Influence of octahedral tilting and composition on electrical properties of the Li0.2 − xNaxLa0.6TiO3 (0 ≤ x ≤ 0.2) series

The Rietveld analysis of ND patterns of polycrystalline Li_0.2 − xNa_xLa_0.6TiO₃ (0 ≤ x < 0.2) samples, recorded between 300 and 1075 K, shows an orthorhombic–tetragonal transformation, in which the octahedral tilting along the b axis is eliminated at ~ 773 K, but the vacancy ordering along the c axis remains. In Li rich samples, conductivity (10^− 3 Ω^− 1 cm^− 1 at 300 K) departs from the Arrhenius behaviour, decreasing activation energies from 0.37 to 0.14 eV when octahedral tilting is eliminated. Successive Maxwell–Wagner blocking processes, detected in the real part of dielectric constant plots, have been ascribed to the Li blocking at interior domains, grain-boundary and electrode–electrolyte interfaces. The substitution of Li⁺ by Na⁺ decreases the amount of vacant A-sites, decreasing several orders of magnitude the conductivity when the amount of vacancies approaches the vacancy percolation threshold (n_p = 0.27). Below the percolation threshold, Li ions only display local mobility, remaining confined into small domains of perovskites.     

Li mobility in Li0.5 − xNaxLa0.5TiO3 perovskites (0 ≤ x ≤ 0.5): Influence of structural and compositional parameters

The dependence of Li mobility on structure and composition of Li_0.5 − xNa_xLa_0.5TiO₃ perovskites (0 ≤ x ≤  0.5) has been investigated by means of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. At 300 K, all samples display a rhombohedral superstructure (R-3c S.G.), where octahedra are out of phase tilted along [111] direction of the ideal cubic cell. The elimination of the octahedral tilting is responsible for the rhombohedral–cubic transformation, detected near 1000 K. In these perovskites, La and Na cations are randomly distributed in A sites, but Li ions are fourfold coordinated at unit cell faces of the cubic perovskite. Lithium conductivity, σ_300 K, decreases with the sodium content, decreasing from values typical of fast ionic conductors, 10^− 3 S/cm, to those of good insulators, 10^− 10 S/cm, when the interconnectivity between vacant A sites is lost (x > 0.3). In samples with x < 0.3, dc conductivity displays a non-Arrhenius behaviour, decreasing activation energy from ~ 0.37 to 0.25 eV when the sample is heated between 77 and 500 K. The temperature dependence of B_Li factors shows the existence of two regimes for Li motion. Below 373 K, Li ions remain partially located near square oxygen windows that connect contiguous A sites, but above 400 K, extended Li motions become dominant. The additional decrease of activation energy from 0.25 to 0.16 eV (low-temperature ⁷Li NMR value), should require the full elimination of octahedral tilting which is only produced above 1000 °C.     

Defect chemistry and oxygen transport of (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2), Sr: Part I: Defect chemistry

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La_0.6Sr_0.4 − xM_x)_0.99Co_0.2Fe_0.8O_3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr²⁺ ions with Ca²⁺ ions (smaller ionic radius) and Ba²⁺ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba²⁺ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr²⁺ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low p_O2 showed several phase transitions.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Oxygen nonstoichiometry and electrical conductivity of the solid solutions La2−xSrxNiOy (0≤x≤0.5)

Oxygen nonstoichiometry and electrical resistance of a series La_2−xSr_xNiO_y solid solutions, where x=0.0, 0.2 and 0.5 in argon flows at oxygen partial pressures 1.5, 10.2, 49.2, 100 and 286 Pa within the temperature range of 20–1050°C were studied. Nickelate oxygen desorption/sorption spectra when heating–cooling at constant rate demonstrated strong dependence of cation composition of the samples. Unlike La_1.5Sr_0.5NiO_y compounds those of La₂NiO_y and La_1.8Sr_0.2NiO_y have weakly bonded oxygen, capable to exchange reversibly with the gas phase at the temperatures higher than 250°C. The equilibrium values of oxygen nonstoichiometry and specific resistance for the these nickelates were determined at 300–1050°C and p_O2=1.5–286 Pa as a functions of temperature versus oxygen partial pressure. All nickelate studied appear to be p-type conductors with metal electric conductivity at equilibrium states.     

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.     

