Electrical properties of pure and Li2O-doped CuO/Fe2O3 system precalcined at different temperatures

The electrical properties of pure and Li₂O-doped CuO/Fe₂O₃ solids were investigated. Pure and variously doped solids were subjected to thermal treatment at 1073–1273 K and the amount of dopant was varied between 0.84 to 3.36 mol%. The effect of precalcination temperature and amount of Li₂O added on the electrical conductivity σ, activation energy E_a and dielectric constant * were studied. The variation of ′ and ″ as a function of frequency for pure and variously doped solids precalcined at different temperatures was also investigated. The results obtained were discussed.     

Description peculiarities of viscous and elastic properties of dense molecular liquids on the basis of the model of Lennard-Jones (n−6) fluid

Results previously obtained in molecular dynamics experiment with Lennard-Jones (n−6) (L-J (n−6)) fluid were applied for the determination of viscous and elastic properties of real molecular fluids (shear viscosity coefficient and pressure). Parameters σ and of real liquids (liquid hydrocarbons) were determined by fitting p–ρ–T data of model fluids to experimental p–ρ–T data of real liquids. Using the data obtained in that way, parameters σ and viscous and elastic characteristics of real liquids were determined. The comparison of experimental and calculated viscous and elastic characteristics revealed lesser dependence of viscous properties from n in comparison with elastic properties.     

BaO-Li2O-B2O3三元系中BaB2O4-Li2B2O4和BaB2O4-Li2O截面相平衡关系的研究

本文用X射线和差热分析方法对BaO-Li₂O-B₂O₃三元系中的两个截面:BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O作了研究。在BaB₂O₄-Li₂B₂O₄赝二元系中发现了一个新的化合物4BaB₂O₄·Li₂B₂O₄。化合物在930±3℃由包晶反应形成,并与Li₂B₂O₄形成共晶反应。共晶温度为797±3℃,共晶点组分为79mol％Li₂B₂O₄。在BaB₂O₄-Li₂O截面中也存在化合物4BaB₂O₄·Li₂B₂O₄,其包晶反应温度从930±3℃随Li₂O含量增加下降到908±3℃。在组分60mol％Li₂O处形成另一个新的化合物2BaB₂O₄·3Li₂O。该化合物在630±3℃也是由包晶反应形成,并与Li₂O和Li₂CO₃分别形成共晶反应,共晶温度分别为400±3℃和612±3℃。在BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O体系中都没有观察到固溶体。用计算机程序分别对化合物4BaB₂O₄·Li₂B₂O₄和2BaB₂O₄·3Li₂O的X射线粉末衍射图案进行了指标化,其结果:4BaB₂O₄·Li₂B₂O₄的空间群为Pmma,a=13.033?,b=14.630?,c=4.247?,每个单胞包含两个化合式单位;2BaB₂O₄·3Li₂O的空间群为Pmmm,a=4.814?,b=9.897?,c=11.523?,每个单胞也含有两个化合式单位。 关键词：     

Anisotropic dielectric properties of PbYb1/2Ta1/2O3 single crystals

PbYb_1/2Ta_1/2O₃ single crystals were obtained for the first time. They were grown by the flux method. The PbOPbF₂B₂O₃ system was used as a solvent. Dielectric investigations were carried out in 1 0 0_c, 1 1 0_c and 1 1 1_c pseudocubic directions. These studies pointed to anisotropy of dielectric properties. Frequency-independent ε′(T) and ε″(T) maxima related to the antiferroelectric–paraelectric (AFE—PE) phase transition are observed for all directions at 562 K. The frequency-dependent ε′(T) and ε″(T) maxima near 400 K related to the ferroelectric (FE)–AFE phase transition are observed only in 1 1 1_c direction. The hysteresis loops were observed in this direction only. These results point that ferroelectric relaxor properties appear only in 1 1 1_c direction. We propose to consider the ferroelectric phase as ferrielectric one.     

