Electrical conductivity and chemical stability of perovskite-type BaCe0.8-xTixY0.2O3-δ

Here we report the synthesis, chemical stability, and electrical conductivity of Ti-doped perovskite-type BaCe_0.8-x Ti _x Y_0.2O_3-δ (x = 0.05, 0.1, 0.2, and 0.3; BCTY). Samples were synthesized by conventional solid state (ceramic) reaction from corresponding metal salts and oxides at elevated temperature of 1,300–1,500 °C in air. The powder X-ray diffraction confirmed the formation of a simple cubic perovskite-type structure with a lattice constant of a = 4.374(1), 4.377(1), and 4.332(1) ? for x = 0.05, 0.1, and 0.2 members of BCTY, respectively. Like BaCe_0.8Y_0.2O_3-δ (BCY), Ti substituted BCTY was found to be chemically not stable in 100% CO₂ and form BaCO₃ at elevated temperature. The bulk electrical conductivity of BCTY decreased with increasing Ti content and the x = 0.05 member exhibited the highest conductivity of 2.3 × 10⁻³ S cm⁻¹ at 650 °C in air, while a slight increase in the conductivity, especially at low temperatures (below 600 °C), was observed in humidified atmospheres.     

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.     

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.     

Magnetic phases in Pr0.5Sr0.5Mn1 ? xCoxO3 (x ≤ 0.5) solid solutions

The magnetic and magnetotransport properties of Pr_0.5Sr_0.5Mn_{1 − x} Co _x O₃ (x ≤ 0.5) solid solutions have been investigated using neutron diffraction methods. The magnetization and electrical conductivity have been measured in magnetic fields up to 140 kOe. It has been established that, during cooling in the temperature range from 160 to 110 K, the compounds of compositions with a cobalt content x ≤ 0.07 undergo a structural phase transition from the high-temperature ferromagnetic phase to the antiferromagnetic phase. A further substitution of cobalt for manganese leads to a stabilization of the inhomogeneous dielectric ferromagnetic state, whereas a state of the cluster spin-glass type has been revealed in compositions with x = 0.15 and 0.20. At x ≥ 0.25, a new magnetic phase with a Curie temperature up to 210 K is formed as a result of the magnetic interaction between manganese and cobalt ions. A magnetic phase diagram of the system under investigation has been constructed.     

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.     

Low-temperature electrical conductivity and the superconductor-insulator transition induced by indium impurity states in (Pb0.5Sn0.5)1 ? xInxTe solid solutions

A study is reported of the low-temperature electrophysical (including superconducting) characteristics of the (Pb_0.5Sn_0.5)_{1 − x} In _x Te semiconducting solid solutions with an indium content variable within x = 0.05–0.20. A decrease in the impurity content x in the material has been found to bring about a decrease in the superconducting transition temperature T _c and the onset of an “insulating” state of the material. These effects manifest themselves in an increase in the low-temperature (T = 4.2 K) resistivity of (Pb_0.5Sn_0.5)_0.95In_0.05Te by more than three orders of magnitude as compared to that of (Pb_0.5Sn_0.5)_0.8In_0.2Te. A decrease in the In content in the solid solution also gives rise to a radical change in the shape of the temperature dependence of the electrical resistivity from a metallic behavior in the material with x = 0.20 (decrease in the electrical resistivity with decreasing temperature in the range 300–4.2 K) to a semiconducting behavior in a sample with x = 0.05 (exponential increase in the resistivity at T < 25 K). This transition to the insulating state with decreasing content of the impurity should be assigned to the displacement of the impurity band of quasi-local indium states toward the top of the light-hole valence band of the material and its emergence into the band gap of the solid solution.     

