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.     

Study of structure and properties of ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the ternary system ZnO–Bi₂O₃–P₂O₅ were prepared and studied in two compositional series 50ZnO–xBi₂O₃–(50 − x)P₂O₅ and (50 − y)ZnO–yBi₂O₃–50P₂O₅. Two distinct glass-forming regions were found in the 50ZnO–xBi₂O₃–(50 − x)P₂O₅ glass series with x = 0–10 and 20–35 mol.% Bi₂O₃. All prepared Bi₂O₃-containing glasses reveal a high chemical durability. Small additions of Bi₂O₃ (∼5 mol.%) improve thermal stability of glasses. All glasses crystallize on heating within the temperature range of 505–583 °C. Structural studies by Raman and ³¹P MAS NMR spectroscopies showed the rapid depolymerisation of phosphate chains within the first region with x = 0–15 and the presence of isolated Q⁰ phosphate units within the second region with x = 20–35. Raman studies showed that bismuth is incorporated in the glass structure in BiO₆ units and their vibrational bands were observed within the spectral region of 350–700 cm⁻¹. The evolution of properties and the spectroscopic data are both in accordance with a network former effect of Bi₂O₃.     

Synthesis and electrical properties of Bi2V1 ? xGexO5 + y solid solutions

A continuous series of Bi₂V_{1 − x} Ge _x O_{5 + y} solid solutions has been prepared by solid-state reactions, and their polymorphism and electrical properties have been studied. The solid solutions with 0 < x ≤ 0.2 are isostructural with the monoclinic phase α-Bi₂VO_5.5, and those with 0.2 < x ≤ 0.3 are isostructural with the orthorhombic phase. In the range 0.6 ≤ x < 1, the solid solutions have the orthorhombic Bi₂GeO₅ structure. The solid solutions with 0.4 ≤ x ≤ 0.5 have a tetragonal structure. Increasing the germanium content suppresses the ferroelectric phase transition in the Bi₂VO_5.5-based solid solutions, without changing the transition temperature. With increasing vanadium content, the conductivity of the solid solutions gradually increases, from 3 × 10⁻⁵ (x = 1) to 3 × 10⁻¹ S/cm (x = 0) at 550°C. Original Russian Text ? E.P. Kharitonova, V.I. Voronkova, 2007, published in Neorganicheskie Materialy, 2007, Vol. 43, No. 1, pp. 60–65.     

Effects of Gd doping on the sintering and microwave dielectric properties of BiNbO<Subscript>4</Subscript> ceramics

Gd³⁺ was chosen as a substitute for Bi³⁺ in BiNbO₄ ceramics, and the substitution effects on the sintering performance and microwave dielectric properties were studied in this paper. The high temperature triclinic phase was observed only in the Bi_0.98Gd_0.02NbO₄ ceramics when sintered at 920 °C. Both bulk densities and dielectric constant (ε_r) increased with the sintering temperature, while decreased with the Gd content. The quality factor (Q) exhibited a correlation to the Gd content and the microstructures of Bi_1−x Gd _x NbO₄ ceramics. At the sintering temperature of 900 °C, Bi_0.992Gd_0.008NbO₄ ceramics exhibited microwave dielectric properties of ε_r ∼ 43.87, Q × f ∼ 16,852 GHz (at 4.3 GHz), and its temperature coefficient of resonant frequency (τ_f) was found to be near-to-zero.     

Combustion synthesis and characterization of Ba<Subscript>2</Subscript>NdSbO<Subscript>6</Subscript> nanocrystals

Nanocrystalline Ba₂NdSbO₆, a complex cubic perovskite metal oxide, powders were synthesized by a self-sustained combustion method employing citric acid. The product was characterized by X-ray diffraction, differential thermal analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The as-prepared powders were single phase Ba₂NdSbO₆ and a mixture of polycrystalline spheroidal particles and single crystalline nanorods. The Ba₂NdSbO₆ sample sintered at 1500°C for 4 h has high density (∼ 95% of theoretical density). Sintered nanocrystalline Ba₂NdSbO₆ had a dielectric constant of ∼ 21; and dielectric loss = 8 × 10⁻³ at 5 MHz.     

