Potassium ion conducting K2 ? 2 x Fe2 ? x P x O4 solid electrolytes

Potassium ion conducting solid electrolytes based on potassium monoferrite have been prepared by substituting pentavalent phosphorus cations for Fe³⁺. The highest conductivity of K_{2 − 2x} Fe_{2 − x} P _x O₄ is achieved in the range x = 0.05−0.10: 7.1 × 10⁻³ S/cm at 300°C and 1.6 × 10⁻¹ S/cm at 700°C. The rise in the conductivity of KFeO₂ upon phosphorus doping is due to the formation of potassium vacancies. Original Russian Text ? E.I. Burmakin, G.Sh. Shekhtman, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 8, pp. 995–998.     

Phase composition and structure of La1 ? x Ca x MnO3 + δ (0 ≤ x ≤ 0.2) solid solutions

A structural phase diagram of La_{1 − x} Ca _x MnO_{3 + δ} (0 ≤ x ≤ 0.2) solid solution in air has been constructed for the first time, and the equilibrium T-x fields of the monoclinic, orthorhombic, and rhombohedral phases in this system have been outlined. The transitions between these phases are accompanied by sharp changes in lattice parameters, suggesting that they are first-order. Original Russian Text ? S.Kh. Estemirova, A.M. Yankin, S.G. Titova, V.F. Balakirev, Yu.E. Turkhan, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 11, pp. 1387–1392.     

The morphotropic phase boundary and electrical properties of (1?? x )Pb(Zn1/2W1/2)O3– x Pb(Zr0.5Ti0.5)O3 ceramics

Ceramics in the solid solution of (1 − x)Pb(Zn_1/2W_1/2)O₃–xPb(Zr_0.5Ti_0.5)O₃ system, with x = 0.80, 0.85, 0.90, and 0.95, were synthesized with the solid-state reaction technique. The perovskite phase formation in the sintered ceramics was analyzed with X-ray diffraction. It shows that the rhombohedral and the tetragonal phases coexist in the ceramic with x = 0.90, indicating the morphotropic phase boundary (MPB) within this pseudo-binary system. Dielectric and ferroelectric properties measurements indicate that the transition temperature decreases while the remanent polarization increases with the addition of Pb(Zn_1/2W_1/2)O₃. In the composition of x = 0.85 which is close to the MPB in the rhombohedral side, a high piezoelectric property with d ₃₃ = 222 pC/N was observed.     

Electrical conductivity and thermal stability of (1 ? x )CsH2PO4/ x SiP y O z ( x = 0.2–0.7) composites

The physicochemical properties of (1 − x)CsH₂PO₄/xSiP _y O _z (x = 0.2–0.7) composites containing fine-particle silicon phosphates as heterogeneous additives have been studied at different humidities. The introduction of silicon phosphates suppresses the superionic phase transition of CsH₂PO₄ and increases the low-temperature conductivity of the materials, which depends significantly on humidity. The CsH₂PO₄-SiP _y O _z materials offer high conductivity (∼3 × 10⁻³ to 10⁻² S/cm at ∼110–230°C) at low water vapor pressures (3 mol % H₂O). Amorphization of the CsH₂PO₄ in the composites markedly changes its thermodynamic properties. The effect of long-term isothermal holding (210°C, 3 mol % H₂O) on the conductivity of the composites has been studied. Original Russian Text ? V.G. Ponomareva, E.S. Shutova, G.V. Lavrova, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 9, pp. 1131–1136.     

Structural and luminescent property of gallium chalcogenides GaSe1? x S x layer compounds

Structural and luminescence properties of GaSe_1−x S _x (0 ≤ x ≤ 1) series optical materials have been studied by X-ray diffraction, photoluminescence (PL), and piezoreflectance (PzR) measurements. Powder X-ray diffraction patterns showed the whole series layers present three different kinds of stacking formula with respect to the compositional change of sulfur from x = 0 to x = 1. The comparison of PL and PzR spectra reveals that the GaSe_1−x S _x layers have three different kinds of stacking phase from x = 0 to x = 1. The PL results show the whole series GaSe_1−x S _x layers emit the luminescences from red to blue visible region. The PL and PzR spectra of the GaSe_1−x S _x are analyzed. The structural variation in between the layers is discussed.     

Structure of Sr1 ? xPbxFeO3 ? δ (0 < x < 0.5) perovskite-like materials

We have synthesized Sr_{1 − x} Pb _x FeO_{3 − δ} (x = 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5) perovskite-like materials and studied their structure by X-ray diffraction, M?ssbauer spectroscopy, and electron microscopy. According to the X-ray diffraction data, the Pb solubility limit in the perovskite structure is x ≈ 0.15. The materials with x = 0.05 and 0.1 contained Pb_1.33Sr_0.67Fe₂O₅ inclusions 10–30 nm in size. Using chronopotentiometry and temperature-programmed desorption, we have estimated oxygen mobility in the materials with x = 0.05 and 0.1. The results demonstrate that Pb doping increases oxygen mobility in the strontium-ferrite-based materials.     

