Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Phase relations and thermodynamic properties of compounds in the pseudobinary system BaO-Y2O3

The coexisting phases in the pseudobinary system BaO-Y2O3 have been identified by equilibrating samples containing different amounts of component oxides at 1173, 1273 and 1373 K. Only two ternary oxides, BaY2O4 and Ba3Y4O9, have been found to be stable in the temperature range of investigation. Solid state galvanic cells: Pt, O2+BaO+BaF2double vertical barBaF2+2mol%Al2O3double vertical barBaF2+BaY2O4+Y2O3+O2, Pt and Pt, O2+BaO+BaF2double vertical barBaF2+2mol% Al2O3double vertical barBaF2+BaY2O4+Ba3Y4O9+O2, Pt have been employed for determining the Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from the component oxides in the range 850 to 1250 K. A composite solid electrolyte incorporating Al2O3-dispersed BaF2 was used in the cells. To prevent interaction between the Al2O3 powder and electrode materials, the solid electrolyte was coated with pure BaF2. The Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from component oxides are given by: Δf0 (BaY2O4, s)=−128,310+5.211T (±580) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K) and ΔGfo(Ba3Y4O9, s)= −317,490 −24.704T (±1100) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K).

Ba3ZnTa2-xNbxO9 and Ba3MgT2-xNbxO9: synthesis, structural and dielectric studies

Oxides of the families Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9 were obtained by the solid state reaction route at 1573 K and were found to crystallize in the disordered (cubic) perovskite structure. In Ba3ZnTa2-xNbXO9 and Ba3MgTa2-xNbxO9 the entire range (0 less than or equal to x less than or equal to 1) of solid solutions could be synthesized. The dielectric constant decreases with increase in frequency for all compositions in the range 40 Hz to 100 kHz (epsilon (r) varies from 16 to 22). The dielectric loss (D) shows a broad maximum for both Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9. The maxima is centered around 2 kHz in the former and near 10 kHz in the latter. (C) 2001 Elsevier Science Ltd. All sights reserved.

Dynamics and local structure of colossal magnetoresistance manganites

We report Extended X-ray Absorption Fine Structure and anelastic spectroscopy measurements on on hole doped manganese oxides La1-xCaxMnO3 which present the colossal magnetoresistance effect. EXAFS measurements were realized both in the absence and presence of an applied magnetic field of 1.1 Tesla, in a wide temperature range (between 330 and 77 K) and at various dopings (x = 0.25 and x = 0.33). The magnetic field orders the magnetic moments so favouring the electron mobility and the reduction of Mn-O octahedra distortions. We observe the presence of four short and two long Mn-O distances (1.93 and 2.05 Angstrom respectively) above and also below the metal-insulator phase transition. The overall distortion decreases but does not completely disappear in the metallic phase suggesting the possible coexistence of metallic and insulating regions at low temperatures. The magnetic field reduces the lattice distortions showing evidence of a microscopic counterpart of the macroscopic colossal magnetoresistance. We also present preliminary anelastic relaxation spectra in a wide temperature range from 900 K to 1 K on a sample with x = 0.40, in order to study the structural phase transitions and the lattice dynamics. A double peak has been observed at the metal-insulator transition in the imaginary part of Young's modulus. This double peak indicates that the metal-insulator transition could be a more complex phenomenon than a simple second order phase transition. In particular the peak at lower temperatures can be connected with the possible presence of inhomogeneous phase structures. Another intense dissipation peak has been observed corresponding to the structural orthorhombic-trigonal transition around 750 K.

Bi2−xPbx(Ca, Sr)n+1CunO2n+4+δ (n = 1, 2, 3, and 4) family of superconductors

Superconducting oxides of the Bi1.5Pb0.5(Ca, Sr)n+1CunO2n+4+δ series with n = 1, 2, 3 and 4 have been characterized. The superconducting transition temperature increases markedly with n up to n = 3, but the Tc of the n = 4 member is not much higher than that of the n = 3 member. The Tc does not change significantly in Bi2−xPbxCaSr2Cu2O8+δ with x (0.1 < x ≤ 0.5).

Structural aspects of high-temperature cuprate superconductors

High-temperature superconductivity constitutes the most sensational discovery of recent times. Since these new superconductors are complex metal oxides, chemistry has had a big role to play in the investigations. For the first time, stoichiometry, structure, bonding, and such chemical factors have formed central themes in superconductivity, an area traditionally dominated by physicists. These oxide superconductors have given a big boost to solid-state chemistry.

An investigation of the PrBa2Cu3O7-δ system

Members of the PrBa2Cu3O7–delta system possessing the orthorhombic structure over a wide range of oxygen stoichiometry (delta=–0.5 to +0.5) have been prepared and characterized. Similar compositions with a tetragonal structure have also been prepared. None of the oxides is superconducting, independent of the structure or stoichiometry. Praseodymium seems to be present to a small extent in the 4+ state in oxygen-excess (negative delta) samples. Orthorhombic PrBa2Cu3O7–delta samples show the presence of twins suggesting that twins arise from orthorhombicity and have no relation to the superconductivity. A neutron diffraction study of a near-stoichiometric sample has shown a disordered orthorhombic structure with 72% occupancy of the 01 (chain) sites and with no interchange between Pr and Ba sites.

