Study of superconducting state parameters of alkali–alkali binary alloys by a pseudopotential

A detailed study of the superconducting state parameters (SSP) viz. electron–phonon coupling strength λ, Coulomb pseudopotential μ^*, transition temperature T_C, isotope effect exponent and effective interaction strength N_OV of ten alkali–alkali binary alloys i.e. Li_1−xNa_x, Li_1−xK_x, Li_1−xRb_x, Li_1−xCs_x, Na_1−xK_x, Na_1−xRb_x, Na_1−xCs_x, K_1−xRb_x, K_1−xCs_x and Rb_1−xCs_x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ^* is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω₀ of alkali–alkali binary alloys.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

Perovskite-like system (Sr,La)(Fe,Ga)O3−δ: structure and ionic transport under oxidizing conditions

The maximum solid solubility of gallium in the perovskite-type La_1−xSr_xFe_1−yGa_yO_3−δ (x=0.40–0.80; y=0–0.60) was found to vary in the approximate range y=0.25–0.45, decreasing when x increases. Crystal lattice of the perovskite phases, formed in atmospheric air, was studied by X-ray diffraction (XRD) and neutron diffraction and identified as cubic. Doping with Ga results in increasing unit cell volume, while the thermal expansion and total conductivity of (La,Sr)(Fe,Ga)O_3−δ in air decrease with gallium additions. The average thermal expansion coefficients (TECs) are in the range (11.7–16.0)×10⁻⁶ K⁻¹ at 300–800 K and (19.3–26.7)×10⁻⁶ K⁻¹ at 800–1100 K. At oxygen partial pressures close to atmospheric air, the oxygen permeation fluxes through La_1−xSr_xFe_1−yGa_yO_3−δ (x=0.7–0.8; y=0.2–0.4) membranes are determined by the bulk ambipolar conductivity; the limiting effect of the oxygen surface exchange was found negligible. Decreasing strontium and gallium concentrations leads to a greater role of the exchange processes. As for many other perovskite systems, the oxygen ionic conductivity of La_1−xSr_xFe_1−yGa_yO_3−δ increases with strontium content up to x=0.70 and decreases on further doping, probably due to association of oxygen vacancies. Incorporation of moderate amounts of gallium into the B sublattice results in increasing structural disorder, higher ionic conductivity at temperatures below 1170 K, and lower activation energy for 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.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

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.     

Conductivity relaxation in zirconium fluoride glasses: effect of substitution of Zr by Y ions

The electrical conductivity and the conductivity relaxation of (55−x)ZrF₄–15BaF₂–xYF₃–30LiF glasses were studied in the temperature range from 300 K to just below the glass transition temperature and in the frequency range from 10 Hz to 2 MHz. No large changes in the conductivity were observed with the substitution of Zr⁴⁺ by the Y³⁺ ions. The activation energy remained almost constant up to 20 mol.% YF₃ content and increased for higher YF₃ content in the glass compositions. The frequency dependent conductivity was analyzed in terms of modulus formalism. The distribution parameter for the conductivity relaxation times remained almost unchanged with the substitution of YF₃ with an increase for 40 mol.% YF₃ content. The distribution of relaxation times of the present glasses was much broader than that for the YF₃-free zirconium fluoride glasses. The glass decoupling index decreased and the modulus relaxation rate increased with the increase of YF₃ content in the glass compositions with an anomaly for the composition having 20 mol.% YF₃ content.     

Niobium based tetragonal tungsten bronzes as potential anodes for solid oxide fuel cells: synthesis and electrical characterisation

In this paper we report studies on a range of niobate based tungsten bronzes, with a view to analysing their potential as anode materials in SOFCs. Six systems were studied, (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃, Sr_0.6−xLa_xTi_0.2+xNb_0.8−xO₃, (Sr_0.4−xBa_x)Na_0.2NbO₃, (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃, Ba_0.5−xA_xNbO₃ (A=Ca, Sr), and Ba_0.3NbO_2.8, and the electrical conductivities were examined over a range of oxygen partial pressures (10⁻²⁰–1 bar). All the systems showed good conductivity in low oxygen partial pressures, with values as high as 8 S cm⁻¹ at 930°C (P(O₂)=10⁻²⁰ bar). As the oxygen partial pressure was raised the conductivity dropped showing in most cases an approximate [P(O₂)]^−1/4 dependence and good re-oxidation kinetics. Of all the samples studied the (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃ and (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃ systems appear most promising for potential use as anode materials in SOFCs.     

