Impact of Pb substitution on the formation of high <Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconducting phase in BSCCO system derived through sol-gel process

Sol-gel process was employed to synthesize the Pb-BSCCO system having general composition Bi_2−xPb_xSr₂Ca₂Cu₃O_10−δ, where x=0.2, 0.4 and 0.8. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), dilatometry and vibrating sample magnetometer (VSM) were employed to study the materials produced at different stages. Two-stage heating firstly at 300 and then 800°C was adopted in order to avoid the burning of the materials and formation of carbonates. The carbonate formation was avoided by heating the materials firstly at 300°C for 2 h and without intermediate cooling moved to the furnace having temperature 800°C and hold for 2 h. The sintering behaviour of samples was studied by dilatometry and the results revealed that the sample having x=0.4 was stabled up to a temperature of 700°C while samples having x=0.2 and 0.8 to a temperature of 625°C. The maximum shrinkage was observed at 850°C in all the samples. On the basis of dilatometry results, the samples were sintered at 845°C for 60 h to observe the superconducting phases. The highest volume fraction of high superconducting phase (2223) was noticed in the sample containing x=0.4 having onset T _c=110 K.     

Production of bscco bulk high <Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconductors by sol-gel method and their characterization by ftir and XRD techniques

The production of bulk high T _c superconducting phase (2223) by EDTA-gel (ethylenediaminetetraacetic acid) techniques has been investigated. It is shown that close control of pH is necessary for the production of a well-complexed precursor which allows subsequent decomposition in two stages at 300 and 800°C. The problem of carbonate formation was investigated experimentally and solved. Precursors are characterised by Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) and the sintering behaviour was monitored by dilatometry. At least three different phases Bi₂Sr₂Ca_x−1Cu_xO_8+y (BSCCO); where x=1, 2, 3 were identified within superconducting pellets using XRD, named as Bi₂Sr₂CuO₇ (2201), Bi₂Sr₂CaCu₂O₉ (2212) and Bi₂Sr₂Ca₃O₁₀ (2223). The superconducting properties of the sintered samples were studied by vibrating sample magnetometer (VSM). Transition to a superconducting state around 80 K appeared in samples (sintered at 845°C) containing the Bi₂Sr₂Ca₁Cu₂O_y (2212) phase. Liquid phase sintering of the samples aided the formation of Bi₂Sr₂Ca₂Cu₃O_x (2223) phase at high temperature (860°C), which showed a superconducting transition temperature of 108 K.     

The application of microbalance technique in study of the high temperature superconductors

Many physical-chemical properties of oxide superconductors depend on oxygen content and its distribution in the sample. Investigations of the thermal decomposition of the oxide superconductors in dynamic vacuum are valuable, particularly in view of the high oxygen diffusion coefficient in these cuprates. Dynamic vacuum protects against the readsorption of oxygen from the environment. Samples of the high-temperature superconductors were synthesised from stoichiometric mixtures of high-purity oxides and carbonates.The lattice parameters of all preparations were controlled, in both initial and final experiments using a Stadi P (Stoe) diffractometer with a positron-sensitive detector (CuK radiation). The oxygen content was measured by iodometric titration with a reproducibility of at least 0.02.DC four probe resistivity measurements were performed on pellets to which copper contacts were attached by using silver paint. Thermogravimetric analyses (TG) were performed by using a Cahn RG ultramicrobalance system.The purpose of the present paper is to show the application of microbalance technique in study of high-temperature superconductors.This revised version was published online in November 2005 with corrections to the Cover Date.     

Application of conduction calorimetry for study of the reactivity of C2S in the system C2S-C4A3¯S-C¯S-H

A conduction calorimeter was used to determine the effect of the ignition temperature on the hydration reactivity of C₂S in the system C₂S-C₄A₃¯S-C¯S relevant to sulphoaluminate belite cement. The results thus obtained showed that the kinetics and mechanism of hydration of the system C₂S-C₄A₃¯S-C¯S are influenced by the temperature of C₂S synthesis. The hydration reactivity of C₂S increases with increasing temperature of ignition.     

