A facile synthesis of ZnS nanocrystallites by pyrolysis of single molecule precursors,Zn (cinnamtscz)<Subscript>2</Subscript> and ZnCl<Subscript>2</Subscript> (cinnamtsczH)<Subscript>2</Subscript>

ZnS nanocrystallites were synthesised by pyrolysis method using Zn (cinnamtscz)₂ and ZnCl₂ (cinnamtsczH)₂ (cinnamtsczH = cinnamaldehyde thiosemicarbazone) as single source precursors. The prepared ZnS nanocrystallites were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, UV-Vis and fluorescence spectroscopy. The peak broadening in XRD and emission at shorter wavelength in fluorescence spectra showed the presence of nanocrystallites. The blue shift in UV-Vis absorption spectroscopy also proved the formation of nanocrystallites. TEM images show presence of plate-like and spherical ZnS nanoparticles obtained from Zn(cinnamtscz)₂ and ZnCl₂ (cinnamtsczH)₂ respectively.     

Superconductivity,Magnetism, and Magnetoresistancein RuSr<Subscript>2</Subscript>R<Subscript>1.4</Subscript>Ce<Subscript>0.6</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10–δ</Subscript> (R = Eu,Sm)

Samples with nominal compositions RuSr₂R_1.4Ce_0.6Cu₂O_10–δ (R = Eu, Sm) were synthesized and their superconducting (SC) and magnetic properties were compared. A coexistence of AFM and FM ordering below the FM transition temperature was established in the two samples. It was shown that their SC properties are affected by a spontaneous vortex phase (SVP). The first critical fields of the two samples were calculate — H_cl≈ 70 Oe for R=Eu and 60 Oe for R=Sm. It was shown that the improved superconducting properties of the Sm-containing sample do not affect its FM behavior. A sizable magnetoresistance was observed in the two samples at T<T _c.     

Acousto-optic properties of LiBi(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> single crystals grown at low temperature gradients

This paper reports the starting charge composition and process parameters for low thermal gradient (<1°C/cm) Czochralski growth of uniform bulk LiBi(MoO₄)₂ crystals. The acousto-optic figure of merit (M ₂) of a LiBi(MoO₄)₂ crystal has been measured in different directions.     

Luminescence of Pb<Superscript>2+</Superscript> in MAl<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = Ca,Sr)

Pb²⁺ doped SrAl₂B₂O₇ was prepared by solution combustion synthesis. The synthesized material was determined by powder XRD. The photoluminescence properties of the synthesized phosphor were investigated at room temperature using a spectrofluorometer. The emission peak of Pb²⁺ doped SrAl₂B₂O₇ was observed at 420 nm upon excitation at 277 nm. The Stokes shift of SrAl₂B₂O₇:Pb²⁺ was calculated to be 12 292 cm⁻¹. The luminescence behavior of Pb²⁺ in both SrAl₂B₂O₇ and CaAl₂B₂O₇ was discussed. The text was submitted by the authors in English.     

Synthesis and electrical properties of Gd<Subscript>2</Subscript>MO<Subscript>5</Subscript> (M = Zr,Hf)

Polycrystalline Gd₂ZrO and Gd₂HfO₅ have been prepared by heat-treating coprecipitated oxide mixtures, and their order-disorder phase transitions have been studied in the range 20–1600°C. The materials have been shown to consist of nanostructured grains with a nanodomain size of ∼40 nm. Their electrical conductivity has been determined by impedance spectroscopy in air between 300 and 1000°C. The 1000°C conductivities of Gd₂ZrO₅ and Gd₂HfO₅ are 3.7 × 10⁻³ and 1.8 × 10⁻³ S/cm, and the respective effective activation energies are 1.37 and 1.56 eV.     

