Chemical vapor transport: A viable approach to controlling the composition of intermetallic phases promising for catalyst engineering

A “dry” process is described for preparing activated metals via removal of the active component from an intermetallic phase using selective chemical vapor transport. In closed vapor transport systems containing the intermetallic phases Ni_xGa_{1 ? x} and Cu_xGa_{1 ? x} , gallium transport leads to the development of steady states, and the composition of the intermetallic phase is determined by the sample and charge temperatures. To produce catalytically active materials, the active component should be removed under more nonequilibrium conditions, e.g., in flowing transport agent vapor. For nickel-based structures, the catalytic activity of substances prepared by a conventional process has been compared to that of substances synthesized using selective chemical vapor transport.     

Effects of scandium addition on the in vitro degradation behavior of biodegradable Mg–1.5Zn–0.6Zr alloy

Heretofore, recognitions of the systematic effects of scandium addition on corrosion behavior of biodegradable magnesium alloys are not yet clear. In the present study, a series of Mg–1.5Zn–0.6Zr–xSc (ZK21–xSc, x?=?0, 0.2, 0.5, 1.0 wt.%) alloys were casted and investigated with respect to the immersion and electrochemical degradation behavior. The hydrogen evolution, pH monitoring, ion release and mass loss results demonstrated that ZK21–0.2Sc alloy exhibited the lowest corrosion rate. The surface morphology analyses displayed that an obvious uniform corrosion occurred in ZK21–xSc alloys with Sc content below 0.5, while localized corrosion occurred in ZK21–1.0Sc alloy. Corrosion potentials of ZK21–xSc alloys shifted toward more positive with the increasing Sc content. But ZK21–0.2Sc alloy exhibited the lowest corrosion current density and the largest corrosion film resistance. Compared with other developed Mg alloys, the ZK21–0.2Sc alloy demonstrated a superior degradation behavior.     

Effects of Ge<Superscript>4+</Superscript> acceptor dopant on sintering and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoceramics

Lead-free (K_0.5Na_0.5)(Nb_1-xGe _x )O₃ (KNN-xGe, where x = 0-0.01) piezoelectric ceramics were prepared by conventional ceramic processing. The effects of Ge⁴⁺ cation doping on the phase compositions, microstructure and electrical properties of KNN ceramics were studied. SEM images show that Ge⁴⁺ cation doping improved the sintering and promoted the grain growth of the KNN ceramics. Dielectric and ferroelectric measurements proved that Ge⁴⁺ cations substituted Nb⁵⁺ ions as acceptors, and the Curie temperature (T_C) shows an almost linear decrease with increasing the Ge⁴⁺ content. Combining this result with microstructure observations and electrical measurements, it is concluded that the optimal sintering temperature for KNN-xGe ceramics was 1020°C. Ge⁴⁺ doping less than 0.4 mol.%can improve the compositional homogeneity and piezoelectric properties of KNN ceramics. The KNN-xGe ceramics with x = 0.2% exhibited the best piezoelectric properties: piezoelectric constant d₃₃ = 120 pC/N, planar electromechanical coupling coefficient k_p = 34.7%, mechanical quality factor Q_m = 130, and tanδ = 3.6%.     

Chemical vapor transport as a means of controlling the composition of condensed phases

A new method is proposed for controlling the composition (nonstoichiometry) of low-volatile inorganic compounds. The basic principle of the method is the introduction (or removal) of one of the components into the low-volatile compound using reversible selective chemical vapor transport (CVT). Theoretical analysis is used to identify the process parameters determining the direction of mass transport: source temperature T₁, source composition x₁, and sample temperature T₂. Using nonequilibrium thermodynamics concepts, steadystate conditions are found under which mass transport ceases. A new type of phase diagram, x₂-T₁-T₂, is proposed, which describes the state of CVT systems under steady-state conditions without mass transport. The CVT process is used to prepare GaSe crystals with different deviations from stoichiometry. The crystals are characterized using x-ray diffraction and cathodoluminescence spectroscopy. The stability regions of two GaSe polytypes in the T-x phase diagram are located. CVT is used to control the compositions of phases in the In-S system. The advantages of the CVT method are analyzed with application to control over the composition of inorganic compounds.     