The Amenability Studies on Beneficiation of Low Grade Phyllite Deposits of Tungsten From Degana, Rajasthan

The phyllite deposit of Degana, Rajasthan, containing tungsten values in the form of wolframite, (Fe, MnWO sub 4 ) finely dispersed in the quartz groundmass, has been quantitatively analysed to give 0.063% WO sub 3 , 6.66% Fe sub 2 O sub 3 , 14.30% Al sub 2 O sub 3 and 67.4% SiO sub 2 . The major gangue minerals identified are quartz, iron oxides and mica along with minor amounts of graphite, fluorite and sulphides. The amenability of the ore to gravity concentration, magnetic separation and a combination of the processes has been studied. A combination of tabling on --100 mesh ground ore and dry magnetic separation of the tabled concentrate gave a final concentrate containing 1.834% WO sub 3 with an overall recovery of only 4.6%. The complex mineralogy combined with fine dispersion of very low W values have contributed to the low recoveries and grades. Graph, photomicrographs. 10 ref.--AA

A comparative study of superconducting LaBa2Cu3O7−δ and La3−xBa3+xCu6O14+δ

Based on X-ray diffraction and electron microscopy it is shown that oxides of the general formula La Ba2Cu3O7−δ become tetragonal when δ deviates slightly from 0. This tetragonal structure is similar to that of La3−xBa3+xCu6O14+δ, with a cubic perovskite subcell and triple periodicity. Electron micrographs of these tetragonal oxides show 90° microdomains. Orthorhombic LaBa2Cu3O7−δ with high Tc (not, vert, similar77 K) is found only when δ reverse similar, equals 0; this sample is subject to formation of twins. Fluorine substitution seems to favor superconductivity.

Reducibility of Ce1-xZrxO2: origin of enhanced oxygen storage capacity

We combine first-principles calculations with EXAFS studies to investigate the origin of high oxygen storage capacity in ceria-zirconia solid solution, prepared by solution combustion method. We find that nanocrystalline Ce0.5Zr0.5O2 can be reduced to Ce0.5Zr0.5O1.57 by H-2 upto 850 degrees C with an OSC of 65 cc/gm which is extremely high. Calculated local atomic-scale structure reveals the presence of long and short bonds resulting in four-fold coordination of the cations, confirmed by the EXAFS studies. Bond valence analysis of the microscopic structure and energetics is used to evaluate the strength of binding of different oxide ions and vacancies. We find the presence of strongly and weakly bound oxygens, of which the latter are responsible for the higher oxygen storage capacity in the mixed oxides than in the pure CeO2.

Improved synthesis of carbon nanotubes with junctions and of single-walled carbon nanotubes

Pyrolysis of thiophene over nickel nanoparticles dispersed on silica is shown to yield Y-junction carbon nanotubes with smaller diameters than those obtained by the pyrolysis of organometallic-thiophene mixtures. In the presence of water vapour, the pyrolysis of organometallic-hydrocarbon mixtures yields single-walled nanotubes, as well as relatively narrow-diameter carbon nanotubes with Y-junctions. Pyrolysis-of organometallic-hydrocarbon mixtures, in the absence of water vapour, only gives nanotubes with T- and Y-junctions.

Crystal structure and ionic conductivity of a new bismuth tungstate,Bi3W2O10.5

The compound Bi3W2O10.5 was synthesized by the solid-state technique from Bi2O3 and WO3 in stoichiometric quantities. Single crystals were grown by the melt-cooling technique and the crystal structure was solved in the tetragonal 141in space group with a = 3.839 (1) A, c = 16-3S2 (5) A, V = 241.4 (1) angstrom(3), Z = 4 and was refined to an R index of 0.0672. The structure represents a modification of the Aurivillius phase and consists of [Bi2O2](2+) units separated by WO8 polyhedra. a.c. impedance studies indicate oxide ion conductivity of 2.91 10(-5) cm(-1) at 600 degrees C.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

A density matrix renormalization group study of low-lying excitations of polythiophene within a Pariser-Parr-Pople model

Symmetrized density-matrix-renormalization-group calculations have been carried out, within Pariser-Parr-Pople Hamiltonian, to explore the nature of the ground and low-lying excited states of long polythiophene oligomers. We have exploited C-2 symmetry and spin parity of the system to obtain excited states of experimental interest, and studied the lowest dipole allowed excited state and lowest dipole forbidden two photon state, for different oligomer sizes. In the long system limit, the dipole allowed excited state always lies below the lowest dipole forbidden two-photon state which implies, by Kasha rule, that polythiophene fluoresces strongly. The lowest triplet state lies below two-photon state as usual in conjugated polymers. We have doped the system with a hole and an electron and obtained the charge excitation gap and the binding energy of the 1(1)B(u)(-) exciton. We have calculated the charge density of the ground, one-photon and two-photon states for the longer system size of 10 thiophene rings to characterize these states. We have studied bond order in these states to get an idea about the equilibrium excited state geometry of the system. We have also studied the charge density distribution of the singly and doubly doped polarons for longer system size, and observe that polythiophenes do not support bipolarons.

A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr2Fe1+xMo1-xO6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.