Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Studies of phosphazenes. Part 15. Chloro(phenoxy)cyclotetraphosphazenes, N4P4Cl8-n(OPh)n

The reaction of N4P4Cl8(1) with sodium phenoxide (or phenol in the presence of triethylamine) has been studied under a variety of experimental conditions. The chloro(phenoxy)-derivatives, N4P4Cl8-n(OPh)n[n= 1 or 2 (mixture of four non-geminal isomers), 3(mixture of non-geminal isomers), 4(mixture of isomers), 5(mixture of isomers), 6(mixture of four non-geminal isomers), or 8], have been isolated by column chromatography over silica gel. Attempts to separate geometric isomers were unsuccessful. Structural elucidation of the products is based on the 31P n.m.r. data for the chloro-precursors and 1H and 31P n.m.r. spectra of the dimethylamino- and/or methoxy-derivatives. The chlorine-replacement pattern is discussed.

Pressure-Induced transitions in amorphous TlxSe100-x alloys

The electrical resistivity of bulk semiconducting amorphous TlxSe100-x alloys with 0 ≤ x ≤ 25 has been investigated up to a pressure of 14 GPa and down to liquidnitrogen temperature by use of a Bridgman anvil device. All the glasses undergo a discontinuous pressure-induced semiconducting-to-metal transition. X-ray diffraction studies on the pressure-recovered samples show that the high-pressure phase is the crystalline phase. The pressure-induced crystalline products are identified to be a mixture of Se having a hexagonal structure with a = 4·37 Aring and c = 4·95 Aring and TlSe having a tetragonal structure with a = 8·0 Aring and c = 7·0 Aring

Co-assembly of a Nafion-Mesoporous Zirconium Phosphate Composite Membrane for PEM Fuel Cells

Synthesis of mesoporous zirconium phosphate (MZP) by co-assembly of a tri-block copolymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide and phosphorous trichloride as inorganic precursors is reported. MZP with a specific surface area of 84 m(2) g(-1) average pore diameter of about 17 nm and pore volume of 0.35 cm(3) g(-1) has been prepared, and characterised by X-ray diffraction (XRD) and transmission electron microscopy. Nafion-MZP composite membrane is obtained by employing MZP as a surface-functionalised solid-super-acid-proton-conducting medium as well as all inorganic filler with high affinity to absorb water and fast proton-transport across the electrolyte membrane even under low relative humidity (RH) conditions. The composite membranes have been evaluated in H-2/O-2 polymer electrolyte fuel cells (PEFCs) at varying RH values between 18 and 100%; a peak power density of 355 mW cm(-2) at a load current density of 1,100 mA cm(-2) is achieved with the PEFC employing Nafion-MZP composite membrane while operating at optimum temperature (70 degrees C) under 18% RH and ambient pressure. On operating the PEFC employing Nafion-MZP membrane electrolyte with hydrogen and air feeds at ambient pressure and a RH value of 18%, a peak power density of 285 mW cm(-2) at the optimum temperature (60 degrees C) is achieved. In contrast, operating under identical conditions, a peak power density of only similar to 170 mW cm(-2) is achieved with the PEFC employing Nafion-1135 membrane electrolyte.

A H-1-NMR STUDY OF BILIRUBIN IX-ALPHA SOLUBILIZATION BY CHOLATE MICELLES - APPLICATION OF NUCLEAR OVERHAUSER EFFECTS

The solubilization of bilirubin IX-Alpha in aqueous solution by sodium cholate micelles has been examined by 270 MHz 1H-NMR spectroscopy. Incorporation of bilirubin into the micelles is accompanied by specific shifts of bilirubin vinyl and bridgehead protons and the C18 and C19 methyl groups of the steroid. The observed chemical shifts show a monotonic concentration dependence suggesting that changes in aggregation size are continuous. Nuclear Overhauser effects (NOE) have been shown to be a useful probe or micellization. A 4:1 cholate/bilirubin mixture has been investigated by difference NOE spectroscopy. The observation of intermolecular nuclear Overhauser effects between peripheral protons of bilirubin and cholate are diagnostic of spatially proximate groups. Inter-cholate nuclear Overhauser effects increase in magnitude upon bilirubin incorporation suggesting closer packing of steroid molecules on solubilization of the pigment. Intramolecular nuclear Overhauser effects observed for solubilized bilirubin are consistent with a compact intramolecularly hydrogen-bonded conformation resembling that determined for bilirubin in the solid state.