A comparison of corrosion inhibition of magnesium aluminum and zinc aluminum vanadate intercalated layered double hydroxides on magnesium alloys

The magnesium aluminum and zinc aluminum layered double hydroxides intercalated with NO ₃ ^- (MgAl-NO₃-LDH and ZnAl-NO₃-LDH) were prepared by the coprecipitation method, and the magnesium aluminum and the zinc aluminum layered double hydroxides intercalated with VO _x ^- (MgAl-VO _x -LDH and ZnAl-VO _x -LDH) were prepared by the anion-exchange method. Morphologies, microstructures and chemical compositions of LDHs were investigated by SEM, EDS, XRD, FTIR, Raman and TG analyses. The immersion tests were carried to determine the corrosion inhibition properties of MgAl-VO _x -LDH and ZnAl-VO _x -LDH on AZ31 Mg alloys. The results showed that ZnAl-VO _x -LDH possesses the best anion-exchange and inhibition abilities. The influence of treatment parameters on microstructures of LDHs were discussed. Additionally, an inhibition mechanism for ZnAl-VO _x -LDH on the AZ31 magnesium alloy was proposed and discussed.     

Structural and dielectric properties of PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions synthesized at high pressures and temperatures

(1 ? x)PbMg_1/3Nb_2/3O₃ · xPbZrO₃ (1 ? x)PMN · xPZ) solid solutions have been synthesized at a pressure of 5 GPa and temperatures from 1300 to 1700 K, and their structural and dielectric properties have been studied. The composition dependences of the average unit-cell parameter and dielectric permittivity for the solid solutions indicate that the PMN-PZ system has a morphotropic phase boundary near x = 0.65. The solid solutions have a cubic structure for x < 0.65, a rhombohedral structure in the range 0.65 < x < 0.9, and an orthorhombic structure (similar to that of PbZrO₃) for x > 0.9. The temperature and frequency dependences of dielectric permittivity suggest that the (1 ? x)PMN · xPZ samples with x < 0.65 consist of two ferroelectric phases: a relaxor with antipolar dipole order and a normal ferroelectric with a diffuse phase transition. The effect of annealing temperature on the ferroelectric state of the samples with x < 0.65 is examined. In the composition range 0.65 < x < 0.9, the samples have normal ferroelectric properties, independent of annealing temperature.     

Inhomogeneous State of the Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Doped with Manganese

Basing on electron spin resonance (ESR) data for Bi₂Te₃ doped by Mn ions we argue that this compound can be inhomogeneous and consists of two components with the different structures. Its main phase Bi _2?x Mn _x Te ₃ is intertwined with the microscopical inclusions of MnBi phase. The integral volume of these intermetal clusters is less than 1 % but nevertheless they exert the serious impact on the dynamic magnetic properties of the entire system. These inclusions are ferromagnetic with the Curie temperature of 630 K, while the main bulk phase Bi _2?x Mn _x Te ₃ has x= 0.05 orders at T _c= 10 K (qualitatively this twophase picture is valid not only for this given x). Below this temperature two ferromagnetic phases coexist. Since the integral spontaneous polarization in MnBi phase is averaged out due to its random orientations in different clusters the time-reversal symmetry of Bi ₂Te ₃ doped by Mn ions is violated only at the low-temperature ferromagnetic transition.     

Inhomogeneous magnetic states in Mn<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb (0.6 ≤ x ≤ 1.0) solid solutions

Mn_{2 ? x} Zn _x Sb (0.6 ≤ x ≤ 1.0) solid solutions are shown to undergo magnetic phase separation (coexistence of two magnetic phases in a structurally homogeneous material) using a combination of characterization techniques (magnetometry, X-ray diffraction, neutron diffraction, Mössbauer spectroscopy, and resistivity measurements). A model is presented for the coexistence of two magnetic phases in the two-sublattice ferrimagnet Mn₂Sb diamagnetically diluted with zinc.     

Improvement of the Magnetization of Barium Hexaferrites Induced by Substitution of Nd<Superscript>3+</Superscript> Ions for Fe<Superscript>3+</Superscript> Ions

Barium hexagonal ferrites (BaNd _x Fe_12?x O ₁₉) have been synthesized by initial high-energy milling of the precursors and calcining subsequently. The as-prepared samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). XRD and SEM examinations reveal that a high-crystallized hexagonal BaNd _x Fe_12?x O ₁₉ with lamellar morphology is obtained when the precursor is calcined at 1200^°C in air for 3 h. The hexagonal crystalline structure of BaFe₁₂ O ₁₉ is not changed after doping Nd³⁺ ions in BaFe₁₂ O ₁₉. However, lattice parameters a and b values increase with an increase in Nd content at first, then decrease. Nd substitution may improve the magnetic properties of BaNd _x Fe_12?x O ₁₉. BaNd_0.1Fe_11.9 O ₁₉, obtained at 1050^°C, has the highest specific saturation magnetization value (80.81 emu/g) and magnetic moment (16.21 μ _B); BaNd_0.2Fe_11.8 O ₁₉, obtained at 950^°C, has the highest coercivity value, 4075.19 Oe.     

