Phase Formation,Crystal Structure and Electrical Properties of La212 Type Compound Substituted by Silver or Praseodymium

The La212 type compounds substituted by silver or praseodymium are prepared by solid state reaction method. It is found that compounds La_2‐xSr_xCa_0.5Pr_0.5Cu₂O₆, La_1.6Pr_0.4Ca_1‐xSr_xCu₂O₆ and La_2‐xPr_xCa_0.5Sr_0.5Cu₂O₆ can be formed for x=0.4‐1.1, 0‐0.5 and 0‐1.5, respectively. A new member of La212 type compounds, La_2‐xAg_xCaCu₂O₆ is also prepared. Their structures are verified by Rietveld structure refinement to belong to the structure type of La212 cuprate oxide with space group I4/mmm. Their electrical properties are investigated. La_1.65Ag_0.35CaCu₂O₆ displays metal‐like behavior and its resistivity decreases with the decrease of temperature from 300K to 4.2K.     

Some structural considerations on the perovskite‐type A1‐ySryCo1‐xFexO3‐δ solid solution series

Solid solution series of La_1‐ySr_yCo_1‐xFe_xO_3‐δ were extensively studied in the past as cathode materials for solid oxide fuel cells. However, the crystal structure behavior of La_1‐ySr_yCo_1‐xFe_xO_3‐δ solid solution series when La‐ions are replaced with another rare‐earth ion or metallic alkaline earth metal is at present not fully understood. Here we report X‐ray powder diffraction measurements performed on samples of the Sm_0.8Sr_0.2Co_1‐xFe_xO_3‐δ solid solution series. This study demonstrates that the average A‐cation radius, as well as the Fe content (x), affects the structural modification of the A_1‐ySr_yCo_1‐xFe_xO_3+δ solid solution series significantly. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave dielectric properties of La(1‐2x/3)Bax(Mg0.5Sn0.5)O3 ceramics

This study examined the potential applications of microwave dielectric properties of La_(1‐2x/3)Ba_x(Mg_0.5Sn_0.5)O₃ ceramics in rectenna. The La_(1‐2x/3)Ba_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid‐state method with various sintering temperatures. An apparent density of 6.62 g/cm³, a dielectric constant of 20.3, a quality factor of 51,700 GHz, and a temperature coefficient of resonant frequency of ‐78.2 ppm/K were obtained for La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mechanosynthesis and Mechanolysis of Solid Solutions of La2O3 with Some Rare Earth Oxides

The effect of the mechanoactivation on Y₂O₃, Nd₂O₃ and CeO₂, on mixtures of La₂O₃ with each of these oxides as well as on the solid solutions La₂O₃–CeO₂ is studied. The activation causes a decrease of the individual oxides' unit cell parameters. The formation of solid solutions of La2O₃ with the oxides studied is found. Under the conditions of activation in air no decomposition of La₂O₃–CeO₂ solid solution is detected. The solution is, however, destroyed when the activation is carried out in the presence of acids.     

Mechanism of formation of barium cuprate-based solid solutions with perovskite-like structure doped with cadmium and yttrium oxides

The influence of Y₂O₃ and CdO content on the phase composition, structure, and electrical properties of Y₂O₃-CdO-BaO-CuO ceramics was studied. The concentration limits of the existence of the orthorhombic perovskite-like Y_xBa_{2 ? x} Cd_yCu_{1 ? y} O_{3 + δ} solid solutions (where 0.20 ≤ x ≤ 0.37 and y ≤ 0.2) and their unit-cell parameters are determined.     

Synthesis and structure of nanocrystalline La0.50Ba0.50MnO3

Nanocrystalline manganite La_0.50Ba_0.50MnO₃ was synthesized by the soft-chemical method. For this purpose, the sol-gel method was modified and improved. A trihydric saturated alcohol, e.g., glycerol, was suggested as a new organic matrix. The crystal structure of the composite was studied by X-ray powder diffraction at room temperature. A La_0.50Ba_0.50MnO₃ powder annealed in air at T = 500°C is characterized by a perovskite-like cubic structure with the unit-cell parameter a = 3.869 Å. The chemical composition of the sample was studied by electron-probe X-ray microanalysis. The La: Ba: Mn cation ratio in the material was 1: 1: 2. The surface topography was examined with a scanning electron microscope. The crystallite size was ～30 nm. The dependence of the crystal structure and the surface topology on the annealing temperature was studied. The high-temperature treatment in air resulted in the growth of larger, micrometer-size, crystallites.     

