Synthesis and characterization of a NASICON phase of variable composition Na1 − x Ni1 − x Sc1 + x (MoO4)3 (0 ≤ x ≤ 0.5)

Subsolidus phase ratios in the Na₂MoO₄-NiMoO₄-Sc₂(MoO₄)₃ system have been studied using X-ray diffraction, differential thermal analysis, and vibrational spectroscopy. A phase of variable composition Na_{1 ? x} Ni_{1 ? x} Sc_{1 + x} (MoO₄)₃ (0 ≤ x ≤ 0.5) having NASICON structure (space group \(R\bar 3c\) ) and a triple molybdate crystallizing in triclinic system (space group \(P\bar 1\) ) have been obtained. The high conductivity of Na_{1 ? x} Ni_{1 ? x} Sc_{1 + x} (MoO₄)₃ allows the phase of variable composition to be regarded as a promising sodiumion-conductive solid electrolyte.     

Vibrational spectra and electrophysical properties of a NASICON phase of variable composition Na1 − x Co1 − x Sc1 + x (MoO4)3 (0 ≤ x ≤ 0.5)

Subsolidus phase ratios of the Na₂MoO₄-CoMoO₄-Sc₂(MoO₄)₃ system have been studied by X-ray diffraction, differential thermal analysis, and vibrational spectroscopy. A phase of variable composition Na_{1 ? x} Co_{1 ? x} Sc_{1 + x} (MoO₄)₃, 0 ≤ x ≤ 0.5 having NASICON structure (space group \(R\bar 3c\) ) and triple molybdate NaCo₃Sc(MoO₄)₅ crystallizing in triclinic system (space group \(P\bar 1\) ) have been obtained. The high conductivity of Na_{1 ? x} Co_{1 ? x} Sc_{1 + x} (MoO₄)₃ allows the phase of variable composition to be regarded as a promising sodium-ion conducting solid electrolyte.     

Ionic conductivity and crystal chemistry of ramsdellite type compounds,Li2+x(LixMg1−xSn3)O8, 0 ≤ x ≤ 0.5 and Li2Mg1−xFe2xSn3−xO8, 0 ≤ x ≤ 1

Solid solution phases Li_2+x(Li_xMg_1−xSn₃)O₈: 0 ≤ x ≤ 0.5 and Li₂Mg_1−xFe_2xSn_3−xO₈: 0 ≤ x ≤ 1, both with ramsdellite type structure, have been synthesized by solid state reaction at 1773 and 1523 K, respectively. The relationship of the ramsdellite structure to the recently illustrated, tetragonal-packed structure is given. The Li_2+x(Li_xMg_1−xSn₃)O₈ solid solutions exhibit conductivities 4 × 10⁻⁶–5 × 10⁻⁴ (Ω cm)⁻¹ at 573 K and corresponding activation energies, 0.93−0.74 eV. The highest conductivity was observed for Li_2.3(Li_0.3Mg_0.7Sn₃)O₈, x = 0.3. In the solid solution series Li₂Mg_1−xFe_2xSn_3−xO₈, the highest conductivity was exhibited by Li₂Fe₂Sn₂O₈, 2 × 10⁻⁵ (Ω cm)⁻¹ at 573 K.     

Nonstoichiometry and structural intergrowth in the CaFexMn1−xO3−y (0 ≤ x ≤ 1) system

An electron diffraction and microscopy study of the CaFe_xMn_1−xO_3−y system treated at 1100°C in air has been performed. An increase of y is accompanied by an increase of the cubic perovskite substructure parameter, the nonstoichiometry being accommodated in several ways. The system contains two solid solutions of the perovskite-type (P) and of the brownmillerite-type (B) and also an intermediate phase (x = 0.6) which makes disordered intergrowth with the B-type solid solution. These results are discussed in terms of multitwinning, randomly dispersed oxygen deficiency, and ordered and disordered intergrowth formation.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Electroconductivity and nature of ion transfer in La1 − x Sr x Sc1 − y Mg y O3 − α system (0.01 ≤ x = y ≤ 0.20) in dry and humid air

The conductivity and ion and proton transfer numbers were measured in La_{1 ? x} Sr _x Sc_{1 ? y} Mg _y O_{3 ? α} system (x = y = 0.10–0.20). The partial conductivities (total ion, proton, oxygen, hole) and their effective activation energies were calculated. The measurements were carried out in air with respect to humidity (pH₂O = 0.04?2.65 kPa) within the temperature range from 630 to 920°C.     