The third-order optical nonlinearity of The pyrochlore phase 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 thin film on quartz

The xPb(Mg_1/3Nb_2/3)O₃–(1−x)PbTiO₃ (PMNT) (with x=0.7) thin film is prepared on quartz substrates prepared using a sol–gel process. The PMNT thin film has a well-crystallized pyrochlore phase structure. The sign and magnitude of both real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ of the thin film have been determined by the Z-scan technique performed at 800 nm with a femtosecond laser. The nonlinear refraction index coefficient γ, the nonlinear absorption coefficient β of the thin film are 1.37×10⁻¹² cm²/W and −6.73×10⁻⁸ m/W, respectively. The real and imaginary part of the third-order nonlinear susceptibility of the film are 1.06×10⁻¹⁷ and −1.65×10⁻¹⁹ m²/V², respectively. The results suggested that the nonlinearity is dominated by the refractive for the film.     

An electrochemical investigation of Li intercalation in the sol-gel LiMn2O4 spinel oxide

An alternative approach for obtaining the LiMn₂O₄ spinel phase is provided by the use of the sol-gel method in aqueous solution. The main electrochemical properties of the sol-gel LiMn₂O₄ phase are reported. In addition to chronopotentiometric and voltammetric experiments, the kinetics of the electrochemical insertion–extraction of lithium in Li_xMn₂O₄ (0.25<x<1) has been investigated using ac impedance spectroscopy. The strong variation of the chemical diffusion coefficient D_Li vs x, in the range 10⁻⁸–10⁻¹¹ cm² s⁻¹ (D_Li is found to be maximum for x=0.55) is critically discussed.     

Ionic conduction properties of layer-type oxides NaxMx/2Ti1−x/2O2 (M=Ni, Co; 0.60≤x≤1.0)

Layer-type oxide Na_xM_x/2^IITi_1−x/2^IVO₂ (M=Co, Ni; 0.60≤x≤1.0) has been prepared by solid state reactions. In both series, two structural variants of type -NaFeO₂ (O3) and β-RbScO₂ (P2) have been obtained consecutively as x decreases with a borderline composition around x_c0.7. With the decrease of x, the ionic conductivity has been found to increase up to 8.4×10⁻² S cm⁻¹ at 770 K (Na_0.67Co_0.33Ti_0.67O₂). Compositions of P2 have been found to exhibit the conductivity values two to five times greater than those of O3, primarily due to the larger rectangular threshold available for the diffusion of Na⁺ ions. Such a structural effect has also been considered to depend on the polarizability of alkali ion. HT-XRD and ²³Na-NMR data of Na_0.67Co_0.33Ti_0.67O₂ strongly suggest that the diffusion of Na⁺ ion is deeply related with the local distortion of trigonal prismatic sites, leading to the change of activation energy around 430 K.     

Thermal vibration in superionic conducting glass 5Agl–3Ag2O–2V2O5

The X-ray diffraction measurement for superionic conducting glass 5Agl–3Ag₂O–2V₂O₅ was carried out at 12, 100, 200 and 290 K. The temperature dependence of structure factor S(Q) of 5Agl–3Ag₂O–2V₂O₅ has been discussed based on the theoretical treatment that includes thermal vibration of atoms in noncrystalline materials. The effective overall Debye–Waller temperature parameter B increases with the increase of temperature.     

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⁺.     

Effect of WO3 on the spectroscopic properties in Er/Yb co-doped bismuth–borate glasses

The spectroscopic properties of Er³⁺/Yb³⁺ co-doped Bi₂O₃–B₂O₃–WO₃ (BBW) glasses were analyzed and discussed. The effect of WO₃ content on the absorption spectra, the Judd–Ofelt parameters Ω_t (t=2, 4, 6), emission spectra and the lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition were also investigated. With the substitution of WO₃ for B₂O₃, the measured lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition increase from 0.98 to 1.31 ms and from 38.2% to 49.2%, respectively. The effective width of emission band and the emission cross-section both decrease slightly. And the emission spectra is analyzed via the different curve (σ_e−σ_a) of BBW glasses, the influence of OH⁻is also discussed.     