Twin Structure of (La,Nd)GaO3 Solid Solutions

For La_1‐xNd_xGaO₃ crystals the La‐Nd substitution leads to decrease of spontaneous strains and for composition with x≈0.32 the six possible twin states of orthorhombic phase (m3mFmmm) may be degenerated in three twin states inhered in m3mF4/mmm species when a distorted perovskite pseudocell becomes tetragonal. The {110} and {112} reflection twins and axial twins with compositional planes close to (211) and (21‐1) (S‐walls) were identified in La_1‐xNd_xGaO₃ (x=0.07, 0.12, 0.20) solid solutions crystals. All observed twins are typical for crystals with GdFeO₃ type perovskite‐like structure. It has been shown that for x≤0.2 and x≥0.5 orientations of S‐walls weakly depend on La/Nd ratio, whereas in the range of 0.2<x<0.5 they depend strongly on the solid solution composition. The tilt angle between two twin states across twin boundary in La_1‐xNd_xGaO₃ (x<0.6) solid solutions is smaller than that between two twins in pure LaGaO₃ or NdGaO₃.     

On the effects of Ga3+ and La3+ ions in MgCu ferrite: Humidity‐sensitive electrical conduction

Pure and gallium or lanthanum substituted MgCu ferrites, Mg_0.5Cu_0.5Fe_2‐xM_xO₄ (with x = 0 or 0.2 and M = La or Ga) have been prepared by solid state reaction. Sintering experiments were carried out at different temperatures between 900 and 1100°C. The phase composition and lattice parameters were determined by XRD, while the effect of Ga and La substitutions on the granular structure was studied by SEM. Experimental results revealed that the densification behaviour and some physical properties are in close relation with the structural changes of pure ferrite caused by the presence of La and Ga substitutions. The gallium containing compound, Mg_0.5Cu_0.5Fe_1.8Ga_0.2O₄, is monophasic and contains a great number of pores, whereas the lanthanum containing compound, Mg_0.5Cu_0.5Fe_1.8La_0.2O₄, is biphasic and exhibits a high density. The humidity characteristics show that the gallium ion enhances the humidity sensitivity of the MgCu ferrite sintered at 1000°C. This interesting effect is promising for the future of the Ga‐substituted MgCu ferrite to be used as sensitive material for fabrication of ceramic humidity sensors. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on electrical conduction behavior of La1‐3xCaxBaxSrxMnO3 synthesized by chemical route

In the manganite La_1‐xM_xMnO₃ (M = Ca, Ba, Sr) the doping concentration introduces a mixed valency (Mn³⁺, Mn⁴⁺) which governs the magnetic and electrical properties of the compound. The perovskite oxides La_1‐3xCa_xBa_xSr_xMnO₃ (x = 0.00, 0.05, 0.10) were prepared by chemical method. Single‐phase formation is confirmed by XRD studies. The electrical behavior of compositions with x = 0.00, 0.05 and 0.10 in the system La_1‐3xCa_xBa_xSr_xMnO₃ was studied in the temperature range 300‐420 K. It is observed that conductivity decreases with increasing temperature as well as dopants concentration. Metallic behavior of these compositions decreases with increasing dopants concentration (x). The microstructures of these samples have been characterized using scanning electron microscopy (SEM). (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of Electrical Conduction Behaviour of the System Sr1-xLaxSn1-xCoyO3 (x = y ⩽ 0.5; x ⩽ 0.5, y = 0.00; x = 0.00; y ⩽ 0.05)

Single phase solid solution forms in the Sr_1-xLaSn_1-xCo_yO₃ (x = y) system for x⩽0.05 in the samples prepared by solid state ceramic method. A few compositions were prepared in the Sr_1-3x/2La_xSnO₃ and SrSn_1-yyCo_yO_3-y/2 to understand the role of La³⁺ and Co³⁺ in the electrical conduction behaviour of the system. Resistivity increases with incorppration of La³⁺ ions and decreases with doping of Co³⁺ ions. These results have been explained in terms of the defect structures of these materials.     

Growth and characterization of large La1‐xPbxMnO3+δ (x=0.32–0.35) crystals

Large crystals of La_0.63Pb_0.37Mn O_3+δ with small La(Pb)‐ deficiency of about 0.005‐0.01 at.% were grown by high temperature solution growth method. The structure of the grown crystals was determined as rhombohedral with R‐3 space group by single‐crystal X‐ray diffractometry. The surface morphology of the crystals and the exact chemical composition was examined by scanning electron microscopy and energy dispersive X‐ray analysis methods, respectively. The IR‐transmission spectrum reveals the presence of Mn³⁺O₆‐ and Mn⁴⁺O₆‐ octahedra in the lattice of La_0.63Pb_0.37Mn O_3+δ crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase Transformations in the Y2BaCuO5, «Ba3Cu5O8» and Y2BaCuO5‐«BaCuO2» Systems

Peritectic interaction of Y₂BaCuO₅ and Y₂BaCuO₉‐d phases with the Y‐Ba‐Cu‐O system flux melt has been modeled. The sequence of phase transformations in the Y₂BaCuO₅‐«Ba₃Cu₅O₈» and Y₂BaCuO₅‐«BaCuO₂» systems when forming the YBa₂Cu₃O₇‐d single crystal compound has been established.     