Magnetic properties of (Cu0.5Ga0.5)1 − x Fe x Cr2S4 solid solutions

Magnetic properties are studied and a magnetic phase diagram is constructed for (Cu_0.5Ga_0.5)_{1 ? x} Fe _x Cr₂S₄ solid solutions formed between chromium chalcogenide spinels (Cu_0.5Ga_0.5)Cr₂S₄ and FeCr₂S₄.     

Synthesis and properties of fuel cell anodes based on (La0.5 + x Sr0.5 − x )1 − y Mn0.5Ti0.5O3 − δ (x = 0–0.25, y = 0–0.03)

Results are presented of studying electrochemical properties of perovskite-like solid solutions (La_{0.5 + x} Sr_{0.5 ? x} )_{1 ? y} Mn_0.5Ti_0.5O_{3 ? δ} (x = 0–0.25, y = 0–0.03) synthesized using the citrate technique and studied as oxide anodic materials for solid oxide fuel cells (SOFC). X-ray diffraction (XRD) analysis is used to establish that the materials are stable in a wide range of oxygen chemical potential, stable in the presence of 5 ppm H₂S in the range of intermediate temperatures, and also chemically compatible with the solid electrolyte of La_0.8Sr_0.2Ga_0.8Mg_0.15Co_0.05O_{3 ? δ} (LSGMC). It is shown that transition to a reducing atmosphere results in a decrease in electron conductivity that produced a significant effect on the electrochemical activity of porous electrodes. Model cells of planar SOFC on a supporting solid-electrolyte membrane (LSGMC) with anodes based on (La_0.6Sr_0.4)_0.97Mn_0.5Ti_0.5O_{3 ? δ} and (La_0.75Sr_0.25)_0.97Mn_0.5Ti_0.5O_{3 ? δ} and a cathode of Sm_0.5Sr_0.5CoO_{3 ? δ} are manufactured and tested using the voltammetry technique.     

Electron microscopy study of the “cubic” perovskite phase SrFe1−xVxO2.5+x (0.05 ≤ x ≤ 0.1)

The oxygen-deficient “cubic” perovskite phase SrFe_1−xV_xO_2.5+x (0.05 ≤ x ≤ 0.10) quenched from 1473 K has been investigated by electron microscopy. Samples show a microdomain structure composed of ordered grains less than 20 nm. Oxygen vacancies form a brownmillerite-type superlattice in each microdomain, while six orientation variants have been observed within a particle; the oxygen vacancies in one domain are stringed along one of the six possible 〈110〉_C directions of the cubic host lattice. The domain size decreases as x or oxygen content increases. Vacancy arragements within the domains observed in high-resolution lattice images indicate that good structural coherence exists between microdomains and that a basic cubic perovskite skeleton is framed throughout a particle; they also suggest that vacancy content decreases in the boundary regions.     

La0.7Mg0.3(Ni1-xCox)3.5 (0≤x≤0.5)储氢合金电化学性能

近年来,具有AB2和AB5复合结构的LaNi3系和La2Ni7系储氢材料由于具有较高的储氢量而引起了人们的关注[1]. 它们可在较温和条件下快速吸放氢, 且理论吸氢量分别为LaNi5的1.25倍及1.11倍.     