Investigation of the static and dynamic magnetic properties of CoFe2O4 nanoparticles

We have investigated the magnetic behavior of cobalt ferrite nanoparticles with a mean diameter of 7.2 nm. AC susceptibility of colloidal cobalt ferrite nanoparticles was measured as a function of temperature T from 2 to 300 K under zero external DC field for frequencies ranging from f=10 to 10,000 Hz. A prominent peak appears in both χ′ and χ″ as a function of T. The peak temperature T₂ of χ″ depends on f following the Vogel–Fulcher law. The particles show superparamagnetic behavior at room temperature, with transition to a blocked state at T_B^m94 K in ZFC and 119 K in AC susceptibility measurements, respectively, which depends on the applied field. The saturation magnetization and the coercivity measured at 4.2 K are 27.3 emu/g and 14.7 kOe, respectively. The particle size distribution was determined by fitting a magnetization curve obtained at 295 K assuming a log-normal size distribution. The interparticle interactions are found to influence the energy barriers yielding an enhancement of the estimated magnetic anisotropy, K=6×10⁶ erg/cm³. Mössbauer spectra obtained at higher temperatures show a gradual collapse of the magnetic hyperfine splitting typical for superparamagnetic relaxation. At 4.2 K, the Mössbauer spectrum was fitted with two magnetic subspectra with internal fields H_int of 490, 470 and 515 kOe, corresponding to Fe³⁺ ions in A and B sites.     

Analysis of frequency-dependent series resistance and interface states of In/SiO2/p-Si (MIS) structures

In this work, the investigation of the interface state density and series resistance from capacitance–voltage (C–V) and conductance–voltage (G/ω−V) characteristics in In/SiO₂/p-Si metal–insulator–semiconductor (MIS) structures with thin interfacial insulator layer have been reported. The thickness of SiO₂ film obtained from the measurement of the oxide capacitance corrected for series resistance in the strong accumulation region is 220 Å. The forward and reverse bias C–V and G/ω−V characteristics of MIS structures have been studied at the frequency range 30 kHz–1 MHz at room temperature. The frequency dispersion in capacitance and conductance can be interpreted in terms of the series resistance (R_s) and interface state density (D_it) values. Both the series resistance R_s and density of interface states D_it are strongly frequency-dependent and decrease with increasing frequency. The distribution profile of R_s–V gives a peak at low frequencies in the depletion region and disappears with increasing frequency. Experimental results show that the interfacial polarization contributes to the improvement of the dielectric properties of In/SiO₂/p-Si MIS structures. The interface state density value of In/SiO₂/p-Si MIS diode calculated at strong accumulation region is 1.11×10¹² eV⁻¹ cm⁻² at 1 MHz. It is found that the calculated value of D_it (≈10¹² eV⁻¹ cm⁻²) is not high enough to pin the Fermi level of the Si substrate disrupting the device operation.     

Formation of Li2O in a chemically Li-intercalated V2O5 xerogel

We studied the electronic structure of a chemically Li-intercalated V₂O₅ xerogel. The technique used in the study was V 2p and O 1s X-ray absorption spectroscopy (XAS). The V ions in the as-prepared V₂O₅ xerogel are mostly in a pentavalent V⁵⁺ state. The spectra show that the V ions are partially reduced to V⁴⁺ and V³⁺ states upon Li intercalation. The results also show that low Li intercalation (x<1) affects mostly O 2p–V 3d mixed states, whereas for higher Li intercalation (x>1), this mechanism saturates and leads to Li₂O formation.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

Thermal-expansion anomalies and spontaneous magnetostriction of Lu2Fe17−xSix intermetallic compounds

The thermal expansion of Lu₂Fe_17−xSi_x solid solutions has been measured by X-ray powder diffraction. The magnetic ordering in all compounds within the homogeneity range (x3.4) is accompanied by a large spontaneous volume magnetostriction, distributed anisotropically over the principal axes of the hexagonal crystal structure. The volume effect ω_s in the ground state reaches 14.7×10⁻³ in Lu₂Fe₁₇ and decreases monotonously to 8.9×10⁻³ for x=3.4, following the reduction of magnetic moment. Despite a still large ω_s, the Invar behavior observed in Lu₂Fe₁₇ changes to a positive thermal expansion for x>1 due to an increasing Curie temperature.     

Phase transition in Pb4.9A0.1Ge2.7Si0.3O11 (A=Ca,Sr,Ba) ferroelectrics

Polycrystalline samples of modified lead germanate Pb_4.9A_0.1Ge_2.7Si_0.3O₁₁ (A=Ca,Sr,Ba) have been prepared by solid-state reaction technique. X-ray studies have been carried out to check the formation of single-phase composition and to obtain preliminary structural data. Measurements of dielectric permittivity () and loss (tan δ) have been studied both as a function of frequency (10²–10⁴ Hz) and temperature (room temperature to 180°C). Phase transition was observed in all three cases but with different T_c value. From the plots of conductivity vs. temperature using dielectric data, collected at 10 kHz activation energy was calculated to investigate the conduction mechanism in them.     

