Structural investigations of V<Subscript>2</Subscript>O<Subscript>5</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–CaO glass system by FT-IR and EPR spectroscopies

xV₂O₅·(100 − x)[0.7P₂O₅·0.3CaO] glass system was obtained for 0 ≤ x ≤ 35 mol% V₂O₅. In order to obtain information regarding their structure, several techniques such as X-Ray diffraction, FT-IR, and EPR spectroscopies were used. X-Ray diffraction patterns of investigated samples are characteristic of vitreous solids. FT-IR spectra of 0.7P₂O₅·0.3CaO glass matrix and its deconvolution show the presence in the glass structure of all structural units characteristic to P₂O₅. Their number are increasing for x ≤ 3 mol% V₂O₅ then, for higher content of vanadium ions, the number of phosphate structural units are decreasing leading to a depolymerization of the structure. The structural units characteristic to V₂O₅ were not evidenced but their contribution to the glass structure can be clearly observed. EPR revealed a well resolved hyperfine structure (hfs) typical for vanadyl ions in a C_4v symmetry for x ≤ 3 mol% V₂O₅. For 5 < x < 20 mol% V₂O₅ the spectra show a superposition of two EPR signals one due to a hfs structure and another consisting of a broad line typical for associated V⁴⁺–V⁴⁺ ions. For x ≥ 20 mol% V₂O₅ only the broad line can be observed. The composition dependence of the line-width suggests the presence of dipole–dipole interaction between vanadium ions up to x ≤ 5 mol% V₂O₅ and superexchange interactions between vanadium ions for x > 5 mol% V₂O₅.     

structure and transport properties of Li1-2xCo1+xVO4 lithium ionic conductors

Li_1-2xCo_{1 +x} VO₄ (0 ≤x ≤ 0.25) spinel solid solutions were synthesized and characterized by x-ray diffraction and IR spectroscopy. The materials were found to have a cubic structure in the composition range 0 ≤x ≤ 0.1 and an orthorhombic structure forx> 0.1. The observed lattice distortions were shown to correlate with Co content. The conductivity of the solid solutions was measured as a function of temperature and oxygen partial pressure. The ionic and electronic (n andp) conductivities were determined. The conduction in the solid solutions was shown to be dominated by Li⁺ ions.     

Synthesis of Ba<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript>−Sr<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript> solid solution and their dielectric properties

Oxides of the type, Ba_3-xSr_xZnNb₂O₉ (0 ≤x ≤3), were synthesized by the solid state route. Oxides calcined at 1000°C show single cubic phase for all the compositions. The cubic lattice parameter (a) decreases with increase in Sr concentration from 4.0938(2) forx = 0 to 4.0067(2) forx = 3. Scanning electron micrographs show maximum grain size for thex = 1 composition (∼ 2 μm) at 1200°C. Disks sintered at 1200°C show dielectric constant variation between 28 and 40 (at 500 kHz) for different values of x with the maximum dielectric constant atx = 1.     

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.     

High-temperature equilibrium between YBa2Cu3-xCoxO6+δ solid solutions and oxygen

The equilibrium oxygen content of YBa₂Cu_3-xCo_xO_6+δ (0.2 ≤x ≤ 0.8) solid solutions was determined by coulometric titration at temperatures in the range 600–850°C and oxygen pressures 1 ≤po ₂ ≤ 10⁵ Pa. The partial enthalpy and entropy of oxygen dissolution were evaluated as a function of composition. The thermodynamic functions were found to change sharply near the high- and low-oxygen limits of the solid solution. The results are interpreted in terms of a quasi-chemical model considering three inequivalent oxygen sites in the basal plane.     

Preparation of La2-x Sr x NiO4 (x = 0-1.3) conducting oxides via a citrate route

La_2-x Sr_xNiO₄ (x = 0-1.3) oxide materials were prepared by the citrate and ceramic routes. The citrate precursors and final products were characterized by thermal analysis (DTA + TG), x-ray diffraction, scanning electron microscopy, IR spectroscopy, and specific surface and conductivity measurements. The use of citrate mixtures leads to the formation of amorphous precursors to La₂O₃, NiO, and La_2-xSr_xNiO₄ (x <-0.4); reduces the temperature required for obtaining solid solutions by 150–200‡C as compared to the ceramic route; and enables the preparation of fine powders (≤5 Μm) and dense ceramics. Deceased.     