Synthesis,structure and characterization of ceramic Ca4Bi2Ti4Nb6O30

The polycrystalline samples of Ca₄Bi₂Ti₄Nb₆O₃₀ (herein designated CBTN) were synthesized by the conventional ceramic method. Preliminary X-ray structural study of the compound showed the formation of a single phase solid solution having orthorhombic structure in the paraelectric phase. Measurements of the dielectric constant (ε) and dielectric loss (tan δ) as a function of temperature (−180–200°C) at 1 kHz and 10 kHz and also as a function of frequency (10² Hz to 10⁴ Hz) at five different temperatures [−180°C, −40°C, − 10°C 26°C (room temperature) and 75°C] have shown a dielectric anomaly and a phase transition at − 13 ±1°C in CBTN.     

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.     

Synthesis and electrochemical application of carbon nanotubes obtained from hexachloroethane

Carbon nanotubes (CNTs) with the average inner (outer) diameter of 10–20 nm (20–40 nm) and length up to 100s of nanometers were synthesized via Wurtz reaction at 400 °C for 12 h, using C₂Cl₆ and Na as reactants. These CNTs, having more defects because of the sp³ bonding raw material of C₂Cl₆, were used as electrode material to detect dopamine (DA) via cyclic voltammetry. The results show that there exists linear relation between peak currents and DA concentration in the range of 2 × 10⁻⁷∼2.8 × 10⁻⁴ mol L⁻¹.The linear regression equation is expressed as Ip (μA) = 0.089 + 0.134c (μmol L⁻¹). This CNTs-modified electrode showed high sensitivity with detection limit of 1 × 10⁻⁷ mol L⁻¹.     

Structure and piezoelectric properties of new (Bi0.5Na0.5)1?x?yBax(Yb0.5Na0.5)yTiO3 lead-free ceramics

New lead-free ceramics (Bi_0.5Na_0.5)_1−x−yBa_x(Yb_0.5Na_0.5)_yTiO₃ (x = 0.02–0.10 and y = 0–0.04) have been prepared by an ordinary sintering technique and their structure and piezoelectric properties have been studied. X-ray diffraction shows that Ba²⁺ and Yb³⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure and a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases is formed at 0.04 < x < 0.10. The partial substitutions of Ba²⁺ and Yb³⁺ for A-site ions of Bi_0.5Na_0.5TiO₃ decrease effectively the coercive field E _c and improve significantly the remanent polarization P _r. The ceramics with x = 0.06 and y = 0–0.02 situate within the MPB and possess the lower E _c and larger P _r, and thus exhibit optimum piezoelectric properties: d ₃₃ = 155–171 pC/N and k _p = 29.2–36.7%. The temperature dependences of the dielectric and ferroelectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T _d.     

Li-storage and cycling properties of spinel,CdFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as an anode for lithium ion batteries

Cadmium ferrite, CdFe₂O₄, is synthesized by urea combustion method followed by calcination at 900°C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) techniques. The Li-storage and cycling behaviour are examined by galvanostatic cycling, cyclic voltammetry (CV) and impedance spectroscopy in the voltage range, 0·005–3·0 V vs Li at room temperature. CdFe₂O₄ shows a first cycle reversible capacity of 870 (± 10) mAhg⁻¹ at 0·07C-rate, but the capacity degrades at 4 mAhg⁻¹ per cycle and retains only 680 (± 10) mAhg⁻¹ after 50 cycles. Heat-treated electrode of CdFe₂O₄ (300°C; 12 h, Ar) shows a significantly improved cycling performance under the above cycling conditions and a stable capacity of 810 (± 10) mAhg⁻¹ corresponding to 8·7 moles of Li per mole of CdFe₂O₄ (vs theoretical, 9·0 moles of Li) is maintained up to 60 cycles, with a coulombic efficiency, 96–98%. Rate capability of heat-treated CdFe₂O₄ is also good: reversible capacities of 650 (± 10) and 450 (± 10) mAhg⁻¹ at 0·5 C and 1·4 C (1 C = 840 mAg⁻¹) are observed, respectively. The reasons for the improved cycling performance are discussed. From the CV data in 2–15 cycles, the average discharge potential is measured to be ∼0·9 V, whereas the charge potential is ∼2·1 V. Based on the galvanostatic and CV data, ex situ-XRD, -TEM and -SAED studies, a reaction mechanism is proposed. The impedance parameters as a function of voltage during the 1st cycle have been evaluated and interpreted. Dedicated to Prof. C N R Rao on his 75th birthday, and his contributions to science for the past 56 years     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Rubidium ion conducting Rb2 ? 2xAl2 ? xAxO4 (A = Nb, Ta) solid electrolytes

Rb_{2 − 2x} Al_{2 − x} A _x O₄ (A = Nb, Ta) solid solutions have been synthesized, and their conductivity has been measured as a function of temperature and composition. The highest rubidium ion conductivity in the Rb_{2 − 2x} Al_{2 − x} A _x O₄ solid solutions is 3.16 × 10⁻³ S/cm at 300°C and ∼ 2 × 10⁻² S/cm at 700°C. The high rubidium ion conductivity of the synthesized solid electrolytes is mainly due to the formation of rubidium vacancies when Nb⁵⁺ or Ta⁵⁺ substitutes for Al³⁺ and to the specific features of the crystal structure of RbAlO₂.     

