Oxygen overdoping in superconducting and non-superconducting Y1−xPrxBa2Cu3Oy

We present the evolution of magnetic and structural properties of Y_1−xPr_xBa₂Cu₃O_y (x0.5 and x=1) single crystals and polycrystalline materials when the oxygen concentration y is varied from under- to overdoping. We have found a monotonous evolution of the Pr Néel temperature for x=1 samples and a maximum of the superconducting critical temperature for the x0.5 samples. The structural properties as detected by X-ray diffraction and Raman spectroscopy show no instabilities when crossing the optimal doping region as was found in the x=0 material.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

Coercivity mechanism in nanophase (Nd–Pr)–Fe–B melt spun alloys

The nucleation mechanism to predict coercivity values in melt-spun exchange-coupled (Nd_1−xPr_x)_yFe_94−yB₆ alloys for various Nd:Pr ratios x, and Fe:RE ratios y, was tested using the dependence of the anisotropy constant K₁ on Pr content x for the minimum nucleation field H_N^min in the modified Brown's equation. Very good agreement was found between experimental data and theoretical values, confirming the predominance of the nucleation of reverse domains over the wall pinning process in the coercivity mechanism of melt spun REFeB alloys.     

Preparation, characterization and oxide ion conductivity in U-substituted Bi4V2O11

A Bi₂V_{1 − x − y}U_xBi_yO_{5.5 + 0.5x − y} solid solution derived from Bi₄V₂O₁₁ has been prepared and characterized with x up to 0.125 for y = 0. Partial substitution of U⁶⁺ for V⁵⁺ in Bi₄V₂O₁₁ leads to the stabilization at room temperature of the high-oxide ion conducting γ-phase, in contrast with other M⁶⁺ dopants which stabilize the β-phase. The lower conductivity in U substituted system compared with BICUVOX.10 is attributed to its higher activation energy. Conductivity values and activation energies of the U substituted phases compare well with Bi₂UO₆.     

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.     

Effect of Sn doping on the magnetic and transport properties of LaMnO3+δ

We report the influence of the Sn doping on the magnetotransport properties of the LaMnO_3+δ perovskite. Two series of samples with nominal LaSn_xMn_1−xO_3+δ (I series) and La_{(1−x)/(1+x)}Sn_xMn_1−xO_3+δ (II series) compositions (x=0, 0.025, 0.05 and 0.10) were prepared at T_s=750°C. The M(T) data under 0.01 and 0.5 T for the I series reveal a depressed magnetization as the Sn content increases suggesting the presence of magnetic clusters with a superparamagnetic behavior. Resistivity measurements indicate an insulator material for all Sn content independently of the applied magnetic field. On the contrary, for the II series the M(T) and M(H) data reveal FM behavior and an improvement of the magnetization as Sn increases. These samples show magnetoresistance. The magnetotransport properties are discussed in terms of the presence of A-site cation vacancies.     

Effect of Pr and Ca substitution on superconductivity in Y(1−x−yPrxCay)Ba2Cu3O7−δ

Pr substituted at constant Ca concentration for Y in (Y_1−x−yPr_xCa_y)Ba₂Cu₃O_7−δ superconductors have been prepared under identical conditions and the temperature dependence of the electrical resistivity of these samples are measured. The resistively determined values of T_c decrease linearly with increasing x (0 ≤ x ≤ 0.2) for constant y = 0.10 and 0.15 which provides convincing evidence that the suppression of superconductivity by Pr is mainly due to magnetic pair breaking. The suppression of superconductivity can also be correlated to the observed changes in oxygen content determined by iodometric analysis and to the average Cu-valences. However, it is found that the observed suppression of T_c cannot be compensated by appropriate hole doping with Ca.     