Melt synthesis of oxide phosphors with K2NiF4 structures: CaLa1? x Eu x GaO4

In order to synthesize compounds of various Perovskite-related structures, we have utilized a novel “melt synthesis technique” for phosphors rather than the conventional solid state reaction techniques. The solid state reactions require multi-step processes of heating/cooling with intermediate grindings to make homogeneous samples. However, for the melt synthesis, it is possible to make a homogeneous sample in a single step within a short period of time (1–60 s) due to the liquid phase reaction in the molten samples, which were melted by strong light radiation in an imaging furnace. In this study, we have prepared a red-phosphor CaLaGaO₄:Eu³⁺ which has a perovskite—related layered K₂NiF₄ structure. Well-crystallized CaLa_1−x Eu _x GaO₄ samples with the K₂NiF₄ structure have been obtained up to x = 0.25, but there was the formation of an olivine phase when x = 0.5–1.0. The red emission at 618 nm increased with the increasing value of x up to x = 0.25.

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Electrical properties of p -Si1 ? x Ge x Au-Based p - i - n structures and Schottky barriers

We have studied the properties of Si_{1 − x} Ge _x -based p-i-n structures and Schottky barriers in which the i-region had been produced via compensation with gold. The results demonstrate that the use of a guard ring in p-Si_{1 − x} Ge _x 〈Au〉 structures reduces the room-temperature reverse leakage current by two to three orders of magnitude. Such structures have sufficiently small reverse currents and a barrier on the order of 0.75 eV. p-Si_{1 − x} Ge _x 〈Au〉-based guard-ring structures are suitable for the fabrication of IR and nuclear detectors. Original Russian Text ? I.G. Atabaev, N.A. Matchanov, E.N. Bakhranov, M.U. Khazhiev, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 7, pp. 775–780.     

Preparation and Magnetic Properties of?(La1?xSr1+x)(Mn0.5Co0.5)O4

A series of single phase (La_1−x Sr_1+x ) (Mn_0.5Co_0.5)O₄ (0≤x≤0.40) materials with a tetragonal K₂NiF₄ structure was prepared by a solid state reaction method at 1400 or 1450 °C with a short period of heating time. Powder X-ray diffraction (XRD) and the Rietveld refinement method were employed for the structural analysis. Unit cell a- and c-axes decrease with increasing amount of Sr substitution. A discrepancy between the zero-field-cooled and the field-cooled magnetization is observed in all samples investigated below a characteristic temperature, T ^*, which likely arises from the canted nature of spins or the random freezing of spins. It appears that T ^* decreases with increasing amount of Sr substitution, which is possibly due to the enhancement of chemical pressure induced by Sr and a corresponding increases of the valence of Mn and/or Co.     

Stabilization of the anatase phase of Ti1?xSnxO2 (x < 0.5) nanofibers

We experimentally investigate the stabilization of the anatase phase of Ti_1−x Sn _x O₂ (x < 0.5) nanofibers when synthesized by an electrospinning method. The as-spun nanofibers became nano-grained, polycrystalline nanofibers after calcination and the diameters of the nanofibers depend on Sn content. Stabilization of the anatase phase in Ti-rich compositions and incorporation of Sn ions were confirmed by X-ray diffraction, Raman, X-ray absorption near-edge structure, and photoluminescence (PL) spectroscopies. Results from the PL study also demonstrated the tunable nature of the optical properties, with the emission maximum shifting towards higher wavelength with increasing Sn concentration.      

Elastic and inelastic properties of (Co0.45Fe0.45Zr0.1) x (Al2O3)1 ? x nanocomposites

The elastic (Young’s modulus) and inelastic (internal friction) properties of amorphous (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 − x} nanocomposites with various relative contents of the metallic and dielectric phases have been studied. In the region of low temperatures, the composites exhibit a peak of the internal friction (at ∼240 K), the intensity of which increases with the content of the metallic phase. For compositions above the percolation threshold, the temperature dependence of the internal friction exhibits exponential growth above 300°C, which is related to the migration of vacancy-like defects in the amorphous structure of the metallic phase.     