Synthesis and characterization of nano-sized BaxSr1?xSO4 (0 ≤ x ≤ 1) solid solution by a simple surfactant-free aqueous solution route

A facile aqueous solution route has been employed to synthesize Ba _x Sr_1−x SO₄ (0 ≤ x ≤ 1) solid solution nanocrystals at room temperature without using any surfactants or templates. The as-synthesized products were characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), scanning electron microscopy (SEM), and differential scanning calorimetry-thermogravimetry (DSC-TG). The Ba _x Sr_1−x SO₄ solid solution nanocrystals exhibit an orthorhombic structure and an ellipsoidal-shaped morphology with an average size of 80–100 nm. The lattice parameters of Ba _x Sr_1−x SO₄ solid solution crystals increase with increasing x value. However, they are not strictly coincident with the Vegard’s law, which indicates that the as-obtained products are non-ideal solid solutions. The Ba _x Sr_1−x SO₄ solid solution nanocrystals have an excellent thermal stability from ambient temperature to 1300°C with a structural transition from orthorhombic to cubic phase at about 1111°C.     

Phase diagram and electric properties of the (Mn, K)-modified Bi0.5Na0.5TiO3–BaTiO3 lead-free ceramics

In this study, the phase diagram and electric properties were demonstrated for a (Mn, K)-modified Bi_0.5Na_0.5TiO₃ (BNT)-based solid solution. (0.935−x) Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃−0.065BaTiO₃ with 0.5% mol Mn doping was prepared by a conventional solid-state reaction method. A morphotropic phase boundary (MPB) formed between the ferroelectric rhombohedral and tetragonal phases around x of 0.04 with the MPB tolerance factor t of 0.984–0.986. The temperature and composition dependence of the dielectric, piezoelectric, ferroelectric properties along with the strain characteristics were investigated in detail and a phase diagram was presented. Around the MPB region, the maximum values of piezoelectric constant d₃₃^* d_{33}^{*} of 290 pC/N, d ₃₃ of 155 pC/N, dielectric constant e₃₃^T /e₀ \varepsilon_{33}^{T} /\varepsilon_{0} of 1059 and low dielectric loss tangent tan δ of 0.017 were obtained. In addition, the authors also suggest that the solid solution with composition x of 0.24, exhibiting both high-depolarization temperature T _d of 182 °C, d₃₃^* d_{33}^{*} of 156 pC/N, d ₃₃ of 130 pC/N, will be favorable for high-temperature actuator and sensor applications.     

Water vapor absorption and proton conductivity of (Ba1−x La x )2In2O5+x

The proton conductivity of (Ba_1−x La _x )₂In₂O_5+x system has been investigated as a function of the La content, temperature and amount of absorbed water. The proton conductivity increased with La content up to x = 0.10, to reach a maximum of 1.12 × 10⁻⁵ (S/cm) at 400 °C. From that point on, it decreased. From the results of thermogravimetry and mass spectra, we confirmed that the water was absorbed in the (Ba_1−x La _x )₂In₂O_5+x system, in a maximum quantity of 0.14 mol/mol (sample). The proton conductivity increased monotonically with the quantity of water uptake, suggesting that this variable is one of the dominant parameter of proton conductivity in this system.     

Processing, sintering characteristics and dielectric properties of barium-substituted Pb(Mg1/3Nb2/3)O3–PbTiO3 solid solution