Sinteractivity, proton conductivity and chemical stability of BaZr0.7In0.3O3-δ for solid oxide fuel cells (SOFCs)

In³⁺ was used as dopant for BaZrO₃ proton conductor and 30 at%-doped BaZrO₃ samples (BaZr_0.7In_0.3O_3-δ, BZI) were prepared as electrolyte materials for proton-conducting solid oxide fuel cells (SOFCs). The BZI material showed a much improved sinteractivity compared with the conventional Y-doped BaZrO₃. The BZI pellets reached almost full density after sintering at 1600 °C for 10 h, whereas the Y-doped BaZrO₃ samples still remained porous under the same sintering conditions. The conductivity measurements indicated that BZI pellets showed smaller bulk but improved grain boundary proton conductivity, when compared with Y-doped BaZrO₃ samples. A total proton conductivity of 1.7 × 10⁻³ S cm⁻¹ was obtained for the BZI sample at 700 °C in wet 10% H₂ atmosphere. The BZI electrolyte material also showed adequate chemical stability against CO₂ and H₂O, which is promising for application in fuel cells.     

Modification of the optical spectra of mixed K2CoxNi1–x(SO4)2?6H2O crystals

We propose a new method for obtaining K₂Co _x Ni_1–x (SO₄)₂⋅6H₂O (x = 0, 0.4, 0.8, 1) crystals, involving the use of the chlorides (CoCl₂⋅6H₂O and NiCl₂⋅6H₂O) in an aqueous solution instead of the widely used sulfates. We have studied the transmission spectra of the grown single crystals in the range λ = 200–900 nm and the IR reflectance spectra in the 2.5–20 μm region. We have observed a change in the position and intensity of the absorption bands as a function of the composition of the crystals. Based on the Tanabe–Sugano diagrams, we determined the crystal field splitting (D_q) and its dependence on the nickel concentration. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 126–130, January–February, 2009.     

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.     

Electronic properties of LiMn2?xTixO4

Ti-substituted LiMn₂O₄ (LiMn_2−x Ti _x O₄, x=0, 0.15, 0.30, 0.45, 0.60, and 0.75) has been synthesized using solid-state reactions. Their crystal and electronic structures were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). XRD data suggested that the lattice parameters of LiMn_2−x Ti _x O₄ increase due to the replacement of Mn by Ti ions. XPS results indicated that the substituted Ti ions were in +4 oxidation state; consequently, the normal oxidation state of Mn ions has been detected by measuring the binding energy splitting of Mn 3s states, which decreases with the content of substituted Ti. The valence band spectra suggested that the intensity of e _g level of Mn 3d orbitals increased due to the increase of the Mn³⁺/Mn⁴⁺ ratio.     

Total cross sections for scattering of electrons from O2, H2O, H2, O3, CO and CO2 at 100－2000eV

A complex optical model potential rewritten by the concept of bonded atom, which considers the overlap of electron clouds, is employed to calculate the total cross sections for electron scattering from several simple molecules (O_2, H_2O, H_2, O_3, CO and CO_2) consisting of C, H and O atoms in an incident energy range of 100－2000eV by the use of the additivity rule at Hartree－Fock level. In the study, the complex optical potential composed of static, exchange, correlation polarization plus absorption contributions firstly uses the bonded-atom concept. The quantitative molecular total cross section results are compared with experimental data and with the other calculations wherever available and good agreement is obtained. It is shown that the additivity rule along with the complex optical model potential rewritten by the concept of bonded atom can be used successfully to calculate the total cross section of electron－molecule scattering above 100eV, whereas the rule together with the complex optical model potential not rewritten by the concept of bonded atom is only successfully used above 300－500eV. So, the introduction of the bonded-atom concept in the complex optical potential can improve the accuracy of the total cross section calculations.     

Synthesis and study of photocatalytic activity of nanoscale quasi-one-dimensional Ti1 ? xVxO2 (0 ≤ x ≤ 0.13) and Zn1 ? xCoxO (0 ≤ x ≤ 0.3) oxides

A original method of synthesis of quasi-one-dimensional Ti_{1 − x} V _x (OCH₂CH₂O)₂ (0 ≤ x ≤ 0.13) and Zn_{1 − x} Co _x (HCOO)(HOCH₂CH₂O) (0 ≤ x ≤ 0.3) has been developed. The synthesis products were used as a basis for nanoscale extended Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O oxides. The compounds obtained and products of their thermolysis were investigated by X-ray diffraction, microscopy, IR spectroscopy, thermogravimetry, and chemical analysis; the shape and size of particles were determined by scanning electron microscopy. The good prospects of Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O solid solutions as photocatalysts for hydroquinone oxidation are shown.     