Material design of new lithium ionic conductor, thio-LISICON, in the Li2S–P2S5 system

A new lithium ionic conductor of the thio-LISICON (LIthium SuperIonic CONductor) family was found in the binary Li₂S–P₂S₅ system; the new solid solution with the composition range 0.0≤x≤0.27 in Li_3+5xP_1−xS₄ was synthesized at 700 °C and characterized by X-ray diffraction measurements. Its electrical and electrochemical properties were studied by ac impedance and cyclic voltammetry measurements, respectively. The solid solution member at x=0.065 in Li_3+5xP_1−xS₄ showed the highest conductivity value of 1.5×10⁻⁴ S cm⁻¹ at 27 °C with negligible electronic conductivity and the activation energy of 22 kJ mol⁻¹ which is characteristic of high ionic conduction state. The extra lithium ions in Li₃PS₄ created by partial substitution of P⁵⁺ for Li⁺ led to the large increase in ionic conductivity. In the solid solution range examined, the minimum conductivity was obtained for the compositions, Li₃PS₄ (x=0.0 in Li_3+5xP_1−xS₄) and Li₄P_0.8S₄ (x=0.2 in Li_3+5xP_1−xS₄); this conductivity behavior is similar to other thio-LISICON family with the general formula, Li_xM_1−yM_y′S₄ (M=Si, Ge, and M′=P, Al, Zn, Ga, Sb). Conduction mechanism and the material design concepts are discussed based on the conduction behavior and the structure considerations.     

Investigation of 1.3 μm emission in Nd-doped bismuth-based oxide glasses

Nd₂O₃-doped 43Bi₂O₃–xB₂O₃–(57−x)SiO₂–1.0Nd₂O₃ (x=57, 47, 39, 28.5, 19.5, 10, 0 mol%) bismuth glasses were prepared by the conventional melt-quenching method, and the Nd³⁺: ⁴F_3/2→⁴I_13/2 fluorescence properties had been studied in an oxide system Bi₂O₃–B₂O₃–SiO₂. The Judd–Ofelt analysis for Nd³⁺ ions in bismuth boron silicate glasses was also performed on the basis of absorption spectrum, and the transition probabilities, excited-state lifetimes, the fluorescence branching ratios, quantum efficiency and the stimulated emission cross-sections of ⁴F_3/2→⁴I_13/2 transition were calculated and discussed. The stimulated emission cross-sections of 1.3 μm were quite large due to a large refractive index of the host. Although the effective bandwidths decreased with increasing SiO₂ content, quantum efficiencies and stimulated emission cross-sections enhanced largely with increasing SiO₂ content.     

Electric conductivity and relaxation in ZnF2–AlF3–PbF2–LiF glasses

The electric conductivity of ZnF₂–AlF₃–PbF₂–LiF glasses has been studied in the frequency range 10 Hz–2 MHz and in the temperature range from 300 K to just below the glass transition temperature. The conductivity decreases with the increase in the LiF content in the composition, which results from the trapping of F⁻ ions by Li⁺ ions. Small values of the stretching exponent β are observed for the present glasses. The value of the decoupling index decreases with an increase in LiF content, consistent with the composition dependence of the conductivity.     

Davydov splitting and two-photon excitation of cadmium tungstate (CdWO4) single crystal phosphorescence

Phosphorescence characteristics of CdWO₄ excited by one-photon (λ = 308 nm) and two-photon (λ = 570–590 nm) processes were measured. A Davydov splitting of 120 ± 20 cm⁻¹ was obtained in the phosphorescence spectra, suggesting a diffusion coefficient of about 1.2 × 10⁻² cm² s⁻¹, and a diffusion length of about 3.1 × 10⁻⁴ cm for the room temperature measured lifetime of 8μs. The phosphorescence quantum efficiency was less than 2% at low temperatures (only 0.25% at room temperature), indicating that the dominant decay mechanism was radiationless. The radiative lifetime was thus estimated as 1–2 ms. The two-photon phosphorescence excitation is characterized by an absorption cross-section of the order of 10⁻⁴⁹cm⁴s.     

Preparation and characterization of superionic materials in a new mixed system (Cu(1−x)AgxI)–(Ag2O)–(P2O5), (0.05≤x≤0.25)

In this paper attempts have been made to prepare superionic glassy electrolytes in the mixed system 30(Cu_(1−x)Ag_xI)–46.66(Ag₂O)–23.33(P₂O₅), where x=0.05, 0.1, 0.15, 0.2 and 0.25, respectively, using the melt quenching process. The solid samples were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy and silver ionic transport number studies. XRD analysis and FT-IR spectroscopic results have provided details regarding the various phases present in the new system and also indicated the formation of composite materials consisting of glassy and crystalline phases. The transport number measurements have indicated the formation of superionic solids having Ag⁺ ions as the mobile species in the present system.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