Oxygen-ion diffusion and electrical conduction of La2Mo2?2 x Fe x O9?δ systems

Based on the novel oxygen ion conductor La₂Mo₂O₉, a series of Fe-doped samples of La₂Mo_2−x Fe _x O_9−δ (x = 0, 0.025, 0.05, 0.1) was prepared by conventional solid-state reaction method. The structure, phase transition, oxygen ion diffusion and electrical conductivity were studied with X-ray diffraction (XRD), differential scanning calorimeter (DSC), direct current (dc) resistivity, and dielectric relaxation (DR) measurements. One DR peak associated with the short-distance diffusion of oxygen vacancies was observed in both temperature and frequency spectra. The activation energy for oxygen ion diffusion in Fe-doped La₂Mo₂O₉ samples was smaller than that in un-doped samples. Fe doping can increase the ionic conductivity of La₂Mo_2−x Fe _x O_9−δ samples as well as the ionic transference number in the temperature range from 680°C to 400°C in comparison with the un-doped samples, although the electronic conductivity slightly increases. It is found that because of the small solubility of Fe₂O₃ in La₂Mo₂O₉ (<5%), Fe doping cannot suppress the phase transition that occurred around 570°C, but 2.5% K doping at La site at the same time (e.g. in sample La_1.95K_0.05Mo_1.95Fe_0.05O_9−δ ) can completely suppress this phase transition and increase conductivity at lower temperatures.     

Structural and dielectric properties of Na1?xBaxNb1?x(Sn0.5Ti0.5)xO3 ceramics

Lead-free (1 − x)NaNbO₃/xBa(Ti_0.5Sn_0.5)O₃ (x = 0.1, 0.125, 0.15, 0.175, 0.2, and 0.3) ceramics were elaborated by the conventional ceramic technique. Sintering has been made at 1523 K for 2 h. The crystal structure was investigated by X-ray diffraction with CuKα radiation at room temperature. As a function of composition, these compounds crystallize with tetragonal or cubic symmetry. Dielectric measurements show that the materials have a classical ferroelectric behavior for compositions in the range 0.10 ≤ x ≤ 0.15 and relaxor one for compositions in the range 0.15 < x ≤ 0.30. Temperatures T _C or T _m decrease as x content increases. The ferroelectric behavior has been confirmed by hysteresis characterization. For x = 0.1, a piezoelectric coefficient d ₃₁ of 42.146 pC N⁻¹ was obtained at room temperature. The evolution of the Raman spectra was studied as a function of temperature for x = 0.1.     

The effect of Sm substitution on properties of Bi1.6Pb0.4Sr2Ca2? x Sm x Cu3O y superconductors

The effect of the partial substitution of Ca by Sm in the Bi-2223 superconducting samples have been investigated in terms of X-ray diffraction (XRD), EDXRF (Energy Dispersive X-ray Fluorescent), magnetoresistivity, critical temperature, transport critical current density, and ac susceptibility measurements. The samples were prepared by the conventional solid-state reaction method. XRD patterns are used to calculate lattice parameters and phase ratio of the Bi-2223 samples. The volume fraction was determined from the intensities of Bi-2223 and Bi-2212 peaks. The room temperature XRD patterns of the samples showed the presence of Bi-2223 phase decreases with increasing the Sm content. We estimated the transition temperature of the samples from the resistivity versus temperature measurements in dc magnetic fields up to 0.6 T. We observed that transition temperature, T _c , and transport critical current density, , depend on the Sm substitution. They both decrease with increasing the Sm substitution. We extracted the peak temperature, T _p , and the pinning force density from our previous ac susceptibility measurements. The pinning force density decreased with increasing the Sm content. The possible reasons for the observed decreases in critical temperature and critical current density due to Sm substitution were discussed.     

Effect of heat treatment in sulfur and mercury vapors on the magnetic susceptibility of Hg1 ? x Mn x Te1 ? y S y crystals

We have studied the effect of heat treatment in mercury and sulfur vapors on the magnetic susceptibility of Hg_{1 − x} Mn _x Te_{1 − y} S _y crystals. Measurements were performed by the Faraday method in the temperature range 77–300 K at H= 318 kA/m before and after heat treatments. The results demonstrate that the behavior of the magnetic susceptibility can be understood in terms of Mn-S-Mn-S, Mn-Te-Mn-Te, and (mixed) Mn-Te-Mn-S clusters of different sizes with indirect antiferromagnetic exchange interaction between the Mn atoms through the chalcogen atoms. Heat treatment in sulfur and mercury vapors leads to the formation of new clusters or changes (increases or decreases) the size of already existing clusters. Original Russian Text ? P.D. Maryanchuk, E.V. Maistruk, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 5, pp. 549–554.     

Electronic Properties and Superconductivity of Electron-Doped La1?x/2Pr1?x/2CexCuO4

La_1−x/2Pr_1−x/2Ce _x CuO _y (LPCCO) samples with doping level up to 20% have been synthesized and their electronic and superconductive properties are studied. X-ray diffraction revealed that the LPCCO system is a pure phase system with a T’214 structure. Magnetic and resistive measurements show that the system is superconducting at 0.08≤x<0.20 with T _cmax=25 K at x=0.12. An anti-ferromagnetism transition was also observed in under-doped PLCCO (x=0.05) with the window width of the anti-ferromagnetism phase being significantly narrower than that NCCO and PCCO systems. The behavior of the Ce doping is compared with Sr doping in this system, and the mechanism is discussed.     

