Electron doping versus antisite defects: Structural and magnetic properties of Sr2−xLaxCrMoO6 and Sr2−xLaxCr1+x/2Mo1−x/2O6 perovskites

This study reports the synthesis, structure and magnetic properties of Sr_2?xLa_xCrMoO₆ and Sr_2?xLa_xCr_1+x/2Mo_1?x/2O₆ samples. Although both series exhibit similar crystal structures, Sr_2?xLa_xCrMoO₆ samples present an effective electron doping revealed by a significant expansion of the unit cell with increasing x. In Sr_2?xLa_xCr_1+x/2Mo_1?x/2O₆ samples instead, the Cr-excess leads to a non electron doped system. Both series show a large amount of antisite defects whose number increases as La-content increases. Neutron diffraction patterns reveal the existence of long-range magnetic ordering for all samples but the magnetic peaks are very broad for Sr₂CrMoO₆ indicating a short coherence length of the magnetic ordering. This coherence length is increased upon replacing Sr by La. In both systems there is a clear increase of the magnetic transition temperature with increasing the La-content. The samples show ferromagnetic contributions at low temperature as deduced from the magnetic hysteresis loops typical of hard ferromagnetic materials. However, magnetic saturation is not achieved even at 5 T and the magnetic moment at this field is small. The ac magnetic susceptibility reveals the existence of several anomalies suggesting that these compounds are magnetically inhomogeneous. This is probably due to the presence of the large amount of structural defects not homogenously distributed.     

Electrical properties of Ba2(In1 − x Al x )2O5 solid solutions

The electric conductivity of perovskite-like Ba₂(In_{1 ? x} Al _x )₂O₅ solid solutions (0 < x ≤ 0.20) characterized by structural disordering in the oxygen sublattice was studied as a function of temperature and partial pressure of oxygen in an atmosphere with a low content of water vapors ( $p_{H_2 O}$ = 3 × 10^?5 atm). When In³⁺ was partially replaced by Al³⁺, the oxygen ion conductivity increased because of the disordering of oxygen structural vacancies, leading to a significant increase in the total electric conductivity of the samples.     

Effect of hydration on conductivity of Ba4La x Ca2 − x Nb2O11 + 0.5x (x = 0.5, 1, 1.5, 2) phases

Substitution of Ca by La in initial cubic double perovskite Ba₄(Ca₂Nb₂)O₁₁[VO]₁ allowed obtaining phases with a similar structure with a lower content of structural oxygen vacancies, Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} [VO]_{1 ? 0.5x} (x = 0.5, 1, 1.5, 2). The impedance technique was used to measure the temperature dependences of conductivity in the atmosphere of dry and humid air. Transport numbers determined using the EMF method in an oxygen-air and water steam concentration cells point to the predominantly hole nature of conductivity in the high-temperature region (T > 600°C) and to predominance of proton conductivity in the low-temperature region. Activation energies of hole and proton conductivity were calculated. Thermogravimetric measurements were carried out under heating from 25 to 1000°C with simultaneous mass-spectrometric determination of evolved H₂O and CO₂. The properties of the studied Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} (x = 0.5, 1, 1.5, 2) phases were compared with the earlier studied Ba_{4 ? x} La _x (Ca₂Nb₂)O_{11 + 0.5x} phases with similar lanthanum content.     

New Ion Conductor of (Ba1−xLax)2In2O5+x

The structural characterization, thermogravimetric analysis and electrical properties for solid solution system, (Ba_1–xLa_x)₂In₂O_5+x with perovskite-type structure were investigated. X-ray diffraction showed that the orthorhombic phase was in the range of 0.0<x0.3, the tetragonal phase 0.3<x0.5, and the cubic phase 0.5<x. The sharp transition of electrical conductivity shifted to a lower temperature with increasing x and disappeared at the phase boundary between the orthorhombic and tetragonal phases. This perovskite-related oxide exhibited a pure oxide-ion conduction over the oxygen partial pressure range of 1 atm to 10^–3.5 atm, and the electrical conductivity reached the value of 1.610^–1 (S cm^–1) at 1073 K, which was nearly equal to that of the yttria stabilized zirconia. These properties were successfully explained in terms of disordered oxygen ions.This revised version was published online in November 2005 with corrections to the Cover Date.     

Electric properties of oxyfluorides Ba2In2O5−0.5x F x with brownmillerite structure

Synthesis of fluoro-substituted substances based on brownmillerite Ba₂In₂O₅ is carried out. The width of the homogeneity region of the Ba₂In₂O_5?0.5x F _x (0 < x ≤ 0.25) solid solution was established using X-ray analysis. Measurement of temperature dependences of conductivity in atmospheres with different partial pressure of water vapor (pH₂O = 3.3 and 2 × 10³ Pa) showed an increase in conductivity at T ≤ 550°C in a humid atmosphere, which is due to appearance of proton transport. The dependence of conductivity on partial oxygen pressure (pO₂ = 0.21 × 10⁵ to 10^?15 Pa) is studied in the temperature range of 500–1000°C; ion transport numbers are calculated. The method of polarization measurements was used to determine transport numbers of fluoride. Total conductivity is divided into ion (proton, oxygen, and fluoride ion) and electron components. Analysis of concentration dependences of conductivities showed that low concentrations of fluoride allow increasing both the total and partial conductivities (oxygen-ion and proton) and, besides, allow shifting the “order-disorder” phase transition by 100°C to the low temperature range.     