Selective reduction of fullerene C60 by metals in neutral and alkaline media. Interaction of C60 with KOH

The reduction of fullerene C₆₀ by Zn and Mg in DMF was studied both in the presence and absence of KOH. Fullerene C₆₀ was reduced in these systems to form the C₆₀ ^n– (n = 1, 2, and 3) anions. The anions were detected by optical and ESR spectroscopies. It was found that Mg reduced C₆₀ to the monoanion, Mg/KOH and Zn reduced C₆₀ to the dianion, and Zn/KOH reduced C₆₀ to the trianion. Like KCN, potassium hydroxide adds to fullerene upon interaction with C₆₀ in DMF. The reaction of C₆₀ with KOH in benzonitrile was accompanied by the generation of the fullerene monoanion. A possible mechanism of the formation of fullerene monoanions in the presence of KOH is discussed. The degradation of the C₆₀ ^n– anions in air was studied.     

Analysis of thermo-magnetic fluctuations above the glass-transition temperature in Bi1.6Pb0.5Sr2−xEuxCa1.1Cu2.1O8+δ (0.000 ≤ x ≤ 0.180) system

The resistivity of Bi_1.6Pb_0.5Sr_2−xEu_xCa_1.1Cu_2.1O_8+δ (0.000 ≤ x ≤ 0.180) superconductor has been measured as a function of temperature and magnetic field. The resistivity shows a glassy behavior even at higher temperatures and magnetic fields for the Eu-doped samples as compared with the Eu free sample. The values of glass-transition temperature [T_g], magnetic field dependent activation energy [U₀(B)] and the temperature and magnetic field dependent activation energy [U₀(B,T)] are found to be maximum for optimal doping levels (x = 0.135) which shows that the flux lines are effectively pinned in this sample. Also for temperatures below the superconducting transition temperature (T_C), a scaling of measured resistivity curves in magnetic field (B = 0.4 and 0.8 T) is obtained and this scaling is quite useful for better understanding of the behavior of the flux vortices in high temperature superconductors.     

Subsolidus phase equilibria in the system AlVO4−MoO3

The phase equilibria in the solid state in the system AlVO₄?MoO₃ were determined by DTA and XRD methods. The experimental results are presented in the form of a phase diagram. In the subsolidus area, the system AlVO₄?MoO₃ is a real two-component system only within the range AlVO₄?AlVMoO₇.     

Subsolidus phase equilibria in the V9Mo6O40-Cr2(MoO4)3 system

The V₉Mo₆O₄₀?Cr₂(MoO₄)₃ system has been investigated using the differential thermal analysis (DTA) and X-ray phase diffraction methods. The system has been found not to be a real two-component system over the whole component system.     

A study of the compounds present in the three-component system Dy2O3-SeO2-H2O at 100°C

The solubility isotherm of the system Dy₂O₃-SeO₂-H₂O at 100°C was studied and drawn. The selenites present in the system were identified and isolated. A thorough TG, DTG and DTA analysis was made. By modelling the conditions of TG, DTG and DTA analysis, the phases of the thermal decomposition were isolated and identified. The chemistry of the reaction was described.     

Reproducibility of phase changes in the system CuCl2−KCl

The reproducibility of the phase changes at 533–543, 573–593K and 603–623 K in the system CuCl₂?KCl was investigated by DTA analysis, supplemented with röntgenographic analysis. Conclusions were drawn in connection with a liquid melt and the solid state of the system.     

Ab initio study of the Wolff rearrangement of C6H4O intermediate in the gas phase

Ab initio calculations of the geometry and reactivity of 1,2-ketocarbene C₆H₄O as an intermediate in organic reactions were performed using the second-order Møller-Plesset (MP2) perturbation theory in the 6-311G^* basis set. Only the singlet state of the intermediate was considered. An oxirene-like structure (6) with a six-membered ring and a ketene-like structure (5) with a five-membered ring were localized on the potential energy surface. Attempts to locate a quinone type structure characteristic of aliphatic ketocarbenes failed. The energy of structure5 is ?70 kcal mol^?1 lower than that of structure6. Harmonic frequencies and intensities of normal vibrations in the IR spectra of6 and5 were calculated. The activation energy of the Wolff rearrangement6→5 was estimated at 12.5 kcal mol^?1. The geometry of the transition state of this reaction resembles the quinone-like structure.     