Superconductivity mechanism of Ba1−xKxBiO3

Based on the singly occupied a_iσ picture and the mechanism of charge fluctuation, the effective Hamiltonian of the two-band Hubbard model is derived by using the degeneracy perturbation theory for the noncuprate compound Ba_1−xK_xBiO₃. By considering the next-neighbour pairing of two opposite spin holes in coordinate space, the Green's function equation of motion and the superconductivity equation are obtained. Furthermore, how the superexchange interaction and the hopping energy affect the next-neighbour pairing has been reasonably explained, and the superconductivity window is due to the Cooper pairing in coordinate space.     

Superconductivity in Ba2−xSrxYCu3Oz prepared at GPa

The compounds Ba_1.4Sr_0.6YCu₃O_z (7.0≤z<7.4) were synthesized at 2 GPa to clarify the effect of high temperature and pressure on the superconducting properties. The structure as observed by powder X-ray diffraction was tetragonal for z≥7.2, and orthorhombic or tetragonal for z<7.1. It has been revealed that high-pressure syntheses suppress the superconductivity in the compounds with z<7.1. Recovery of the superconducting properties occurs above z≥7.2. The effect of Sr substitution on the superconducting properties was also studied. The magnitude of diamagnetism at 5–30 K decreases monotonically from −0.003 to −0.0002 emu/g Oe with increasing x in Ba_2−xSr_xYCu₃O_z (x≥1.2).     

Normal-state transport properties of Ba1−xKxBiO3 crystals

The normal-state transport properties of Ba_1−xK_xBiO₃ crystals with a wide range of potassium compositions (0≤x≤0.62) were studied. Although the host material BaBiO₃ has a monoclinic structure, the system changes from a monoclinic to an orthorhombic structure with a small doping of potassium (0≤x<0.35) and behaves similar to a doped semiconductor, without exhibiting superconductivity. In the composition range, holes are majority carriers in the transport phenomena. When x exceeds a critical value (0.35), the system goes into a cubic superconducting phase with a single metallic band. The vicinity of the critical composition transport phenomena is easy to understand assuming the existence of two conducting channels that are made up of metallic and semiconducting phases. Maximum T_c exceeding 30 K was observed at x0.4, where carrier density was at its maximum. Overdoping with potassium suppresses superconductivity. In the metallic composition of x>0.45, transport seems to correlate with the phonon mode with an energy distribution of 15–43 meV.     

Structural properties and Raman spectroscopy of orthorhombic (Eu1−xPrx)0.6Sr0.4MnO3 (0≤x≤1.0)

The effect of Pr doping on structural properties and room temperature Raman spectroscopy measurements is investigated in manganites (Eu_1−xPr_x)_0.6Sr_0.4MnO₃ (0≤x≤1.0) with fixed carrier concentration. The result of the Rietveld refinement of x-ray powder diffraction shows that these compounds crystallize in an orthorhombic distorted structure with a space group Pnma. It is evident that, with increasing Pr substitution, three types of orthorhombic structures can be distinguished. The phonon frequencies of the three main peaks, in room temperature Raman-scattering measurements, have been discussed together with their structural characteristics, such as bond-length, bond-angles, and the change of orthorhombic structure type. With the increase of Pr content, the mode at 491  cm⁻¹ also shows a corresponding change. A step effect becomes evident, which seems to indicate the close dependence between the frequency shift of this mode and the change in crystal symmetry. This further supports the notion that the mode at 491  cm⁻¹ is closely correlated with the Jahn–Teller distortion. Moreover, we have found that the lowest frequency peak (assigned as an A_1g phonon mode) depends linearly on the tolerance factor t.     

Quantum critical point, scaling and universality in high Tc(CaxLa1−x)(Ba2−c−xLac+x)Cu3Oy

Using charge transport in sintered ceramic samples it is observed that at all doping, including non superconducting overdoped samples, there exists a temperature in which below it dR/dT < 0. This suggests that either the quantum critical point is not necessarily inside the superconducting dome or that the CuO₂ plane is never overdoped. Data relating experimental Cooper pair density, conductivity and T_c suggest that Homes’ relation might need a more specific definition of the conductivity σ.     