X-ray photoelectron spectroscopy investigation of perovskites La1−x Sr x FeO3−y (0 ≤x < 1.0), prepared via a mechanochemical route

Perovskite-structure oxides La_1?x Sr _x FeO_3?y (x = 0, 0.2, 0.6, 1) were synthesized by the mechanochemical method. In order to refine the stoichiometric composition and the charge state of ions, these samples were studied by X-ray photoelectron spectroscopy (XPS). An investigation of perovskites with x = 0, 0.2, and 0.6 in air at room temperature showed that these samples do not contain oxygen vacancies (y = 0), i.e., they are fully oxidized. Hence, to produce electrical neutrality, these samples should contain iron(4+) cations in an amount proportional to the degree of substitution (x) of strontium(2+) for lanthanum(3+). However, no Fe⁴⁺ cations were found in the oxides. All perovskites contain only Fe³⁺ cations, oxygen ions O^2? along with oxygen ions with reduced electron density (O^?). These data provid evidence of the possible electron density redistribution from oxygen ions to iron cations. The fact that the oxides contain oxygen ions with reduced electron density suggests that weakly bound lattice oxygen in substituted perovskites is represented by O^? ions.     

Synthesis and electrical properties of variable-composition phases Rb1 − x A1 − x R1 + x (MoO4)3 (0 ≤ x ≤ 0.2; A = Mg, Mn, Co, Ni; R = Sc, Yb, Lu)

Subsolidus region of the ternary systems Rb₂MoO₄-AMoO₄-R₂(MoO₄)₃, in which variable-composition phases Rb_{1 ? x} A_{1 ? x} R_{1 + x} (MoO₄)₃ crystallizing in the monoclinic system (space group C2) are formed, was studied. Their crystallographic parameters were calculated; temperature dependences of the electrical conductivity, dielectric constant, and dielectric loss tangent were analized.     

Effect of hydration on conductivity of Ba4La x Ca2 − x Nb2O11 + 0.5x (x = 0.5, 1, 1.5, 2) phases

Substitution of Ca by La in initial cubic double perovskite Ba₄(Ca₂Nb₂)O₁₁[VO]₁ allowed obtaining phases with a similar structure with a lower content of structural oxygen vacancies, Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} [VO]_{1 ? 0.5x} (x = 0.5, 1, 1.5, 2). The impedance technique was used to measure the temperature dependences of conductivity in the atmosphere of dry and humid air. Transport numbers determined using the EMF method in an oxygen-air and water steam concentration cells point to the predominantly hole nature of conductivity in the high-temperature region (T > 600°C) and to predominance of proton conductivity in the low-temperature region. Activation energies of hole and proton conductivity were calculated. Thermogravimetric measurements were carried out under heating from 25 to 1000°C with simultaneous mass-spectrometric determination of evolved H₂O and CO₂. The properties of the studied Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} (x = 0.5, 1, 1.5, 2) phases were compared with the earlier studied Ba_{4 ? x} La _x (Ca₂Nb₂)O_{11 + 0.5x} phases with similar lanthanum content.     

Synthesis of sol–gel Na2Zr x Ti6−x O13 (0≤x≤1) materials and their performance in photocatalytic degradation of organic dyes

In this work we present the synthesis and characterization of four compositions of the solid solution with the general formula Na₂Zr _x Ti_6−x O₁₃ (0≤x≤1) which was prepared by a sol-gel method. The main goal of this work is to evaluate the influence of the incorporation of different amounts of zirconium into the binary phase Na₂Ti₆O₁₃ on two properties: the textural surface and E _g values. This titanate phase crystallizes in a monoclinic unit cell and is built into an octahedral TiO₆ framework forming a rectangular tunnel structure. Additionally, we have compared their photocatalytic performances in degradation of organic dyes under visible light. The heat-treated sol-gel samples were characterized by X-ray powder diffraction, N₂ physisorption, thermal analysis, UV and FT-IR spectroscopy. According to the X-ray powder diffraction results, the new ternary tunnel compound Na₂ZrTi₅O₁₃ was obtained as a single phase at 800°C. The cell parameters for the two end-member phases of that solid solution were refined to confirm that Zr ion was incorporated into the structural framework. This ternary compound had an E _g value of about 2.9 eV. The activity of all heat-treated Na₂ZrTi₅O₁₃ samples was tested in the photocatalytic degradation of methylene blue and Rhodamine B under visible light. The Na₂ZrTi₅O₁₃ calcined at 400°C showed the best performance with 95% of photodegradation of methylene blue and a half time t _1/2 of 15 min.     