Characterization of nonstoichiometric nickel manganite spinels NixMn3−x□3δ/4O4+δ by temperature programmed reduction

Cation deficient spinels Ni_xMn_3−x□_3δ/4O_4+δ (0≤x≤1) have been prepared by thermal decomposition of mixed oxalates Ni_x/3Mn_(3−x)/3(C₂O₄)·nH₂O in air at 623 K. They have been characterised by temperature programmed reduction (TPR) under H₂, the reaction being followed by gravimetric and powder X-ray diffraction measurements. It has been shown that TPR proceeds in several steps. The first steps correspond to the loss of nonstoichiometric oxygen leading to the formation of a stoichiometric oxide. During the following stages the manganese cations are reduced, causing the spinel structure to be destroyed, and the formation of solid solution of NiO in a cubic MnO. Subsequently, Ni²⁺ cations undergo a reduction to metallic nickel, and, finally, a mixture of nonstoichiometric MnO_1−δ and metallic nickel is formed. These oxides contain a high level of vacancies which vary with the nickel content with a maximum of δ≈1 near x=0.6. This nonstoichiometry is ascribed both to the presence of Ni³⁺ and excess of Mn⁴⁺.     

Lithium insertion into Li4V3O8

The lithium insertion characteristics of lithium vanadate, Li₄V₃O₈, were investigated using LiV₃O₈ prepared by the precipitation technique as the starting material. The Li₄V₃O₈ phase was formed by lithiation over x=1.5 in Li_1+xV₃O₈, and the diffusion of lithium in this phase determined the reaction rate of insertion more than x=1.5. Improvement of insertion kinetics in the Li₄V₃O₈ phase extended the lithium insertion limit from x=3.2 to x=4.0, compared with the case of LiV₃O₈ by conventional high temperature synthesis. Lithium insertion proceeds as the single-phase reaction in the range of 3.2<x<4.0.     

Effect of γ-radiation on the phase transition temperature of Li0.5(NH4)0.5SO4

Polycrystalline lithium-ammonium sulphate samples were subjected to X-ray diffraction analysis for determining the lattice parameters of the prepared mixed crystals. The compositions of the samples were determined using X-ray microanalysis.

The Li_0.5(NH₄)_0.5SO₄ samples were irradiated with different doses of γ-radiation in order to investigate the effect of this ionizing radiation on the phase transition temperatures T_c1 and T_c2. The temperature dependence of the d.c. resistivity ρ_d.c. and dielectric constant of irradiated samples showed (i) a shift of T_c1 to higher temperatures; (ii) a shift of T_c2 to lower temperatures; and (iii) the appearance of a new anomaly near 128°C at moderately high γ-doses. The mechanisms giving rise to this behaviour are discussed.     

Dielectric and magnetic properties of xNiFe2O4+(1−x)Ba0.9Sr0.1TiO3 composites

Magnetoelectric composites, namely, xNiFe₂O₄+(1−x)Ba_0.9Sr_0.1TiO₃ were prepared by standard double sintering ceramic method. The X-ray diffraction analysis was carried out to check the phases formed during sintering and to calculate the lattice parameters. Scanning electron microscope (SEM) micrographs were taken to understand the microstructure of the samples. The dielectric constant (ε′) and loss tangent (tan δ) were measured as a function of frequency in the frequency range 100 Hz–1 MHz. Variation of dielectric constant and loss tangent with temperature and composition has been reported. The hysteresis measurements were done to determine saturation magnetization (M_S) and coersivity (H_c). The variation of saturation magnetization and magnetic moment is interpreted in terms of composition.     

Ionic conduction and dielectric relaxation in Ag/Na ion-exchanged aluminosilicate glasses: mixed mobile ion effect and KWW relaxation

Ag⁺/Na⁺ ion-exchanged aluminosilicate glasses with uniform concentration profiles were prepared, and their electrical conductivities were investigated as functions of the ion-exchange ratio and the initial glass compositions. In the case of the ion-exchanged glasses of x20Ag₂O–(1−x)20Na₂O–10Al₂O₃–70SiO₂ in mol%, the conductivity, σ, and its activation energy, E_σ, showed a minimum and a maximum at the same ion-exchange ratio x=0.3, respectively, and the mixed mobile ion effect (MMIE) was observed. The fully ion-exchanged sample attained σ=3.5×10⁻⁵ S/cm at 200 °C, which was 1.5 orders of magnitude larger than that of initial glass. In the case of x25Ag₂O–(1−x)25Na₂O–25Al₂O₃–50SiO₂, the mixed mobile ion effect was also observed at x=0.5. The maximum conductivity of 2×10⁻⁴ S/cm at 200 °C was obtained in the fully ion-exchanged glass sample.