Electrochemical reduction of NO and O2 on La2−x Sr x CuO4-based electrodes

A series of La_2 − x Sr _x CuO₄ (x = 0.0, 0.05, 0.15, 0.25 and 0.35) compounds was investigated for the use of direct electrochemical reduction of NO in an all-solid-state electrochemical cell. The materials were investigated using cyclic voltammetry in 1% NO in Ar and 10% O₂ in Ar. The most selective electrode material was La₂CuO₄, which had an activity of NO reduction that was 6.8 times higher than that of O₂ at 400 °C. With increasing temperature, activity increased while selectivity decreased. Additionally, conductivity measurements were carried out, and the materials show metallic conductivity behavior which follows an adiabatic small polaron hopping mechanism.     

Characterization of superparamagnetic Mg x Zn1−x Fe2O4 powders

Structural and magnetic properties of Mg _x Zn_1−x Fe₂O₄ powders have been studied with respect to the application for thermal cancer therapy (magnetic hyperthermia). Mg _x Zn_1−x Fe₂O₄ (x=0.1–0.5) powders with particle sizes between 5 and 8 nm were produced by citrate method. The X-ray diffraction patterns of the samples correspond to a spinel phase. The lattice constant and the volume of the elementary cell increase when x changes from 0.1 to 0.5. The FTIR-spectra ascertain the spinel phase formation. The Mossbauer studies reveal the presence of extremely small particles, which undergo superparamagnetic relaxation at room temperature. The core-shell model has been applied to explain quadruple doublets. The quadruple splitting at “shells” is bigger than those at “cores” whereas the isomer shifts remain close. Magnetic studies confirm the presence of extremely small particles that behave as superparamagnetic ones.      

Anodic electrodeposition of Ag1− x Cu x O microcrystals

We demonstrate the anodic electrodeposition of copper-doped AgO at high pH using a silver counter-electrode. Precipitates from a mixture of nitrates and NaOH provided source material for the deposition, and application of a moderate anodic voltage (0.9 V) to the substrate led to deposition of crystalline nanoparticles with incorporated copper. Further increase of the NaOH concentration reduced the amount of copper in the crystals, and higher voltages degraded the crystal quality. XRD confirms the underlying structure to be that of AgO, and Auger and energy dispersive x-ray analyses confirm copper concentrations of approximately 3 % in the crystals.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Controlled Growth of SrxBa1−xNb2O6 Hopper- and Cube-Shaped Nanostructures by Hydrothermal Synthesis

Controlling the shape and size of nanostructured materials has been a topic of interest in the field of material science for decades. In this work, the ferroelectric material Sr_xBa_1−xNb₂O₆ (x=0.32–0.82, SBN) was prepared by hydrothermal synthesis, and the morphology is controllably changed from cube-shaped to hollow-ended structures based on a fundamental understanding of the precursor chemistry. Synchrotron X-ray total scattering and PDF analysis was used to reveal the structure of the Nb-acid precursor, showing Lindqvist-like motifs. The changing growth mechanism, from layer-by-layer growth forming cubes to hopper-growth giving hollow-ended structures, is attributed to differences in supersaturation. Transmission electron microscopy revealed an inhomogeneous composition along the length of the hollow-ended particles, which is explained by preferential formation of the high entropy composition, SBN33, at the initial stages of particle nucleation and growth.     

Low Temperature Sol-Gel Preparation of β-Al2TiO5 Thin Films: Spectroscopic Analysis of the Precursors

Two sol-gel syntheses allowed the preparation of -Al₂TiO₅ thin films on silicon substrates at 700°C, reacting aluminum and titanium alkoxides with and without acetylacetone as a chelating agent. Nuclear magnetic resonance (NMR) and mass spectra of the sols allowed identification of the intermediate species formed and to show the formation of an Al-Ti containing polymer establishing that the synthesis without acetylacetone leads to the most extensive polymerization. The formation of -Al₂TiO₅ at low temperatures is attributed to diffusion-limited crystallization process, which takes place in the conditions of high homogeneity at molecular level reached in the sol-gel synthesis. The crystallization of the films was studied as a function of the firing time and temperature and confirmed that -Al₂TiO₅ with better thermal stability was obtained with the synthesis without chelating agent.     