Czochralski growth and characterization of Dy: La3Ga5.5Nb0.5O14 single crystals

Dysprosium (Dy) doped La₃Ga_5.5Nb_0.5O₁₄ single crystals were grown by the traditional Czochralski method along z‐axis. The structure of the crystal has been studied by X‐ray powder diffraction method, and the unit‐cell parameters are calculated to be a=8.22070 Å, c=5.12533 Å and V=299.965 ų. The segregation coefficient of Dy³⁺ in La₃Ga_5.5Nb_0.5O₁₄ crystal was measured by X‐ray fluorescence analysis. For 1 mol% doping level in the melt, the distribution coefficient of Dy³⁺ was determined to be 0.341 wt%. Specific heat, thermal expansion and transmission spectrum of Dy: La₃Ga_5.5Nb_0.5O₁₄ single crystals have been measured. The fluorescence spectra of Dy³⁺: La₃Ga_5.5Nb_0.5O₁₄ crystals were measured at room temperature, and there were four emission transitions occurring at 479, 576, 662 and 754 nm, respectively. The fluorescent lifetimes measurement results show 1.0% Dy: La₃Ga_5.5Nb_0.5O₁₄ possesses shorter fluorescence decay time (303.4 μs) than does 1.0%Dy:LGS (436.12 μs). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the synthesis and characterization of La doped MgB2 superconductor

We report the synthesis of La doped MgB₂ superconductors with nominal compositions Mg_1‐xLa_xB₂ (with x = 0.01, 0.03, 0.05, 0.07) by solid state reaction at ambient pressure. A special encapsulation technique has been used by us to prepare high quality superconducting MgB₂ samples. The bulk polycrystalline samples possess superconducting transition temperature T_c(R=0) ranging between 36‐39 K. It has been found that transport critical current density J_c of the samples change significantly with the doping level of La. A high transport (J_c) value ∼1.9 x 10³ A/cm² at 15 K has been achieved for Mg_0.97La_0.03B₂ sample. The XRD and TEM investigations indicate that the samples prepared by encapsulation method are devoid of MgO, which is generally found when synthesis of MgB₂ is done through sintering of Mg and B powders. The detailed microstructural investigations of Mg_0.97La_0.03B₂ specimens by transmission electron microscopy (TEM) reveal the presence of partial dislocation network, moiré fringes and superlattice structure in the as synthesized samples. The higher transport critical current density observed in Mg_0.97La_0.03B₂ superconductor has been attributed to the partial dislocations which are capable of providing pinning centres. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fluorescence of copper, manganese and antimony ions in phosphate glass host

The paper presents a study based on luminescence characteristics of phosphate glasses containing Cu²⁺, Mn⁴⁺ and Sb³⁺. The glass samples obtained by a wet chemical route belong to Li₂O–BaO–Al₂O₃–La₂O₃–P₂O₅ oxide system. The oxide composition of the glass samples is calculated to obtain a vitreous network composed of metaphosphate chains bonded by modifier ions (Li⁺, Ba²⁺ and La³⁺) and fluorescent ions. The absorption spectra of the samples were acquired in the UV domain in order to establish the excitation wavelength for each fluorescent ion. The absorption peaks of Sb³⁺ ion are ranged at 285 nm and 250 nm, Mn²⁺ ion at 280 nm and 365 nm, Cu²⁺ ion at 295 nm and 313 nm. The luminescence peaks of Cu²⁺, Mn⁴⁺ and Sb³⁺ ions are found in the visible domain at different wavelengths, depending on the oxidation state and coordination symmetry of each fluorescent ion. The fluorescence of Sb³⁺ ion has a strong signal at 450 nm and a weak one at 465 nm, Mn²⁺ ion shows a fluorescence peak at 600 nm and the pair Cu²⁺/Cu⁺ ions reveals a fluorescence emission at 460 nm.     