Thermochemical and luminescent properties of the K<Subscript>2</Subscript>MgV<Subscript>2</Subscript>O<Subscript>7</Subscript> and M<Subscript>2</Subscript>CaV<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = K,Rb, Cs) vanadates

We have studied the compounds K₂MgV₂O₇ and M₂CaV₂O₇ with M = K, Rb, and Cs. These vanadates melt incongruently in the range 635–717°C. Cooling their decomposition products to room temperature leads to the formation of nonequilibrium phase assemblages characteristic of the corresponding oxide systems. The compounds offer broadband photo- and radioluminescence with an essentially white (to the human eye) emission spectrum. A model is proposed for luminescence centers in the vanadates, which involves the formation of defects in vanadium-oxygen groups, and an energy level diagram of the emission centers is constructed in the form of configuration curves in the harmonic oscillator approximation. The luminescent properties of these compounds suggest that they can be used as basic components of cathodo- and roentgenoluminescent screens and white-light-emitting diodes with improved color performance.     

Synthesis of nanocomposites based on MO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> (M = Ca,Sr, Ba) glasses

This work examines the effect of KBF₄ additions on the crystallization behavior of glasses based on the multicomponent systems MO-Bi₂O₃-B₂O₃ with M = Ca, Sr, and Ba. The glass-ceramic composites obtained contain a δ-Bi₂O₃-based crystalline phase with a crystallite size of ≃7 nm, evenly distributed over the glass matrix. The 400°C electrical conductivity of the nanocomposites reaches 2 × 10⁻⁴ S/cm, and the activation energy is 1.1 eV, typical of anion conduction. These values are comparable to those reported for δ-Bi₂O₃ ceramics.     

Gas-sensing properties of nanostructured M<Subscript><Emphasis Type=Italic>x</Emphasis></Subscript>V<Subscript>2</Subscript>O<Subscript>5</Subscript> (M = Na,K, Rb,Cs) oxides

The gas-sensing properties of nanostructured vanadium oxide doped with alkali-metal cations (M _x V₂O₅ with M = Na, K, Rb, and Cs) have been studied by measuring the resistance of films as a function of analyte content using an impedance meter. The results show that the doped vanadium oxide is sensitive to hydrogen, carbon monoxide, and ammonia in the concentration ranges 0.1–80, 0.1–5, and 0.1–5 vol %, respectively. The strongest gas response is offered by Rb_0.47V₂O₅, which is due to the smallest interlayer spacing in the structure of this nanomaterial and to its larger specific surface area.     

Synthesis,X-ray structure analysis,and Raman spectroscopy of R<Subscript>2</Subscript>TiO<Subscript>5</Subscript>-based (R = Sc,Y) solid solutions

Order–disorder transitions in xR₂O₃ · (1 ? x)TiO₂ (R = Sc, 0.4 ≤ x ≤ 0.5; R = Y, 0.5 ≤ x ≤ 0.6) solid solutions with highly imperfect fluorite-derived structures have been studied using monochromatic synchrotron X-ray diffraction and Raman spectroscopy. The results demonstrate that the synthesis process leads to the formation of a fluorite-like (Fm3m) disordered phase and a nanoscale (~10–100 nm) pyrochlore-like (Fd3m) ordered phase of the same composition, coherent with the disordered phase. We have determined their lattice parameters. The Raman spectra of Sc₂TiO₅ (Y₂TiO₅) contain broad lines in low- and high-frequency regions: at 190, 350, and 775 (134, 188, 365, 404, and 727) cm^?1. These lines are characteristic of a pyrochlore-like phase with a varying degree of order and a disordered fluorite-like phase, respectively. The pyrochlore-like phase Y₂Ti₂O₇ has two strong Raman peaks in the low-frequency region: at 312 and 527 cm^?1. The formation of nanodomains with different degrees of order is caused by the internal stress that arises from the high density of structural defects in the unit cells of the solid solutions.     

Phase transitions of the NASICON-type mixed phosphates LiM<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> (M = Ti,Zr) and LiInNb(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The structural phase transitions of LiTi₂(PO₄)₃, LiInNb(PO₄)₃, and LiZr₂(PO₄)₃ have been studied by X-ray diffraction, impedance spectroscopy, ⁷Li NMR spectroscopy, and calorimetry. The results indicate that, as the temperature is raised, the lithium ions in the structure of LiTi₂(PO₄)₃ and LiInNb(PO₄)₃ redistribute between the M1 and M2 sites. The thermal expansion coefficients along the crystallographic axes of LiTi₂(PO₄)₃ and LiInNb(PO₄)₃ are estimated.     