Oxidation state of chromium in (Na0.5Bi0.5TiO3)(1?x)(BiCrO3)x solid solution; investigated by XAS and impedance spectroscopy

X-ray absorption spectroscopy (XAS) and impedance spectroscopy have been used to study the oxidation state of chromium in (Na_0.5Bi_0.5TiO₃)_(1−x)(BiCrO₃) _x solid solution. XAS measurements reveal that chromium ion occupies the octahedral site in Na_0.5Bi_0.5TiO₃ (NBT). The increase in chromium content increases the distortion in chromium-oxygen octahedral. No shift in the Cr–K edge was observed with increase in chromium content. The XAS measurements suggest that chromium exists either as +3 or +5 state in (Na_0.5Bi_0.5TiO₃)_(1−x)(BiCrO₃) _x . The impedance measurements show a considerable increase in the electrical conductivity with increase in chromium content. The activation energy for conduction mechanism was found to lie between 0.50 and 0.7 eV for all the samples. These measurements indicate that main contribution to the conductivity is because of oxygen defects generated by the incorporation of chromium at B-site of NBT.     

Effects of Ga content on thermoelectric properties of P-type Ba8Ga16+ x Zn3Ge27? x type-I clathrates

P-type Ba₈Ga_16+x Zn₃Ge_27−x (x = 0.1, 0.2, 0.3, and 0.4) type-I clathrates were synthesized by combining solid-state reaction with spark plasma sintering (SPS) technology. The effects of slight increase of Ga content on thermoelectric properties have been investigated. The results show that at room temperature the carrier concentration N _p of p-type Ba₈Ga_16+x Zn₃Ge_27−x clathrates increases remarkably compared with that of Ba₈Ga₁₆Zn₃Ge₂₇ compound, which results in the increases of electrical conductivity although carrier mobility μ _H slightly decreases. The thermal conductivity κ of all samples increases with the increase of Ga content. Ba₈Ga_16.2Zn₃Ge_26.8 compound exhibits the highest ZT value of 0.43 at 700 K, which is increased by 13% compared with that of Ba₈Ga₁₆Zn₃Ge₂₇ compound.     

X-ray photoelectron study on Ba0.5Sr0.5CoxFe1?xO3?δ (BSCF: x?=?0.2 and 0.8) ceramics annealed at different temperature and pO2

X-ray diffraction (XRD) and the X-ray photoelectron spectroscopy (XPS) were measured for the sintered BSCF ceramics (Ba_0.5Sr_0.5Co _x Fe_1−x O_3−δ, x = 0.2 and 0.8: BSCF5528 and BSCF5582, respectively), which were annealed at different temperatures (700 and 950 °C) and gases (O₂ and Ar). The unit cell of the annealed BSCF5528 at 950 °C under Ar expanded by 0.8%, while contracting by 0.45% under O₂. The cubic and rhombohedral phases coexist in the BSCF5582 annealed at 700 °C under O₂. The XPS peak areas of lattice oxygen (O²⁻) in O_1s , ~528 eV, and the shoulder peak of Co_2p /Ba_3d in BSCF5582 (~778 eV) increased significantly after being annealed in O₂. The areas of the peaks for BaCO₃ (87.9/90.2 eV) in Ba_4d preferentially were shown to decrease in Ar and increase in O₂.     

Structural and dielectric spectroscopy studies of the M-type barium strontium hexaferrite alloys (Ba x Sr1? x Fe12O19)

The M-type barium hexaferrite Ba _x Sr_1−x Fe₁₂O₁₉ (where 0 < x < 1) alloys were prepared by a new ceramic procedure. The samples were studied using X-ray diffraction and Rietveld analysis, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy, infrared and M?ssbauer spectroscopy. The X-ray analysis indicates that the all the samples present a hexagonal structure. The IR spectra showed three main absorption bands in range of 400–600 cm⁻¹ corresponding to SFO100 and BFO100. The M?ssbauer spectra showed a superposition of five subspectra associated with the five sites of the iron ion, which in the ferric state. The SEM studies showed that the hexaferrites presented grains that varied in the range of 260–305 nm. The dielectric properties: dielectric constant (ε′) and dielectric loss (tg δ) were measured at room temperature in the frequency range from 100 Hz to 40 MHz. The samples present a nonlinear behavior for the dielectric constant at 100 Hz, 1 kHz and 1 MHz. The dielectric constant is not following the linear mixing rule for the samples. The structural, dielectric and magnetic properties of the composite barium hexaferrite phases were discussed in view of applications as a material for permanent magnets, high density magnetic recording and microwave devices.