Atoms state and interatomic interactions in perovskite-like oxides: XXXII. Formation of paramagnetic clusters in the La1−0.33x Ca0.33x Fe x Al1−x O3 and La1−0.33x Sr0.33x Fe x Al1−x O3 solid solutions

Calcium- and strontium-containing lanthanum orthoferrites have been studied using magnetic dilution method. It has been shown that the iron-atom clusters with competing ferro- and antiferromagnetic exchange interactions can exist. By using Mossbauer spectroscopy, Fe(IV) atoms have been found in the La_1?0.33x Ca_0.33x Fe_xAl_1?x O₃ solid solutions and Fe(III) atoms in two different surroundings have been found in the La_1?0.33x Sr_0.33x Fe _x Al_1?x O₃ solid solutions. The compositions of paramagnetic clusters stable at the infinite dilution have been proposed basing of the magnetic susceptibility and Mossbauer spectroscopy data.     

Radiation damage in Si1−x Ge x heteroepitaxial devices

Results are presented of an extended study on the induced lattice defects and their effects on the degradation of Si_1−x Ge _x devices, subjected to a 20 MeV alpha-ray, 1 MeV electron, 1 MeV fast neutron, and 20 and 86 MeV proton irradiations. The degradation of the electrical device performance increase with increasing fluence, while it decreases with increasing germanium content. In the Si_1−x Ge _x epitaxial layers, electron capture levels associated with an interstitial-substitutional boron complex are induced. The radiation source dependence of performance degradation is attributed to the difference of mass and the probability of nuclear collision for the formation of lattice defects.     

Longitudinal conductivity of thin films of La1 − x Sr x F3 − x solid solutions on glass ceramics

The longitudinal conductivity of La_{1 ? x} Sr _x F_{3 ? x} solid solution films (x = 0–0.24) with thicknesses of 40–260 nm grown on glass ceramics at temperatures from room temperature to 300°C and frequencies of 10^?1–10⁶ Hz was studied by impedance spectroscopy. The concentration dependence of film conductivity on the SrF₂ content had a maximum near x = 0.05. An equivalent circuit was constructed on the basis of the impedance plots to describe migration processes. The DC conductivity was evaluated for all samples under study. The activation energies were estimated from the temperature dependences of the DC conductivities of the films. The resulting dependences of electrophysical parameters were compared with those for bulk materials in terms of the relaxation conductivity model.     

Hydrogen content in proton-conducting perovskites CaZr1 − x Sc x O3 − x /2 (x = 0.0–0.2)

The hydrogen content in CaZr_{1 ? x} Sc _x O_{3 ? x/2} (x = 0.00–0.20) and BaZr_0.9Y_0.1O_3-α (for comparison) was studied by powder nuclear microanalysis. The samples were saturated with heavy water (D₂O) vapors at 350 and 400°C in air. The chemical expansion of the CaZr_0.95Sc_0.05O_3-α and BaZr_0.95Y_0.05O_3-α samples at 700°C was measured at different water vapor pressures. A model was suggested to explain the lowered hydrogen content in oxides based on CaZrO₃.     

LaNi_(3.8-x)Al_x(0≤x≤0.5)多相储氢合金的结构及电化学性能

采用真空电弧熔炼法制备了LaN i3.8-xA lx(0≤x≤0.5)储氢合金,并在氩气气氛中进行退火处理。通过X射线衍射(XRD),S ievert′s方法和电化学测试分别分析了合金的物相结构、储氢和电化学性能。研究结果表明:LaN i3.8-xA lx(0≤x≤0.5)合金主要由LaN i5,Ce2N i7,Pr5Co19和Ce5Co19型相组成。随着A l的变化,各相相丰度发生变化,而相丰度的变化影响了合金的滞后和吸/放氢平台压力。随着x的增加,LaN i3.8-xA lx(0≤x≤0.5)合金的放电容量先增大至270 mAh.g-1(x=0.3),然后缓慢降低;在x=0.3时合金显示出较好的充/放电循环稳定性。极化电阻和电化学交流阻抗则随着x的增加缓慢降低,交换电流密度增大,导致高倍率放电有所增大。