Magnetic and Dielectric Properties of <Emphasis Type="Italic">R</Emphasis><Subscript>2</Subscript>CuTiO<Subscript>6</Subscript> Compounds (<Emphasis Type="Italic">R</Emphasis>=Y,La, Pr and Nd)

Magnetic and dielectric properties of the double perovskite compounds of the type R ₂CuTiO₆ (RCTO, where R=Y, La, Pr and Nd) has been studied. Y₂CuTiO₆ (YCTO) crystallizes in a hexagonal unit cell, whereas the other three compounds form into orthorhombic structure. All four compounds show paramagnetic behavior down to 5 K. The dielectric studies show moderate dielectric constant (ε′) and very small dielectric loss (tan δ) for YCTO. The orthorhombic members of RCTO compounds exhibit moderate values of ε′ and tan δ. The dielectric properties are presented and discussed here in the light of the influence of structure and rare-earth ions on the physical properties of RCTO compounds.     

Synthesis of new (Bi,La)<Subscript>3</Subscript>MSb<Subscript>2</Subscript>O<Subscript>11</Subscript> phases (M = Cr,Mn, Fe) with KSbO<Subscript>3</Subscript>-type structure and their magnetic and photocatalytic properties

Synthesis and structure of new (Bi, La)₃MSb₂O₁₁ phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi₃CrSb₂O₁₁, Bi₂LaCrSb₂O₁₁, Bi₂LaMnSb₂O₁₁ and Bi₂LaFeSb₂O₁₁ adopt KSbO₃-type structure (space group, Pn[`3])Pn\overline{3}). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O₆ octahedral network and other two are the identical networks having Bi₆O₄ composition. The magnetic measurements on Bi₂LaCrSb₂O₁₁ and Bi₂LaMnSb₂O₁₁ show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr^+ 3 and Mn^+ 3. The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of ∼ 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.     

CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>-B<Subscript>2</Subscript>Al<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>-H<Subscript>2</Subscript>O (B = Na,K) zeolites

The structures of gismondine and amicite are analyzed in comparison with one another and with those of the zeolites whose compositions lie in the hypothetical plane “CaAl₂Si₃O₁₀”-Na₂Al₂Si₃O₁₀-H₂O. It is shown that the structures are similar to each other and may undergo mutual transformations.     

Dy<Superscript>3+</Superscript>-activated M<Subscript>2</Subscript>SiO<Subscript>4</Subscript> (M = Ba,Mg, Sr)-type phosphors

The alkaline orthosilicates of M₂SiO₄ (M = Ba, Mg, Sr) activated with Dy³⁺ and co-doped with Ho³⁺ are prepared through conventional solid-state method, i.e., mixing and grinding of solid form precursors followed by high-temperature heat treatments of several hours in furnaces, generally under open atmosphere and investigated by X-ray diffraction (XRD) to get phase properties and photoluminescence (PL) analysis to get luminescence properties. The thermal behaviours of well-mixed samples were determined by differential thermal analysis (DTA)/thermogravimetry (TG). The PL spectra show that the 478 and 572 nm maximum emission bands are attributed, respectively, to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions.     

Synthesis and Superconductivity in Ba-doped (Ru,Cu)(Sr,Nd)<Subscript>2</Subscript>(Nd,Ce)<Subscript>2</Subscript>Cu<Subscript>2</Subscript>O<Subscript><Emphasis Type="Italic">z</Emphasis></Subscript> Compounds

We prepared various (Ru_0.5Cu_0.5)(Sr_1.67−x Ba _x Nd_0.33)(Nd_1.34Ce_0.66)Cu₂O _z samples with varying Ba contents by x=0, 0.1, 0.2, 0.33, 0.5 and 0.835. X-ray diffraction revealed that the phase purity of the samples increases as the Ba-doping content increases and single- phase compounds could be obtained for samples with 0.1≤x≤0.33. Contrary to the Ba-free sample, superconductivity could be induced by partially substituting Ba for Sr and superconductivity with onset T _c of about 15 K is observed for the sample with x=0.2. The superconducting behavior of the Ba-doped samples is discussed in conjunction with thermoelectric power measurements.     