Electrical properties of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses exhibiting majority charge carrier reversal

The thermoelectric power and d.c electrical conductivity of x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses were measured. The Seebeck coefficient (Q) varied from +88 μ V K⁻¹ to −93 μV K⁻¹ as a function of V₂O₅ mol%. Glasses with 10 and 15 mol% V₂O₅ exhibited p-type conduction and glasses with 25 and 30 mol% V₂O₅ exhibited n-type conduction. The majority charge carrier reversal occurred at x = 20 mol% V₂O₅. The variation of Q was interpreted in terms of the variation in vanadium ion ratio (V^{5 +}/V^{4 +}). d.c electrical conduction in x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses was studied in the temperature range of 150 to 480 K. All the glass compositions exhibited a cross over from small polaron hopping (SPH) to variable range hopping (VRH) conduction mechanism. Mott parameter analysis of the low temperature data gave values for the density of states at Fermi level N (E_F) between 1.7 × 10²⁶ and 3.9 × 10²⁶ m⁻³ eV⁻¹ at 230 K and hopping distance for VRH (R_VRH) between 3.8 × 10⁻⁹m to 3.4 × 10⁻⁹ m. The disorder energy was found to vary between 0.02 and 0.03 eV. N (E_F) and R_VRH exhibit an interesting composition dependence.     

Influence of strontium on the cubic to ordered hexagonal phase transformation in barium magnesium niobate

Oxides of the type Ba_3-xSr_xMgNb₂O₉ were synthesized by the solid state route. Thex = 0 composition (Ba₃MgNb₂O₉) was found to crystallize in a disordered (cubic) perovskite structure when sintered at 1000C. For higher Sr doping (x ≥ 0.5), there was clearly the presence of an ordered hexagonal phase indicated by the growth of superstructure reflections in the powder X-ray diffraction patterns. In all the compositions there was the presence of a minor amount of Ba_5-xSr_xNb₄O₁₅ phase which increased with Sr substitution up tox = 1 and then it remained nearly constant at about 5%. Samples sintered at 1300C showed the hexagonally ordered phase for the entire range of composition (0 ≤x ≤ 3). The degree of ordering being considerably greater than in the 1000C heated samples as evidenced by several superstructure reflections     

Synthesis and magnetic properties of M<Subscript>0.08</Subscript>Ti<Subscript>0.91</Subscript>V<Subscript>0.09</Subscript>O<Subscript>2 + δ</Subscript> · <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Cr,Mn, Fe,Co, Ni) nanopowders

Using sol-gel synthesis and ion exchange, we have prepared titanium vanadium oxide nanopowders doped with transition-metal ions: M_0.08Ti_0.91V_0.09O_{2 + δ} · nH₂O with M = Cr, Mn, Fe, Co, and Ni. The valence state of the ions in the nanopowders and their morphology and structure have been studied by scanning electron microscopy, X-ray diffraction, IR spectroscopy, and X-ray photoelectron spectroscopy. The M _x Ti_0.91V_0.09O_{2 + δ} · nH₂O oxides dried in air or calcined at 400°C in air are shown to be paramagnets. Vacuum annealing of Co_0.08Ti_0.91V_0.09O_{2 + δ} · nH₂O at 700°C gives rise to a significant ferromagnetic contribution.     

Novel structural properties of the lead–vanadate–tellurate glass ceramics

In this paper, we have examined and analyzed the effects of systematic intercalation of the lead ions on vanadate–tellurate glass ceramics with interesting results. The structural properties of the lead–vanadate–tellurate glass ceramics of compositions xPbO·(100 − x)[6TeO₂·4V₂O₅], x = 0 − 100 mol%, are reported for the first time. It has been shown by X-ray diffraction that single-phase homogeneous glasses with a random network structure can be obtained in this system. Among these unconventional lead–vanadate–tellurate glass ceramics, we found that network formers are good host material for lead ions and are capable to intercalate a variety of species such as Te₂V₂ ⁵⁺O₉, Pb₃(V⁵⁺O₄)₂, Pb₂V₂ ⁵⁺O₇, and V₂O₅-rich amorphous phase. On the other hand, these glass ceramics contain V⁴⁺ and V⁵⁺ ions necessary for the electrical conduction. Based on these experimental results, we propose that the V⁴⁺=O bonds are created by two different mechanisms: the first of reduction of V⁵⁺ ions to V⁴⁺ ions and thus of creation of V⁴⁺=O bonds.     

