vortex motion is clearly visible in the QVL phase, where the distribution of δV(t) is anomalously asymmetric, implying large velocity and/or number fluctuations of driven vortices. For the thin film, in which the QVL phase has not been determined from the static transport measurements, similar unusual vortex motion is observed in nearly the same reduced-temperature regime. We suggest that vortex dynamics in the low-temperature liquid phase of thick and thin films is dominated by common physical mechanisms related to quantum-fluctuation effects.     

An EIS study of La2 − x Sr x NiO4 + δ SOFC cathodes

La_2 − x Sr _x NiO_{4 +  δ} materials were investigated as cathodes for the electrochemical reduction of oxygen on a Ce_1.9Gd_0.1O_1.95 (CGO10) electrolyte using cone-shaped electrodes together with electrochemical impedance spectroscopy. The area-specific resistance (ASR) of the La_2 − x Sr _x NiO_{4 +  δ} nickelates towards the reduction of oxygen is equal to the ASR of perovskites; however, it is not as low as for the best Fe–Co-based perovskites. The lowest ASR is found for the compound La_1.75Sr_0.25NiO_{4 +  δ} with an ASR of 23.8 Ωcm² measured on a cone-shaped electrode in air at 600 °C. It is suggested that difference in oxide ionic conductivity of the nickelates is the main cause for the different activity of the nickelates towards the electrochemical reduction of oxygen.     

Structural and magnetic phases of Bi<Subscript>1−x</Subscript>A<Subscript>x</Subscript>FeO<Subscript>3−</Subscript><Subscript>δ</Subscript> (A = Sr,Pb) perovskites

The Bi_1−xA_xFeO_{3− δ} (A = Sr, Pb) systems have been studied using the X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that around x ∼ 0.06 the crystal symmetry changes from a rhombohedral (space group R3c) to pseudo-tetragonal. In the composition range 0.07 ≤ x ≤ 0.14 the phases with different symmetry of the unit cell coexist independent of synthesis conditions. The neutron powder diffraction shows that the iron ions have average oxidation state close to 3+. The magnetic structure for Bi_0.5Sr_0.5FeO_{3− δ} is found to be G-type antiferromagnetic with magnetic moment of about 3.8 μ_B/Fe³⁺. The weak ferromagnetic state due to magnetoelectric interactions was revealed in the lightly doped rhombohedrally distorted compositions. No evidence for a spontaneous magnetization was observed for the pseudo-tetragonal phases. These compositions show irreversible nonlinear magnetization vs. field behavior apparently due to small local deviations from the collinearity of the magnetic moments.     

Effect of oxygen deficiency on the magnetic, electrical, magnetoelectric, and magnetoelastic properties of La1 ? x Sr x MnO3 ? δ manganites