Effect of Ba ions substitution on multiferroic properties of BiFeO3 perovskite

Dielectric, magnetic and ferroelectric properties of Bi_1‐xBa_xFeO₃(x = 0.1, 0.2 and 0.3) synthesized by solid state reaction method are reported. X‐ray diffraction pattern showed that Bi_1‐xBa_xFeO₃was single phase. Ba substitution has led to a decrease in grain size and hence an increase in the electrical resistivity. The variation of dielectric constant and loss has been studied over a frequency range of 1 kHz – 2 MHz at room temperature. Ba doping leads to effective suppression of the spiral spin structure of BiFeO₃, resulting in the appearance of net magnetization. Improved multiferroic properties of Bi_0.8Ba_0.2FeO₃ ceramic with remnant magnetization and polarization 0.093 emu/g and 0.808 µC/cm², respectively, were obtained. The evidence of ferromagnetism and ferroelectric hysteresis loops in Bi_1‐xBa_xFeO₃system at room temperature makes it a good candidate for potential applications. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

LPE growth of YLaTm and YLaEu garnet films

The growth of films of the composition Y_3?(x+yLa_xR_yFe_5?zGa_zO₁₂, where R = Tm or Eu, on GGG substrates by liquid phase epitaxy from a PbO-B₂O₃ fluxed melt is described. Highly uniform, low defect density films have been grown by means of horizontal dipping using intermittent substrate rotation in conjunction with a novel substrate holder. A furnace with three separate temperature zones was used to optimize the vertical temperature profile. Incorporation of La into the films allows compositions containing Tm to be made whose lattice parameters are matched to GGG and compositions which contain Eu to be made with smaller Eu concentrations than were previously possible. The compositions grown, which contain only trivalent cations, exhibit growth induced anisotropy, high mobility, low coercivity, and sufficient magnetostriction to allow ion implantation to effectively suppress hard bubble formation. Detailed measurements of saturation temperature as a function of oxide concentration show that the La ion contributes differently to the garnet phase than do other commonly used rare earth cations. The kinetics of melt equilibration have been studied and procedures to equilibrate the melt to ensure reproducible film growth are described. Electron microprobe analysis has been used to determine the La distribution coefficient as a function of La concentration, the growth rate of the film, and the melt temperature.     

Influence of simultaneous doping of Tl and Bi on microstructure and critical current density of HgBa2Ca2Cu3O8+δ

It has been found that simultaneous doping of Tl and Bi at Hg site of HgBa₂Ca₂Cu₃O_8+δ HTSC phase induces interesting microstructural variants in the form of long period polytypoid (LPP) like structure embodying native defect substructures. It has been observed that the as synthesized (HgTl_0.2−xBi_x)Ba₂Ca₂Cu₃O_8+δ (with x = 0.05, 0.10, 0.15) phases have superconducting onset transition temperature (T_c) of about ∼133 K. However, the intragrain critical current density (J_c) for the various materials with different compositions varies significantly. It varies from 6.2 × 10⁶ A/cm² to 2.9 × 10⁶ A/cm² at 5 K and 1 T for (HgTl_0.10Bi₁₀)Ba₂Ca₂Cu₃O_8+δ and (HgTl_0.15Bi_0.05)Ba₂Ca₂Cu₃O_8+δ HTSC phase respectively. A correlation between the intragrain J_c and the defect substructures has been found to be present. This correlation has been described and disscussed. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A cooling rate dependent structure of amorphous (AuxCu1−x)91La9

A novel class of metallic glasses of the form (Au_xCu_1?x)₉₁La₉ (x = 0.5, 0.25, 0.6) and (Au_0.5Cu_0.5)_1?yLa_y (y = 10, 11) have been prepared by rapid cooling from the melt. Investigation by means of X-ray diffraction and TEM shows a dependence of the structure on the cooling rate and suggests a phase separated amorphous structure. For sufficiently low cooling rates, crystallization seems to follow phase separation.     

Crystal Structure of (Cr,Cu)(Sr,La)2(La,A)Cu2O8‐δ (1212‐type) and (Cr,Cu)Sr2(Y,Ce)2Cu2O10‐δ (1222‐type) Phases

Conditions of the synthesis, crystal structures, mechanical properties, electrical resistivities and magnetizations of cuprates with the general formula (Cr,Cu)(Sr,La)₂(La,A)Cu₂O_8‐δ where A=Ca or Sr of 1212‐type and (Cr,Cu)Sr₂(Y,Ce)₂Cu₂O_10‐δ of 1222‐type were investigated. The compositions of the cuprates and an amount of the impurity phases in the samples were determined. Rietveld refinement of the structure was carried out. It was found that the formal charges of Cu (FC_Cu) calculated from the electroneutrality of refined phase compositions do not achieve value optimal for the appearence of superconducting phases.