Interaction of R<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si (R = La,Ce, Nd,Dy; <Emphasis Type="Italic">x</Emphasis> = 0–0.05) Silicides with Hydrogen

The interaction of R_{1 – x}Zr _x (R = La, Ce, Nd, Dy; x = 0–0.05) silicides with hydrogen has been studied at hydrogen pressures of up to 250 MPa. At a high pressure and a temperature of 20°C, hydrogen solubility in the solid phase is very low. Raising the reaction temperature leads to disproportionation of the silicides. According to X-ray diffraction data, the disproportionation reaction yields a rare-earth hydride and RSi₂ disilicide.     

Ionic conductivity of BaF<Subscript>2</Subscript> + ZnF<Subscript>2</Subscript> + CdF<Subscript>2</Subscript> + YbF<Subscript>3</Subscript> optical fluoride ceramic

The electrical conductivity of an optical fluoride ceramic in the quaternary system BaF₂ + ZnF₂ + CdF₂ + YbF₃ has been determined in the temperature range 338–722 K using impedance spectroscopy (5 to 5 × 10⁵ Hz). The 500-K ionic conductivity of the ceramic is σ = 3.3 × 10^–4 S/cm, which corresponds to the electrical characteristics of single crystals of the best conducting nonstoichiometric M_1–x R _x F_{2 + x} (M = Sr, Ba; R = La–Nd; x = 0.3–0.5) fluorite phases. We have observed nonmonotonic variation (breaks) in temperature-dependent σ, which is due to competing fluoride ion transport processes in different parts of the ceramic sample. The highly conductive state of the BaF₂ + ZnF₂ + CdF₂ + YbF₃ fluoride ceramic seems to be due to the formation of structural regions corresponding to a Ba_1–x Yb _x F_{2 + x} solid solution.     

Stoichiometry Analysis and Normal-State Properties of SmBa2Cu3−x Ru x O7−δ Superconducting Phase

The electrical resistivity of normal and superconducting states for SmBa₂Cu_3?x Ru _x O_7?δ (Sm-123) phase with 0.00 ≤ x ≤ 0.50, prepared by the conventional solid-state reaction technique, was studied. X-ray powder diffraction (XRD), scanning electron microscope (SEM), particle-induced X-ray emission (PIXE), Rutherford backscattering spectroscopy (RBS) and electrical resistivity measurements were performed in order to investigate the effect of Ru⁴⁺ ions substitution in Sm-123 phase. Both the phase formation and superconducting transition temperature T _c enhance up to x = 0.05. For x > 0.05, suppression of both the phase formation and T _c is observed and the superconductivity is completely destroyed around x = 0.50. The normal-state electrical resistivity was analyzed by the two- and three-dimensional variable range hopping (2D-VRH and 3D-VRH) and Coulomb gap CG. The dominant mechanism for Sm-123 phase is CG with x ≤ 0.20 while is 3D-VRH for x ≥ 0.30.     

Ferromagnetism in Fe-doped BaTiO<Subscript>3</Subscript> Ceramics

Polycrystalline samples of BaTi_1?xFe_xO₃ (x = 0.00–0.30) are prepared by solid-state reaction method and their structural and magnetic properties are studied. Detailed investigation of XRD patterns reveal the coexistence of tetragonal (space group P4mm) and hexagonal phases (space group P6 ₃/mmc) for x ≥ 0.1. Magnetic measurements reveal room-temperature ferromagnetism in x = 0.15–0.3 samples, and their ferromagnetic transition temperature increases from 397 K for x = 0.15 to 464 K for x = 0.3. The initial magnetization curves for x = 0.15–0.3 are analyzed in terms of bound magnetic polaron (BMP) model. The analysis of susceptibility data in the paramagnetic region by Curie-Weiss law confirms the ferromagnetic transition for x ≥ 0.15 and the effective magnetic moment systematically increases with increase in Fe concentration.     

Magnetic Behaviors of Ferromagnetic Semiconductor Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te Grown by MBE

The magnetic and structural properties of MBE-grown films of Zn_1?xCr _x Te were investigated. The magnetization versus magnetic field (M–H) measurement of Zn_1?xCr _x Te (x = 0.01–0.17) showed clear hysteresis loop at low temperatures. The ferromagnetic transition temperature (T_C) estimated from the Arrott-plot analysis increased almost linearly with the Cr composition (x) up to 275 K at x = 0.17. However, in the magnetization versus temperature (M–T) measurement, the irreversibility between the zero-field-cooled (ZFC) and field-cooled (FC) processes was observed. This is typically observed in the magnetic random system such as spin-glass or superparamagnetic phase. In the high resolution transmission microscopy (HRTEM) observations, structural defects such as stacking faults and polycrystalline-like structure were observed at high Cr compositions, whereas any apparent precipitates of different phases were not seen in all the range of Cr compositions examined. The correlation of the observed magnetic randomness with the local structural defects was discussed.     