A sol-gel route for the development of rare-earth aluminum borate nanopowders and transparent thin films

A new sol-gel route was applied to obtain Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and amorphous thin films by using Al(acac)₃, B(OPrⁱ)₃, Y(NO₃)₃·6H₂O, and Er(NO₃)₃·5H₂O as starting materials dissolved in propionic acid and ethyl alcohol mixtures. Our study shows that propionic acid acts as good chelant agent for yttrium and erbium ions while ethyl alcohol allows to dissolve Al(acac)₃. This process makes the resulting sols very stable to obtain homogeneous gels and transparent amorphous thin films. In addition, the propionic acid prevents the sol precipitation, making easy porous- and crack-free thin film depositions. Chemical reactions involved in the complexation were discussed. As-prepared powders and films are amorphous and present a good thermal stability due to their high glass transition (746 °C) and crystallization temperatures (830 °C). This new sol-gel route showed to be adequate to obtain dense and crack-free thin films free of organic and hydroxyl groups that can be considered as promising materials to be used in integrated optical systems.     

Investigation of nu(N-H) and nu(C-N) stretching modes of propylamine (C3H7NH2) in a binary system C3H7NH2 + CH3OH via concentration dependent Raman study and ab initio calculations

Raman spectra of propylamine (C3H7NH2) and its binary mixtures, C3H7NH2 + CH3OH with varying mole fractions of the reference system, C3H7NH2, C were recorded in two widely apart wavenumber regions, 3100-3600 cm(-1) and 1225-1325 cm(-1). In the former region, the two Raman bands at approximately 3305 and approximately 3326 cm(-1), obtained after the line shape analysis, which were assigned to symmetric nu(N-H) and anti-symmetric nu(N-H) stretching modes, respectively, show a downshift upon dilution. However, whereas the nu(N-H) anti-symmetric mode shows a shift of 18.6 cm(-1), the nu(N-H) symmetric mode shows a much smaller shift (5.7 cm(-1)) between neat liquid and high dilution, C = 0.1. This aspect has been explained using the optimized geometries calculated employing ab initio theory (MP2 level) for the neat C3H7NH2 and its different hydrogen-bonded complexes. The linewidth versus concentration plot for the nu(N-H) anti-symmetric stretching mode, however exhibits a distinct maxima at C = 0.4, which has been explained as a slight departure from the concentration fluctuation model. In the latter region, a symmetric peak is observed, which corresponds to nu(C-N) stretching mode, which shows an upshift upon dilution and an almost linear concentration dependence. This has also been explained in terms of the parameters obtained from the optimized geometries of the different hydrogen-bonded complexes.     

Analysis of structural and magnetic phase transition behaviors of La1−xSrxCrO3 by measurement of heat capacity with thermal relaxation technique

The heat capacity, C_p, of the La_1−xSr_xCrO₃ system and its temperature dependence have been measured by a thermal relaxation technique. Both structural and magnetic phase transitions were detected at temperatures that can be surmised from the phase diagram proposed in previous studies. The observed variation in enthalpy after the first-order structural phase transition, ΔH, showed agreement with those measured by differential scanning calorimetry (DSC). A decrease in the variation in C_p in the second-order magnetic phase transition, ΔC_p, with an increase in Sr content was detected, which can be attributed to a decrease in electronic spin configuration entropy with an increase in Sr content. In the dependence of ΔC_p on Sr content, a bending point was also observed at x  0.12, at which the crystal system varies from an orthorhombic-distorted perovskite structure to a rhombohedral-distorted perovskite structure.     

Investigations in the ternary system Ti-Mo-N by means of EPMA and XRD

Arc-melted ternary Ti-Mo-N alloys were heat treated at 1423 K in order to evaluate the compositions of the equilibrium phases. The composition of the bcc phase-Ti _x Mo_1–x with respect to Mo and Ti was determined by electron probe microanalysis (EPMA) and lattice parameter measurements (XRD). In order to avoid the effects of plastic deformation caused by powdering the ductile-Ti _x Mo_1–x alloys, the lattice parameter measurements were carried out on small particles of the compact samples using Debye-Scherrer cameras. The EPMA and XRD results agree within the expected range of accuracy. Apparently the solubility of nitrogen in-Ti _x Mo_1–x is low and does not perceptibly affect EPMA and XRD results. The relationship between the lattice parameter and the nitrogen content of-TiN_1–x was applied to determine the composition of-TiN_1–x in equilibrium with-Ti_xMo_1-x No solid solubility of Mo in TiN_1–x could be detected. The tie lines at 1423 K between the two phases were established.     