Solid solutions in the lead-based relaxor system Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ were modified by minor substitutions of Ba in the Pb-site of the perovskite lattice. The modified compositions were calcined at 830 °C for 3 h to yield fine-grained, single-phase perovskite materials. A small amount of excess MgO(0.05 wt %), which mostly served as a sintering aid, was added to the calcined batches and the resulting mixtures were sintered at temperatures between 1150 and 1250 °C for periods ranging from 3 to 5 h. The substitutions of BaO for PbO in the perovskite solid solution lattice caused a progressive lowering of the Curie point with increasing BaO content. On average, the Curie point decreased by about 10 °C for each mole of BaO substituted for PbO. Among the various Ba-substituted solid solutions studied, the one with a nominal composition Pb_0.99Ba_0.01[(Mg_1/3Nb_2/3)_0.9Ti_0.1]O₃ which has a Curie point located near 28 °C, exhibited excellent dielectric properties. On sintering at 1250 °C for 3 h, this composition yielded a density near 96% of the theoretical density. The peak dielectric constant of the composition at 1 KHz was slightly higher than 22000, and the corresponding tan δ value was 1.5% with a specific resistivity of 2.5 × 10¹² Ω cm^-1. This revised version was published online in November 2006 with corrections to the Cover Date.     

Preparation, proton conduction, and application in ammonia synthesis at atmospheric pressure of La0.9Ba0.1Ga1– x Mg x O3–α

La_0.9Ba_0.1Ga_1–x Mg _x O_3–α (0 ≤ x ≤ 0.25) was prepared by the microemulsion method. A single phase of LaGaO₃ perovskite structure was formed when x was ≥0.15. Electrochemical hydrogen permeation (hydrogen pumping) proved that La_0.9Ba_0.1Ga_1–x Mg _x O_3–α had proton conduction, and the proton conduction was measured by AC impedance spectroscopy method from 400 to 800 °C in hydrogen atmospheres. Among these samples, La_0.9Ba_0.1Ga_0.8Mg_0.2O_3–α has the highest proton conductivity with the values of 9.51 × 10⁻⁴ to 4.68 × 10⁻² S cm⁻¹ at 400–800 °C. Ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in an electrolytic cell using La_0.9Ba_0.1Ga_0.8Mg_0.2O_3–α as electrolyte. The rate of NH₃ formation was 1.89 × 10⁻⁹ mol s⁻¹ cm⁻² at 520 °C upon imposing a current of 1 mA through the cell.     

Recovery of <Superscript>131</Superscript>I and <Superscript>137</Superscript>Cs from a solution simulating NPP trap waters

Sorption of ¹³¹I and ¹³⁷Cs from a solution simulating NPP trap waters on various inorganic and organic sorbents was studied. The highest degree of ¹³¹I recovery (>99%) can be attained with Fizkhimin granulated sorbents based on coarsely porous silica gel containing Ag and Ni in 1: 4 ratio, with K _d for ¹³¹I exceeding 10⁵ ml g⁻¹ at V/m = 10³ ml g⁻¹ and contract time of the solid and liquid phases of 120 min. Elevation of the solution temperature to 40°C does not affect the degree of ¹³¹I and ¹³⁷Cs recovery. The degree of ¹³⁷Cs recovery in all the experiments did not exceed 35%. The degree of ¹³¹I recovery by coprecipitation with AgCl and Ag₄[Fe(CN)₆] was about ∼96% and only 65%, respectively.     

Boron doping of Si<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Si heterostructures grown by silicon sublimation in germane medium

Controlled boron doping of Si_{1 − x} Ge _x epilayers has been achieved during low-temperature growth of SiGe/Si(100) heterostructures by sublimation of boron-doped silicon in a germane medium. Boron-doped single-crystalline silicon plate was sublimed by resistive heating to ∼1300°C. Using this source, heterostructures with selectively doped layers, sharp dopant concentration profiles, and a maximum boron concentration of ∼1 × 10¹⁹ cm⁻³ were obtained.     

Influence of bismuth on properties and microstructures of Sr0.5Ba0.5−xBixTiO3 thin films

The influence of bismuth (Bi) on the dielectric and ferroelectric properties of Sr_0.5Ba_0.5−xBi_xTiO₃ (BST, 0 ≤ x ≤ 0.030 mol) thin films was studied. The results showed that the dielectric constant (ε_r) and dielectric loss (tan δ) decreased, and temperature, T_m, for maximum and ε_r (Curie temperature), moved to lower temperature with increasing Bi content. The P_r, P_s and E_c were 0.22 μC/cm², 0.32 μC/cm² and 60 kV/cm, respectively for Sr_0.5Ba_0.485Bi_0.015TiO₃ thin films measured at 100 Hz, 20 V. The microstructure of BST thinfilms was studied by XRD and TEM. Tetragonal perovskite grains existed in BST thin films, but the grain size decreased with increasing doping ratio in BST. The characteristic absorption band for octahedron [TiO₂] (471.65 cm⁻¹) was shifted to lower wave number.