Graphite intercalation in the graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-R (R = H<Subscript>2</Subscript>O,C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH,C<Subscript>2</Subscript>H<Subscript>5</Subscript>COOH) systems

The electrochemical behavior of graphite in polar solvent-H₂SO₄ electrolytes is studied in a wide range of H₂SO₄ concentrations. The results demonstrate that, with decreasing H₂SO₄ concentration, the charging curves become smoother and shift to higher potentials, the stage index increases, and intercalation compounds are more difficult to obtain. At H₂SO₄ concentrations of 50% and lower, graphite polarization is accompanied by a significant overoxidation, as evidenced by the anomalously small intercalate layer thicknesses: 7.75–7.85 Å. Anodic polarization of graphite in electrolytes consisting of H₂SO₄ and a polar solvent (H₂O and C₂H₅OH) follows the same mechanism as in the case of the formation of graphite bisulfate. In going from water to C₂H₅OH, a less polar solvent, the intercalation threshold increases from 30 to 70% H₂SO₄. It is shown using a set of characterization techniques that, in the graphite-H₂SO₄-R (R = H₂O, C₂H₅OH) systems, the solvent is not intercalated into graphite. Stage I–III ternary graphite intercalation compounds (TGICs) are synthesized for the first time in the graphite-H₂SO₄-C₂H₅COOH system: stage I TGICs at H₂SO₄ concentrations above 70%, stage II in the range 30–70% H₂SO₄, and stage III at H₂SO₄ concentrations down to 10%. The intercalate layer thickness in the TGICs is 7.94 Å. The mechanism of TGIC formation in this system is shown to differ from those in mixtures of H₂SO₄ and other organic acids. Thermal analysis in combination with spectroscopic analysis of gaseous products provides clear evidence for intercalation of propionic acid into the TGIC and indicates that the thermal stability of this compound is lower than that of graphite bisulfate.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 162–169.Original Russian Text Copyright © 2005 by Shornikova, Sorokina, Maksimova, Avdeev.     

Synthesis and high-temperature electrical conductivity of Ln<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and LnYTi<Subscript>2</Subscript>O<Subscript>7</Subscript> (Ln = Dy,Ho)

Ho₂Ti₂O₇ and LnYTi₂O₇ (Ln = Dy, Ho) pyrochlores have been synthesized using hydroxide coprecipitation, mechanical activation, and firing at 1600°C. The bulk and grain-boundary components of their conductivity have been determined for the first time by impedance spectroscopy. The 740°C bulk conductivity of Ho₂Ti₂O₇ is 4 × 10^?4 S/cm, and that of HoYTi₂O₇ is 1 × 10^?3 S/cm, with activation energies E _a = 1.01 and 1.17 eV, respectively, suggesting that these materials are new oxygen-ion conductors. The bulk conductivity of DyYTi₂O₇ (3 × 10^?4 S/cm at 740°C, E _a = 1.09 eV) is almost one order of magnitude lower than that of HoYTi₂O₇ (1 × 10^?3 S/cm at 740°C, E _a = 1.17 eV).     

Formation and growth studies of the (Bi,Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10</Subscript> phase in Ag sheathed tapes

The formation and the thickness growth of the (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ phase in Ag-sheathed tapes have been investigated by scanning electron microscopy on samples sintered at 840°C in a flow of 8.5% O₂ (rest N₂) and quenched in air after sintering for 1 to 50 h. The thickness of the (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ grains was measured statistically after different sintering times. The experimental results show that the average thickness of these grains increases during the entire sintering period, while the average thickness growth rate decreases exponentially with sintering time. The volume fractions of the various phases present during the heat treatment were also measured from micrographs. Detailed studies of the microstructure and phase formation kinetics support the view that the formation of the (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ phase proceeds via a nucleation and growth process. Based on the present observations, a model describing the microstructure evolution is presented.