The electric relaxation analysis was also conducted on both systems, and Kohlrausch–Williams–Watts (KWW) fractional exponent β was obtained as a function of x. The decrease of β was observed near x≈0.3 in the former system, while that of the later system was independent of the ion-exchange ratio. Based on the structural analysis results, the observed behaviors were investigated from the point of view of the occupation of Ag⁺ ions on the non-bridging oxygen-site (NBO-site) and the charge compensation-site (CC-site) of AlO₄ tetrahedral unit.     

Ionic conduction in dilute pseudo-binary systems CuBr–Cu2Se

Ionic conductivity, σ_i, of dilute pseudobinary alloys (CuBr)_1−x(Cu₂Se)_x (x≤0.1) in their γ-phase has been measured by an ac method. The increase of the ionic conductivity propertional to x has been observed, which is attributed to interstitial ions brought by Cu₂Se dissolved in CuBr. It is found that the temperature dependence of mobility of interstitial ions, μ, evaluated by the relation Δσ_i/x=kμ (k is a constant) is bent at the temperature corresponding to the extrinsic–intrinsic transition of the based material CuBr.     

Lithium insertion to ReO3-type metastable phase in the Nb2O5–WO3 system

Lithium insertion to distorted ReO₃-type metastable solid solution Nb_xW_1−xO_3−x/2 (0≤x<0.25) has been studied by chemical and electrochemical methods. In the course of lithium insertion into tetragonal compounds, transition to a cubic phase was found to occur in the region where values of y (in Li_yNb_xW_1−xO_3−x/2) fall between 0.2 and 0.3, and the phase transition was found to depend on the conditions of the reaction. Changes in OCV and lattice parameters in tetragonal region (y<0.2) were discussed from the viewpoint of the ordering of lithium ions. Also, the component diffusion coefficient of lithium in tetragonal compounds Li_0.1Nb_xW_1−xO_3−x/2 (0≤x≤0.23) was found to increase with niobium content when x≤0.10, and to saturate at 4×10⁻⁹ cm²/s.     

Dielectric and modulus behavior of LiFe1/2Ni1/2VO4 ceramics

The polycrystalline sample of LiFe_1/2Ni_1/2VO₄ was prepared by a standard solid-state reaction technique and confirmed by X-ray diffractometry. LiFe_1/2Ni_1/2VO₄ has orthorhombic crystal structure whose dielectric and electric modulus properties were studied over a wide frequency range (100 Hz–1 MHz) at different temperatures (296–623 K) using a complex impedance spectroscopy (CIS) technique. The frequency and temperature dependence of dielectric constant (ε_r) and tangent loss (tan δ) of LiFe_1/2Ni_1/2VO₄ are studied. The variation of ε_r as a function frequency at different temperatures exhibits a dispersive behavior at low frequencies. The variation of the ε_r as a function of temperature at different frequencies shows the dielectric anomaly in ε_r at 498 K with maximum value of dielectric constant 274.49 and 96.86 at 100 kHz and 1 MHz, respectively. Modulus analysis was carried out to understand the mechanism of the electrical transport process, which indicates the non-exponential type of conductivity relaxation in the material. The activation energy calculated from electric modulus spectra is 0.38 eV.     

Lithium-7 NMR investigation of electrochemical reaction of lithium with SnO

We report on solid state ⁷Li NMR measurements of electrochemically lithiated SnO. At low Li contents (Li/SnO≤2), the results are consistent with the formation of amorphous Li₂O. For Li/SnO ratio of 4.3, in addition to the amorphous Li₂O phase, there are at least two distinct Sn/Li alloy environments which are similar to those observed in a reference Li_2.3Sn alloy. However the Li⁺ environments in a sample with Li/SnO ratio equal to 6.4 and an Li_4.4Sn reference alloy differ markedly. The NMR data are thus consistent with the simple model of Li insertion proposed by other groups, involving the formation of Li₂O and Li_xSn alloys (SnO+xLi→Li₂O+Li_x−2Sn), at low and intermediate Li contents. At high Li content, however, the Li_x−2Sn alloy structure is significantly different in the electrochemically lithiated SnO material, compared to that in the reference alloy.