Vitamin D analysis in plasma by high performance liquid chromatography (HPLC) with C(30) reversed phase column and UV detection--easy and acetonitrile-free

Two physiologically important forms of vitamin D exist: vitamin D₂ and vitamin D₃, which by liver based hydroxylase enzymes are converted to 25-hydroxyvitamin D₂ and 25-hydroxyvitamin D₃, respectively. These hydroxylated metabolites of vitamin D are measured in plasma to assess the vitamin D status of animals and humans. Therefore cheap and reliable analytical methods are very much in demand in nutritional and physiological research. After saponification and extraction of plasma or serum samples the current method uses reverse phase high performance liquid chromatography on a C₃₀ column and with UV detection at 265 nm for quantifying vitamin D₂, vitamin D₃, 25-hydroxyvitamin D₂, and 25-hydroxyvitamin D₃. The method proved versatile with respect to plasma lipid content, sample amount, and plasma concentration of the vitamin D metabolites as it was tested using plasma from six different species: cattle, pigs, poultry, mink, horses, and humans. In cattle plasma recoveries were between 86.6 and 101.0%, within day error between 0.9 and 5.9%, and between day error between 0.2 and 1.7%. However, depending on species and sample amount error percentages varied. When running the method on standard reference material^® 972 “Vitamin D in human serum” from the National Institute of Standards and Technology (NIST) (Gaithersburg, USA) the results for 25-hydroxyvitamin D₂ and 25-hydroxyvitamin D₃ concentrations were within the boundaries provided by NIST, reflected by Z-scores between 0.1 and 0.9.     

Structural models for intergrowth structures in the phase system Al2O3-TiO2

The phase system Al₂O₃-TiO₂ was investigated in the compositional range from 48:52 to 62:38 mol% Al₂O₃:TiO₂. The samples were prepared by melting the binary oxides in an arc-imaging furnace and the obtained samples were examined by powder X-ray diffraction. The recorded powder patterns could be interpreted in terms of intergrowth structures consisting of two basic building blocks, which were deduced from the known crystal structures of β-Al₂TiO₅ and Al₆Ti₂O₁₃. The structure of a new ordered compound with the formula Al₁₆Ti₅O₃₄ is proposed. The thermal stability was estimated from DTA and tempering experiments and showed that all prepared samples decompose at temperatures around 800 °C into the binary oxides corundum and titania.     

Study of phase equilibria established up to the solidus line in the system Fe2V4O13−WO3

The phase equilibria established up to the solidus line in the system Fe₂V₄O₁₃−WO₃, one of the intersections of the three-component system Fe₂O₃−V₂O₅−WO₃, have been studied. The system appears not to be a real two-component system.

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Zusammenfassung Es wurde eine Untersuchung des Phasengleichgewichtes durchgeführt, welches bezüglich der Solidus-Linie im System Fe₂V₄O₁₃−WO₃, einer der Zwischenbereiche im Dreikomponentensystem Fe₂O₃−V₂O₅−WO₃, nachgewiesen wurde. Dieses System scheint kein echtes Zweikomponentensystem zu sein.

     

A novel method for the preparation of C18 ester-bonded RP-HPLC packings

Summary A novel procedure had been developed for the preparation of RP packings. A C₁₈ alkyl-chain was bound onto spherical silica (particle size d_p=5 μm, s=300 m²g⁻¹) with glycidoxypropyltrimethoxysilane as coupling agent. Elemental analysis, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) and chromatographic evaluation confirmed the bonding of the packings and their RP behavior.     

Phase equilibria in the Ag4SSe-SnTe system

The phase diagram of the system Ag₄SSe-SnTe is studied by means of X-ray diffraction, differential thermal and metallographic analyses and measurements of the microhardness and the density of the material. This diagram is divided into two eutectic-type subdiagrams by the composition Ag₄SSe·2SnTe. The unit-cell parameters of the intermediate phases 3Ag₄SSe·SnTe (phase A) and -Ag₄SSe·2SnTe (phase B) are determined as follows: for phase A: a=0.7851 nm, b=0.7196 nm, c=0.6296 nm, =101.32°, =85.90°, =111.36°; for phase B: a=0.3662 nm, b=0.3303 nm, c=0.3343 nm, =90.74°, =108.94°, =91.91°. The phase Ag4SSe·2SnTe melts congruently at 615°C and a polymorphic transition of the phase takes place at T _- =110°C.This revised version was published online in November 2005 with corrections to the Cover Date.