Synthesis and crystal structure of Mo6−x Nb x I11 (x = 1–1.5)

A solid solution Mo_{6 ? x} Nb _x I₁₁ (x = 1.1–1.5) containing cluster cores {Mo₅NbI₈} is obtained by the high-temperature reaction of molybdenum, niobium, and iodine (550°C, 70 h, quartz ampule). According to the X-ray diffraction data, heating at 800°C in a molybdenum container results in the decomposition of the solution to Mo₆I₁₂ and Nb₆I₁₁. According to the X-ray structure analysis data, the compounds are isostructural to the high-spin modification Nb₆I₁₁ (space group Pccn). The presence of Nb atoms in the structure changes the structural type from the layered (Mo₆I₁₂) to framework structure, noticeably increases the metalmetal distances (2.661–2.716 Å, 2.695 Å) Mo₆ octahedron with the retention of the distance from the metal (M) to the μ₃-“capped” I atoms, and strongly elongates the M₆-I-M₆ bridges almost to the value observed in Nb₆I₁₁.     

Electrophysical properties of solid solutions of Zn2 − x (Zr a Sn b )1 − x Fe2x O4 compositions

The electrophysical properties of the multicomponent Zn₂ZrO₄ ? Zn₂SnO₄ ? ZnFe₂O₄ system are studied. The electrophysical parameters of solid solutions of Zn_{2 ? x} (Zr _a Sn _b )_{1 ? x} Fe_2x O₄ (x = 0–1.0, Δx = 0.1, a + b = 1) are determined. It is found that the formed solid solutions are semiconductors with electrophysical properties that change in a regular fashion with composition and are distinguished by high values of resistivity (107–1012 Ω cm).     

Longitudinal conductivity of thin films of La1 − x Sr x F3 − x solid solutions on glass ceramics

The longitudinal conductivity of La_{1 ? x} Sr _x F_{3 ? x} solid solution films (x = 0–0.24) with thicknesses of 40–260 nm grown on glass ceramics at temperatures from room temperature to 300°C and frequencies of 10^?1–10⁶ Hz was studied by impedance spectroscopy. The concentration dependence of film conductivity on the SrF₂ content had a maximum near x = 0.05. An equivalent circuit was constructed on the basis of the impedance plots to describe migration processes. The DC conductivity was evaluated for all samples under study. The activation energies were estimated from the temperature dependences of the DC conductivities of the films. The resulting dependences of electrophysical parameters were compared with those for bulk materials in terms of the relaxation conductivity model.     

Mechanical properties of mixed conducting La0.5Sr0.5Fe1−x Co x O3−δ (0≤x≤1) materials

Young’s modulus, strain–stress behavior, fracture strength, and fracture toughness of (0≤×≤1) materials have been investigated in the temperature range 20–1,000°C. Young’s moduli of and , measured by resonant ultrasound spectroscopy, were 130±1 and 133±3 GPa, respectively. The nonlinear stress–strain relationship observed by four-point bending at room temperature was inferred as a signature of ferroelastic behavior of the materials. Above the ferroelastic to paraelastic transition temperature, the materials showed elastic behavior, but due to high-temperature creep, a nonelastic respond reappeared above ∼800°C. The room temperature fracture strength measured by four-point bending was in the range 107–128 MPa. The corresponding fracture toughness of , measured by single edge V-notch beam method, was 1.16±0.12 MPa·m^1/2. The measured fracture strength and fracture toughness were observed to increase with increasing temperature. The fracture mode changed from intragranular at low temperature to intergranular at high temperature. Tensile stress gradient at the surface of the materials caused by a frozen-in gradient in the oxygen content during cooling was proposed to explain the low ambient temperature fracture strength and toughness.     

Rubidium-cationic conductivity of Rb2−2x Ga2−x A x O4 (A = P, V, Nb, Ta) solid electrolytes

Solid solutions based on rubidium monogallate RbGaO₂ with a general formula Rb_2?2x Ga_2?x A _x O₄ (A = P, V, Nb, and Ta) are synthesized. Their crystal structure and temperature and concentration dependences of conductivity are studied. The highest rubidium-cationic conductivity is (1.8–3.9) × 10^?3 S cm^?1 at 400°C and (1.4–2.1) × 10^?2 S cm^?1 at 700°C. These results are compared with the data for rubidium monogallate doped with four-charged cations and solid solutions based on RbAlO₂.     

Atoms state and interatomic interactions in perovskite-like oxides: XXXII. Formation of paramagnetic clusters in the La1−0.33x Ca0.33x Fe x Al1−x O3 and La1−0.33x Sr0.33x Fe x Al1−x O3 solid solutions

Calcium- and strontium-containing lanthanum orthoferrites have been studied using magnetic dilution method. It has been shown that the iron-atom clusters with competing ferro- and antiferromagnetic exchange interactions can exist. By using Mossbauer spectroscopy, Fe(IV) atoms have been found in the La_1?0.33x Ca_0.33x Fe_xAl_1?x O₃ solid solutions and Fe(III) atoms in two different surroundings have been found in the La_1?0.33x Sr_0.33x Fe _x Al_1?x O₃ solid solutions. The compositions of paramagnetic clusters stable at the infinite dilution have been proposed basing of the magnetic susceptibility and Mossbauer spectroscopy data.