Composition dependence of discontinuousmagnetization in CuxFe3-xO4+δ

The spinel series Cu_xFe_3-xO_{4 + δ, 0 ≤ δ ≤ 0.4} (where x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.8 and 1.0) has been investigated by means of X-ray diffraction and Barkhausen jumps. Analysis of X-ray intensity data showed that this system separates into two phases at x < 1. The percentage of phase separation decreases with increasing copper content. The system shows a single phase at x = 1. The mean potential difference, V _B, and the frequency, F _B, of Barkhausen jumps were measured as a function of the magnetizing current. Addition of copper enhances the irreversible motion of domain walls. The sample with x = 1 shows the highest values of V _B and F _B. The potential energy of the walls increases with increasing copper content. This revised version was published online in November 2006 with corrections to the Cover Date.     

Crystal structure and magnetic properties of high-coercivity Sr1 ? xPrxFe12 ? xZnxO19 solid solutions

Sr_1−x Pr _x Fe_{12 − x} Zn _x O₁₉ ferrites with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 have been prepared by solid-state reactions between praseodymium, iron, and zinc oxides and strontium carbonate in air at 1470 K. According to X-ray diffraction results, the samples with x ≤ 0.2 were single-phase and those with 0.3 ≤ x ≤ 0.5 contained, in addition to the magnetoplumbite phase, small amounts of α-Fe₂O₃, ZnFe₂O₄, and PrFeO₃. The mixed-phase samples further fired twice at 1470 K for 4 and 2 h contained no impurity phases at x = 0.3 and contained only α-Fe₂O₃ at x = 0.4 and 0.5. In the composition range 0 ≤ x ≤ 0.3, the a and c cell parameters, unit-cell volume V, and X-ray density ρ_x of the magnetoplumbite phase vary linearly according to the relations a(?) = 5.8869 − 0.0162x, c(?) = 23.027 + 0.449 x, V(?³)= 691.10 + 9.65x, and ρ_x(g/cm³) = 5.102 + 0.230 x. The highest degree of combined heterovalent substitution of Pr³⁺ for Sr²⁺ and Zn²⁺ for Fe³⁺ in the SrFe₁₂O₁₉ ferrite (formation of Sr_1−x Pr _x Fe_{12 − x} Zn _x O₁₉ solid solutions) at 1470 K is x = 0.32−0.36. The saturation magnetization per formula unit (n _s) of the x = 0.1 ferrite exceeds that of SrFe₁₂O₁₉ by 1.7% at 6 K and by 15.2% at 308 K. The 308-K n _s and coercive force (_σ H _c) of the x = 0.2 ferrite exceed those of SrFe₁₂O₁₉ by 7.6 and 8.5%, respectively.     

Phase Relations in the Li–V2O5–Cu System at 600°C and Cathodic Properties of Cu x V2O5

The phase relations in the Li–V₂O₅–Cu system at 600°C are studied by x-ray diffraction. The existence of the known vanadium bronzes M _x V₂O₅ (M = Li, Cu) is confirmed, and the composition ranges of the related solid solutions are determined. -Li _x V₂O₅ (0.22 x 0.49) and -Li _x V₂O₅ (0.88 x 1.0) are shown to dissolve Cu, forming Li _x Cu _y V₂O₅ solid solutions with y = 0.72 – 1.48x and y = 0.58 – 0.18x, respectively. Cu _x Li _y V₂O₅ solid solutions (y= 0.51 – 0.76 x) are only obtained from -Cu _x V₂O₅ (0.24 x 0.67). -Li _x V₂O₅ and -Cu _x V₂O₅ form a continuous series of solid solutions. The cathodic properties of Li–V₂O₅–Cu materials in high-temperature pulsed lithium batteries are investigated.     

Electrical conductivity and thermoelectric power of LaCo<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> solid solutions

Increasing the degree of Ga³⁺ substitution for Co³⁺ ions in LaCo_{1 − x} Ga _x O₃ solid solutions (x = 0–1) considerably reduces their electrical conductivity: at T= 850 K, from 190.5 S/cm in LaCoO₃ to 1.32 × 10⁻⁵ S/cm in the x = 0.95 solid solution. The anomaly in the temperature-dependent conductivity of the solid solutions, due to the broad semiconductor-metal transition, decreases with increasing x. For x ≥ 0.8, there is a very weak or no anomaly. The activation energies for conduction in the samples with x = 0.90 and 0.95 are 0.89 and 0.92 eV, respectively. At room temperature, the materials with 0 ≤ x ≤ 0.3 have a negative thermoelectric power. With increasing temperature, it increases, crosses zero between 435 and 530 K, reaches a maximum in the range 500–650 K, and decreases at higher temperatures.     