Effect of Boron Substitution for Bi on Superconductivity of the Bi-2212 Phase in the Bi-Sr-Ca-Cu-O System

Possibility of boron substitution for Bi and the substitution effect on superconductivity is investigated for the Bi-2212 phase of Bi-Sr-Ca-Cu-O. From X-ray diffraction study, it is found that samples in the (Bi_2?x B _x )Sr₂CaCu₂O _z system are mainly of the single 2212 phase in a composition range of 0.0≤x≤0.6, and both of the lattice parameters a and c change with increasing x up to 0.6. From measurements of the magnetic susceptibility and the electrical resistivity, the superconducting transition temperature is found to increase up to 0.6 with increasing x. These results are considered to show that boron is substitutable for Bi up to x=0.6 in the (Bi_2?x B _x )Sr₂CaCu₂O _z system and that the boron substitution causes the number of hole-carriers to decrease in this system.     

Sintering behavior,phase structure and electric properties of KNNTS-BKNZ ceramics with excessive alkali metals

We investigated the effect of excessive alkali metals on sintering character, phase structure, dielectric, piezoelectric and ferroelectric properties in KNN-based ceramics thoroughly. The 0.96(K_0.48Na_0.52)_1+xNb_0.93Sb_0.02Ta_0.05O₃–0.04Bi_0.5(K_0.12Na_0.88)_0.5ZrO₃ [(KN) _x NTS-BKNZ] lead-free piezoelectric ceramics were prepared by conventional solid-state reaction method. The sintering temperature of (KN) _x NTS-BKNZ ceramics increases gradually while the sintering temperature zone becomes narrow with the increasing x value. For the composition of x?>?0.03, the grains could not grow in all sintering temperature. The coexistence system of rhombohedral and tetragonal phases has been found in (KN) _x NTS-BKNZ ceramics and the T_R?T, T_C, d₃₃, and ε_r show a upward tendency with the increasing x when 0?≤?x?≤?0.03. The maximal piezoelectric coefficient d₃₃ of 415 pC/N was obtained at x?=?0.03. In addition, these ceramics presented good temperature stability. This study exhibits that excessive alkali metals influence sintering character and electrical properties on KNN ceramics deeply. It was believed that this work would be helpful for further understanding the effect of excessive alkali metals on sintering behavior and electric properties in KNN-based ceramics.     

Synthesis and x-ray diffraction study of solid solutions in the Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>ZrO<Subscript>4</Subscript> system

The multicomponent refractory oxide system Zn₂(Ti_aSn_b)_{1 ? x} Zr_xO₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 1: 0, 2: 1, 3: 1, 4: 1; x = 0?1.0; Δx = 0.05) has been studied by x-ray diffraction, using samples prepared by melting appropriate oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions of different compositions.     

Correlation between the electrical and luminescent properties of high-purity gallium arsenide

Epitaxial n-GaAs layers with a background impurity concentration of N_D-N_A<10¹⁵ cm^?3, grown by chloride vapor phase epitaxy in an open system, exhibit correlation between the electrical properties and the long persistence of the edge photoluminescence lines D⁰x and D⁰h related to the hole trapping centers. An increase in the concentration of such trapping centers in n-GaAs leads to a decrease in the mobility of free charge carriers.     

Formation of Compounds in the Ag<Subscript>2</Subscript>O–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–MoO<Subscript>3</Subscript> System on Heating

This paper presents a detailed study of phase formation processes in the AgNO₃–Sb₂O₃–MoO₃ system during heating in air. The compositions of the solid-state reaction products have been determined using thermogravimetry and qualitative X-ray diffraction. The results demonstrate that, at a final heat treatment temperature of 1023 K, synthesis yields a range of Ag_2–xSb_2–xMo _x O₆ compounds with the pyrochlore structure and 0.0 ≤ x ≤ 2.0. The structural parameters of the synthesized phases have been refined by the Rietveld method in space group Fd3?m and their electrical conductivity has been measured.     

Vanadium Addition Effect on the Superconducting Properties of BPSCCO System

To study the vanadium addition effects on the BSCCO superconducting system, bulk samples with the general formula Bi_1.7Pb_0.3V _x Sr₂Ca₂Cu₃O_{10 + δ} (x = 0.0, 0.1, 0.2, 0.3 0.4 and 0.5) were prepared by solid-state reaction method. Energy-dispersive X-ray spectroscopy (EDX) analysis was used to test the proportions and energies of the elements of the compound. The XRD analyses showed an orthorhombic structure with two phases: a high-2223 phase and a low-2212 phase in addition to which an impure phase was found. The highest T _c at 118 K was obtained for the sample with x = 0.2. Scanning electron microscopy (SEM) was used to identify the morphology of the superconducting phase and to investigate the influence of vanadium.