Ramans study of Y1−xPrxBa2Cu3O7−δ and YB2Cu3−xZnxO7−δ single crystals

Single crystals with known T_c values of Y_1−xPr_xBa₂Cu₃O_7−δ (Y---Pr1:2:3) and YBa₂Cu_3−xZn_3−xZn_xO_7−δ (Y---Zn1:2:3) systems are studied by Raman measurements. The Raman spectra for (Y---Pr1:2:3) single crystals show that the frequencies of Ba and O_z modes increase as the Pr content increases. The results are consistent with the hole-localization scheme proposed for the suppression of superconductivity in the polycrystalline Y---Pr1:2:3 systems. On the other hand, in the Y---Zn1:2:3 system, all the Raman modes do not change in frequencies. However, the FWHM of the Cu(2) mode increases with the decrease of T_c, indicating strong scattering of charge carriers by the substituted Zn ions in the CuO₂ planes. The induced disorder in the CuO₂ planes may be related with suppression of T_c in the Y---Zn1:2:3 system. Thus, the suppression mechanism in the Y---Zn1:2:3 systems seems to be different from that in the Y---Pr1:2:3 systems.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Electrochemical behaviour of (La1 − xSrx)sCo1 − yNiyO3 − δ as porous SOFC cathodes

This paper shows that storage at room temperature and ambient atmosphere appears to affect the polarisation resistance significantly and R_P decreased initially with storage time. This improvement was more pronounced when stored in moisturised air. The performance was, however, also found to decrease when stored for sufficiently long periods. The absolute values of the electrode response of these materials are very difficult to reproduce and the performance appears to be largely dependent on the manufacturing process of the powder or the electrode itself. In spite of this, the electrode behaviours exhibited similar patterns with respect to the dependence on T and P_O2. An increase in polarisation resistance with time at SOFC operating conditions was observed, which was related exclusively to the electrode reaction kinetics and not to oxygen concentration polarisation. It was also found to be higher when measured in moisturised air.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

Superconductivity and crystallographic properties of La2 − xMxCuO4 − δ (M = Na, K)

Superconductivity and crystallographic properties of La_{2 − x}M_xCuO_{4 − δ} (M = Na, K) are studied. In the La_{2 − x}M_xCuO_{4 − δ} system, superconductivity is detected for x 0.2. Oxygen content analysis shows that the system has more oxygen vacancies than the La_{2 − x}Sr_xCuO_{4 − δ} system. These oxygen vacancies may reduce the hole concentration, and high Na-doping is needed to produce superconductivity. In the La_{2 − x}K_xCuO_{4 − δ} system, superconductivity is observed for the first time. Resistivity and magnetic susceptibility measurements show that T_c(onset) is 40 K and the Meissner volume fraction is about 4% for x = 0.7. The system changes from orthorhombic to a tetragonal K₂NiF₄ structure at x ≈ 0.3 and only tetragonal samples show superconductivity.     

Viscosity of In100 − xSbx molten alloys in the vicinity of equiatomic composition

The viscosity of In–Sb liquid alloys has been measured in the vicinity of equiatomic concentration (40–60 at.% Sb). The measurements were carried out by a torsional oscillation viscometer. Temperature dependence of viscosity coefficient shows the Arrhenius like behavior with anomalous increase near the melting temperature. It is shown that viscosity isotherms reveal a sharp maximum at equiatomic composition, which becomes smoother with temperature increase.     

Magnetic properties of Gd2(Fe1−x−yCoyTix)17

Serial single-phase Gd₂(Fe_1−x−yCo_yTi_x)₁₇ compounds have been synthesized. These compounds have a crystal structure belonging to rhombohedral lattice with space group. The lattice parameters of compounds decrease with cobalt content and increase with titanium content, respectively. The saturation magnetization decreases with increasing cobalt and titanium contents. The anisotropy fields increase to maximum then decrease with cobalt concentration. The magnetocrystalline anisotropy constants increase with cobalt content from negative to positive maximum and then decrease with Co concentration. The saturation moment of the compounds decreases linearly with cobalt concentration and decreases nonlinearly with titanium concentration.     

Electrical properties of perovskite-type La(Cr1−xMnx)O3+δ

Perovskite-type La(Cr_1−xMn_x)O_3+δ (0.0x1.0) was synthesized using a sol–gel process. The crystal structure of La(Cr_1−xMn_x)O_3+δ changes from orthorhombic to rhombohedral at x=0.6. The Mn⁴⁺ ion content increases monotonically in the range 0.2x1.0. The magnetic measurement of La(Cr_1−xMn_x)O_3+δ indicates that a Mn³⁺ ion is a high-spin state with (d)³(dγ)¹. The variation of the average (Cr, Mn)-O distance is explained by ionic radii of the Cr³⁺, the Mn³⁺, the Mn⁴⁺ ions. Since the log σT–1/T curve is linear and the Seebeck coefficient (α) is independent of temperature, it is considered that La(Cr_1−xMn_x)O_3+δ is a p-type semiconductor and exhibits the hopping conductivity.