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.     

CO2对Ba0.5Sr0.5Co0.8Fe0.2O3−δ表面氧交换的影响

采 用 了 一 种 新 的 脉 冲 同 位 素 交 换 技 术 , 研 究了CO₂对Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ(BSCF)的表面氧交换动力学的毒害作用．当BSCF暴露于CO₂时,由于在材料表面形成了碳酸盐,其表面交换率严重降低．在低CO₂浓度(1%)时,毒害作用从375 oC开始,并且随着温度的上升而变得更加明显．同时,表面交换动力学的下降导致BSCF在CO₂条件下氧渗透性能快速下降．     

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

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     

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.     

Ferromagnetic resonance and magnetic microstructure in nanocomposite films of Cox(SiO2)1 ? x and (CoFeB)x(SiO2)1 ? x

This paper reports on the results of the investigation of the relation between the magnetic microstructure and ferromagnetic resonance (FMR) in ferromagnetic metal-insulator composites by using granular alloys (Co₄₁Fe₃₉B₂₀) _x (SiO₂)_{1 − x} and Co _x (SiO₂)_{1 − x} as an example. A comparative analysis of the properties of FMR spectra and parameters of random magnetic anisotropy leads to correlations between these quantities. It has been found that the main mechanism that determines the FMR line width in the films under investigation is the exchange narrowing mechanism.     

Electrical conductivity and magnetic properties of La1 ? xCaxMn1 ? yFeyO3 ceramic samples (x = 0.67, y = 0, 0.05)

The temperature dependences of the magnetic susceptibility χ(T) and the electrical resistivity ρ(T) of ceramic samples of La_{1 − x} Ca _x MnO₃ with x = 0.67 (LCMO) and La_{1 − x} Ca _x Mn_{1 − y} Fe _y O₃ with x = 0.67 and y = 0.05 (LCMFO) are investigated in magnetic fields B = 50–10⁵ G and the temperature range T = 4.2–400 K. Both samples undergo a transition from the paramagnetic state to a state with charge (orbital) ordering (CO) at temperatures T _CO ≈ 272 K for LCMO and T _CO ≈ 222 K for LCMFO. The behavior of the paramagnetic phase in the temperature range 320–400 K for LCMO and 260–400 K for LCMFO is described by the Curie-Weiss law with effective Bohr magneton numbers p _eff = 4.83 μ_B (LCMO) and 4.77 μ_B (LCMFO), respectively. The disagreement between the observed positive Weiss temperatures (θ ≈ 175 K (LCMO) and θ ≈ 134 K (LCMFO)) and negative Weiss temperatures required for the antiferromagnetic ground state can be explained by the phase separation and transition to the charge-ordered state. The magnetic irreversibility for T < T _CO is accounted for by the existence of a mixture of the ferromagnetic and antiferromagnetic phases, as well as the cluster glass phase. At low temperatures, doping with iron enhances the frustration of the system, which manifests itself in a more regular behavior of the decay rate of the remanent magnetization with time. The temperature dependence of the electrical resistivity in the range of the charge-ordered phase conforms to the variable-range hopping model. The behavior of the electrical resistivity is governed by the complex structure of the density of localized states near the Fermi level, which includes a soft Coulomb gap Δ = 0.464 eV for LCMO and 0.446 eV for LCMFO. It is established that the ratio between the localization radii of charge carriers a for LCMFO and a _und for LCMO is a/a _und = 0.88. Original Russian Text ? V.S. Zakhvalinskiĭ, R. Laiho, T.S. Orlova, A.V. Khokhulin, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 1, pp. 61–68.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.