This paper reports on a study of the effect of oxygen deficiency on the magnetic and electrical properties of the La_{1 − x} Sr _x MnO_{3 − δ} manganites (x = 0, 0.2, 0.4; δ = 0, 0.13, 0.2). In compositions with x = 0 and δ = 0.13 and 0.2, the temperature dependence of the magnetization M (T) can be approximated by the Langevin function with the moment of superparamagnetic clusters μ = 77μ_B (δ = 0.13) and 86μ_B (δ = 0.2) at temperatures of 25 K ≤ T ≤ 250 K, with the exception of a small temperature range near 132 K in which a maximum characteristic of the LaMnO₃ antiferromagnet is seen. These compositions, as well as Sr-doped compositions with δ ≠ 0, reveal a difference between the magnetizations of the sample cooled in a weak magnetic field and in zero field. At T = 6 K in a magnetic field of 16 kOe, the compositions with x = 0.2 and 0.4, δ = 0.13 possess a magnetic moment per formula unit lower than that with δ = 0, as well as reveal an anomalous relation between the Curie temperature T _C and the Curie paramagnetic point gJ, namely, T _C > gJ. The magnetization of compositions with x = 0.2 and 0.4, δ = 0.2 follows the Langevin function with μ = 40μ_B and 130μ_B, respectively. The electrical resistivity of samples with x = 0.4 and δ = 0.13 and 0.2 is one to two orders of magnitude larger than that of the composition with x = 0.4, δ = 0, which evidences partial or complete compensation of acceptor defects (Sr²⁺ ions) by donor defects (doubly charged O²⁻ vacancies). The above properties of oxygen-deficient compositions suggest that they contain an insulating ferro-antiferromagnetic magnetically double-phase state. The magnetoresistance and volume magnetostriction in samples with x = 0.4 and δ = 0, 0.13, and 0.2 are small; indeed, in a magnetic field of 8 kOe, they do not exceed 1.4% and 6 × 10⁻⁶, respectively. On this basis, it is concluded that the unbalanced doubly charged donors (O vacancies) are in the state with antiparallel spins and, thus, do not initiate the formation of ferron-type ferromagnetic clusters. The significance of both compensated and unbalanced doubly charged donors consists in that they give rise to the formation of fractured Mn-O-Mn bonds, which bring about lowering of the magnetic moment per formula unit in compositions with x = 0.2 and 0.4 and δ = 0.13 and the transition to superparamagnetism in compositions with x = 0.2 and 0.4, δ = 0.2. Original Russian Text ? L.I. Koroleva, D.M. Zashchirinskiĭ, T.M. Khapaeva, L.I. Gurskiĭ, N.A. Kalanda, V.M. Trukhan, R. Szymczak, B. Krzumanska, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 12, pp. 2201–2205.     

Confrontation of nucleus deformation and multipole mixture parameters in (2+0 n ?2+01) transitions with rotational band structure for K π = 0 2+ and 0 3+

The difference of the energies of levels Δ _n = E _lev(2⁺0 _n ) − E _lev(0⁺0 _n ) at n = 1, 2, and 3 and the multipole-mixture parameter δ for (2⁺0₂−2⁺0₁) and (2⁺0₃−2⁺0₁) transitions are contrasted against the structure of the K ^π = 0₂⁺ and 0₃⁺ rotational bands that was calculated on the basis of the quasiparticle-phonon model. The values of (Δ₂ − Δ₁), (Δ₃ − Δ₁), and (Δ₂ − Δ₃) are found to correlate with the sign of the parameter δ and with the calculated structure of the K ^π = 0₂⁺ and 0₃⁺ bands. Original Russian Text ? A.M. Demidov, L.I. Govor, V.A. Kurkin, I.V. Mikhailov, 2009, published in Yadernaya Fizika, 2009, Vol. 72, No. 2, pp. 236–240.     

The effect of bias field on the value and temperature dependence of the piezoelectric coefficient d 31 in (1 ? x )Pb(Mg1/3Nb2/3)O3? x PbTiO3 ( x = 0.06, 0.13) single crystals

It is established that, as a result of application of even a small (∼0.5 kV cm⁻¹) bias field E, the maximum of the piezoelectric coefficient d ₃₁ in (1 − x)Pb(Mg_1/3Nb_2/3)O₃ − xPbTiO₃(x = 0.06, 0.13) crystals shifts from the Vogel-Fulcher temperature to the critical point in the E-T phase diagram of a given composition. The field dependence of the d ₃₁(T) peak magnitude has a maximum near the E values corresponding to the critical point. Original Russian Text ? A.S. Emelyanov, S.I. Raevskaya, F.I. Savenko, I.P. Raevski, M.A. Malitskaya, E.I. Sitalo, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 1, pp. 132–133.     

Stable and metastable phases in Nd−Fe binary alloys

Melt-spinning Nd _x Fe_100-x alloys over a wide composition range: 10≤x≤90, has lead to the identification of three metastable phases. Two of these correspond to phases which are stable in late rare earth-iron alloy systems, the third is related to the fcc grain boundary phase observed in sintered Nd−Fe−B permanent magnets. Structural and magnetic data are presented.