Ion-selective properties of metastable (VO)<Subscript>0.09</Subscript>V<Subscript>0.18</Subscript>Mo<Subscript>0.82</Subscript>O<Subscript>3</Subscript> · 0.54H<Subscript>2</Subscript>O

This paper describes a thin-film solid electrode with an ion-sensitive membrane based on the mixed oxide (VO)_0.09V_0.18Mo_0.82O₃ · 0.54H₂O. The electrode is selective for tetravalent vanadium in the concentration range 3 ≤ pC _V ⁴⁺ ≤ 5 and acidity range 4.5 ≤ pH ≤ 6, with a slope close to the theoretical value. In the range 1 ≤ pH < 5, the electrode responds to changes in hydrogen ion concentration, with a slope of 50 ± 2 mV/pH. Its alkali-metal-ion response shows up in the range 1 ≤ pC _M ⁺ ≤ 4 for pH ≥ 6. We examine the effect of the Li⁺, K⁺, Na⁺, Cs⁺, Rb⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Co²⁺, Ni²⁺, Mn²⁺, Al³⁺, Cr³⁺, and VO₂⁺ ions on the potential of the electrode and determine its selectivity coefficients for these cations.     

Structural and magnetic properties of strontium–borate glasses containing iron ions

Glasses of the xFe₂O₃·(100 − x)[B₂O₃·SrO] system, with 0 ≤ x ≤ 30 mol%, were studied by EPR and magnetic susceptibility measurements. EPR spectroscopy and magnetic susceptibility measurements show that the Fe³⁺ ions are localized in sites of distorted octahedral symmetry and in clustered formations containing both Fe³⁺ and Fe²⁺ ions. Dipolar and superexchange interactions involving iron ions were revealed depending on the iron content of the sample.     

Oxidation State of Vanadium in Eu1 – xYxVTa2O9 Solid Solutions

The magnetic susceptibility of Eu_{1 – x} Y _x VTa₂O₉ (0 < x < 0.20) solid solutions was found to vary nonmonotonically with Y content. This result was interpreted as due to changes in the proportion of V⁴⁺ ions. Increasing the synthesis temperature from 1100 to 1300°C was shown to raise the proportion of V⁴⁺ in EuVTa₂O₉ from 9.87 to 12.03%. The highest light yield was observed at x 0.05, corresponding to the smallest V⁴⁺/V⁵⁺ ratio.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

Synthesis, Structure, and Properties of Ammonium Polyvanadomolybdate Xerogels

Powders and films of (NH₄)_{2 – x} H _x V_{12 – y} Mo _y O_{31 ±} · nH₂O (0 x 2, 0 y 3) xerogels with a layered structure were prepared for the first time. According to IR spectroscopy data, the V–O–Mo layers in the xerogels are similar to those in the delta vanadium bronze (NH₄)_0.5V₂O₅. X-ray photoelectron spectroscopy shows that the vanadium and molybdenum in the xerogels are mainly in the oxidation states 5+ and 6+, respectively. The materials also contain small amounts of V⁴⁺and OH^–. The thermal stability of the materials increases with Mo content. The electrical conductivity of the films depends on air humidity and reaches a maximum at the composition (NH₄)_1.5H_0.5V₉Mo₃O_{31 +} · nH₂O. At temperatures in the range 20–70°C and air humidity between 12 and 59%, the activation energy of conduction is very low.     

EPR and magnetic susceptibility studies on V2 O5-P2O5-PbO glasses

EPR and magnetic susceptibility investigations on the glass system with 04+ ion content are explained using a simulation program on the assumption of the superposition of two signals, one with hyperfine structure (hfs) typical for isolated ions and another one consisting of a broad line without hfs characteristic for clustered ions. The hfs is not shown for x<3mol%V₂O₅. The EPR data show the presence of V₄₊ ions in a square-pyramidal co-ordination (C_4V) for 3x20mol%V₂O₅. The progressive disappearance of hfs for high V²O⁵ content (>20 mol %) suggests the increase of the associated ion number coupled by superexchange interactions. This result is consistent with magnetic susceptibility data for >3 mol % where the temperature dependence of magnetic susceptibility is described by the Curie–Weiss type law with a negative paramagnetic Curie temperature. The magnetic susceptibility results allowed the estimation of the V⁴⁺/V⁴⁺ + V⁵⁺ ratio in the sample studied.