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

Effect of hydrogen absorption on the magnetic properties of some Zr-3d laves phase binary and pseudobinary intermetallics

Magnetization measurements have been performed on ZrCr₂, ZrMn₂, Zr(Cr_xFe_1−x)₂(x = 0.2, 0.5, 0.75) and Zr(Cr_x Co_1−x)₂ (x = 0.75, 0.4) before and after hydrogenation. In all cases both the magnetic moments and the magnetic ordering temperatures (whenever present) appeared to be significantly larger in the hydride phases. The increase of the magnetic ordering temperatures is in a qualitative agreement (but not a quantitative one) with the negative pressure effects on T_c in ZrFe₂.     

Isotopically driven transitions in LaPrCaMnO system

The effect of oxygen isotope substitution on transport and magnetic properties is studied for (La_1−yPr_y)_0.7Ca_0.3MnO₃ ceramics and thin films. The temperature dependence of electrical resistivity reveals the metal–insulator transition induced by the ¹⁶O→ ¹⁸O substitution at y=0.75 (ceramics) and y=0.5 (films on LaAlO₃). Neutron powder diffraction at y=0.75 demonstrates a striking difference between magnetic structures in the samples with ¹⁶O and ¹⁸O. Measurements of AC magnetic susceptibility allow us to analyze the magnetic phase diagram and its changes related to the isotope substitution.     

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.     

Luminescence from Si-Si1−xGex/Si1−yCy-Si structures

Near band edge photoluminescence has been obtained from Si_1−yC_y quantum well (QW) and neighboring Si_1−xGe_x/Si_1−yC_y double QW (DQW) structures. Enhanced no-phonon recombination is observed from the DQW structures and it is attributed to a breaking of the k-selection rule in the presence of the heterointerface. The luminescence persists for measurement temperatures up to 30–50 K and the intensity exhibits a quenching behavior with an activation energy equal to 8–20 meV. In electroluminescence only recombination in the Si_1−xGe_x layer has been observed from neighboring Si_1−xGe_x and Si_1−yC_y DQW structures.     

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.     

Observation of unrecoverable domains in two-dimensional-arrayed Pr0.5Ca0.5MnO3−y junctions

Two-dimensional-arrayed 14×14 sandwich-type junctions of Au–Pr_1−xCa_xMnO_3−y (PCMO, x=0.5)–SrRuO₃ were fabricated on SrTiO₃ (0 0 1) substrates. The resistivity–voltage (ρ–V) characteristics of each junction was measured by a two-probe method. The junctions that return to the insulating state after removing the voltage (recoverable) and the ones that remain metallic (unrecoverable) were found to co-exist in one PCMO film. The variation in the lattice constant of the PCMO film, rather than the variation of the composition, is thought to be related to the separation of recoverable–unrecoverable domains. Among several samples with a PCMO layer fabricated under various conditions, the junctions with thin PCMO layers deposited at low temperature showed a pronounced hysteresis in their ρ–V characteristics. The clear hysteresis and good crystallinity of PCMO films were correlated.     

Ferromagnetic Zr1−xMnxCo2 laves phase compounds

Structure and magnetic properties of the Zr_1−xMn_xCo_2+δ alloys were studied for 0 x <0.7, δ=0, 0.45. The cubic C15 Laves phase structure shows Mn solubility up to x≈0.4. The other Laves phase with the hexagonal C36 structure found for x0.5 apparently has a small region of Mn solubility in the vicinity of Zr_0.4Mn_0.6Co₂. Though the parent Mn-free compounds are known to be paramagnetic, the Mn-substituted alloys show ferromagnetic behavior with the Curie temperatures up to 625 K and the room-temperature saturation magnetization of about 100 emu/g. The onset of ferromagnetism with the Mn substitution for Zr may be caused by polarization of itinerant 3d electrons, like it was earlier supposed for the off-stoichiometric ZrCo_2+δ. The universal composition dependencies of the intrinsic magnetic properties for different δ can be obtained, if plotted against the amount of zirconium atoms missing in its sublattice. The room-temperature anisotropy with the noticeable anisotropy field of 24 kOe and the 1 1 0 easy magnetization direction laying in a basal plane was found in the hexagonal Zr_0.5Mn_0.5Co₂.     

Influence of Nd substitution on the superconducting properties of ceramics in the 2212 system Bi2−wPbwSr2−xCa1−yNdx+yCu2O8+z

In the system Bi_2−wPb_wSr_2−xCa_1−yNd_x+yCu₂O_8+z different fractions of Nd are substituted on either Sr of Ca sites in order to introduce intrinsic insulating pinning centres. It is shown that a Nd concentration around x or y = 0.2 is likewise favourable with an average Nd---Nd distance in the range of the coherence length in the a, b-plane. However, clear evidence of flux pinning is only present for charge compensation with Pb²⁺. A simultaneous substitution of the Bi-based 2212 superconductor with moderate amounts of Nd³⁺ and Pb²⁺ improves the superconducting properties by strengthening the flux pinning forces.     

Temporary phase segregation processes during the oxidation of (Fe0.7Mn0.3)0.99O in N2---H2O atmosphere

A two-step thermochemical cycle with the ternary metal oxide system (Fe_{1 − x}Mn_x)₃O₄/(Fe_{1 − x}Mn_x)_{1 − y}O is applied to convert solar energy to chemical energy. Experimental investigations on the water splitting reaction of (Fe_{1 − x}Mn_x)_{1 − y}O revealed temporary formation of a manganese rich rock salt phase and an iron rich spinel phase due to phase segregation processes.     

Structure, oxygen stoichiometry and electrical conductivity in the system Sr-Ce-Co-O

Mixed oxides in the system S-Ce-Co-O were prepared by solid state reaction and by freeze-drying of precursor compounds followed by thermal treatment. Two types of perovskite oxides exist in the system: Solid solutions of the type Sr_{1 − y}Ce_yCoO_{3 − x} and mixed oxides of the type (1 − y)SrCeO₃ − ySrCoO_{3 − x}. Microstructures and phase compositions were determined by electron microscopy and X-ray diffraction. SrCoO_{3 − x} forms a solid solution of ceria on the A-site in the strontium cobaltite lattice up to 0.15 mol Ce. This solid solution corresponds to the high-temperature structure of pure SrCoO_{3 − x} and is characterized by high oxygen exchange and electrical conductivity. The oxygen deficiency x was measured by solid electrolyte coulometry. The oxygen deficiency of solid solutions Sr_{1 − y}Ce_yCoO_{3 − x} increases with temperature and decreases with pO₂ in the ambient atmosphere and with increasing Ce dopant concentration. The pO₂-T-x diagram of the solid solution was determined. The T, pO₂ and dopant concentration dependencies of electrical conductivity were measured by a four-point d.c. technique. By Ce doping strontium cobaltite becomes a stabilized high-conductive material (maximum conductivity: 500 S cm⁻¹ at 400 °C, E_a = 0.025 eV, p-type). Above this temperature the T-coefficient of the conductivity changes from positive (semiconducting) to negative values.     

Spectroscopic study of BixEu1−xVO4 and BiyGd1−yVO4 mixed oxides

The mixed oxides Bi_xEu_1−xVO₄ and Bi_yGd_1−yVO₄ crystallize in a zircon-type structure, for 0 <x < 0.6 and 0 < y < 0.64, and in a fergusonite-type structure, for 0.94 < x < 1 and 0.93 < y < 1. A process of competition between the dominant and the constrained effects of the lone-pair 6s² of Bi³⁺ is discussed. The diffuse reflectance spectroscopic studies of these mixed oxides are presented. The observed broad bands are attributed to charge transfer processes and the sharp peaks in the Bi_xEu_1−xVO₄ spectra are ascribed to intra-configurational 4f – 4ftransitions of the Eu³⁺ ion. The broad absorption shift in BiLnVO₄ (Ln : Eu and Gd) compounds to the longer wavelengths range, when Bi is introduced in the LnVO₄ lattice, is ascribed to charge transfer processes in a Bi-VO₄ center and are interpreted assuming a Jahn-Teller effect in the excited state of Bi³⁺. The concept of an internal pressure of Bi³⁺ ions is also used to explain the broad A-band shifts.