Electron Mean Energy, Secondary Ionization Coefficients And (E/P)Crit In Binary-Mixtures Of Sf6-N2 And Ccl2f2-N2

Measurements of the ratio of diffusion coefficient to mobility (D/ mu ) of electrons in SF6-N2 and CCl2F2-N2 mixtures over the range 80mixture, where alpha = eta ), and the electron mean energies epsilon c.mix corresponding to (E/p)c.mix, are found to vary with the percentage of the electronegative gas in the mixture (F) according to the following relationship: (E/p)c.mix=(E/p)c.N(2)+((E/p)c.A-(E/p)c.N(2)) (1-exp(- beta F/100-F)) and epsilon c.mix= epsilon c.N(2)+( epsilon c.A- epsilon c.N(2)) (1-exp(- beta F/100-F)) where A refers to the attaching gas, either SF6 or CCl2F2 and beta is a constant, equal to 2.43 for SF6 mixtures and 5.12 for CCl2F2 mixtures. In the present study, it has been possible to show that beta is indeed to a factor of synergism. Estimated gamma values (secondary ionisation coefficients) did not show any significant variation with F for F<50.

Laser surface cladding of MRI 153M magnesium alloy with (Al+Al2O3)

Laser surface cladding was carried out on a creep-resistant MRI 153M magnesium alloy with a mixture of Al and Al2O3 powders using a pulsed Nd:YAG laser at scan speeds of 21, 42, 63 and 84 mm/s. The Al2O3 particles partially or completely melted during laser irradiation and re-solidified with irregular shapes in the size range of 5–60 µm along with a few islands as large as 500 µm, within the grain-refined Mg-rich dendritic matrix. More than an order of magnitude improvement in wear resistance after cladding was attributed to the presence of ultra-hard Al2O3 particles, increased solid solubility of Al and other alloying elements, and a very fine dendritic microstructure as a result of rapid solidification in the cladded layer. However, corrosion resistance of the laser cladded alloy was reduced by almost an order of magnitude compared to that of the as-cast alloy mainly due to the presence of cracks and pores in the cladded layer.

Ionisation and attachment in binary mixtures of SF6-N2 and CCl2F2-N2

Experimental results are presented of ionisation (a)a nd electron attachment ( v ) coefficients evaluated from the steady-state Townsend curregnrto wth curves for SFsN2 and CC12FrN2 mixtures over the range 60 S E/P 6 240 (where E is the electric field in V cm" and P is the pressure in Torr reduced to 20'C). In both the mixtures the attachment coefficients (vmu) evaluated were found to follow the relationship; where 7 is the attachment coefficient of pure electronegative gas, F is the fraction of the electronegative gas in the mixture and /3 is a constant. The ionisation coefficients (amlx) generally obeyed the relationship where w2a nd aAa re thei onisation coefficients of nitrogen and the attachinggraess pectively. However, in case of CC12FrN2 mixtures, there were maxima in the a,,,v,a,l ues for CCI2F2 concentrations varying between 10% and 30% at all values of E/P investigated. Effective ionisation coefficients (a - p)/P obtained in these binary mixtures show that the critical E/P (corresponding to (a - q)/P = 0) increases with increase in the concentration of the electronegative gas up to 40%. Further increase in the electronegative gas content does not seem to alter the critical E/P.

Coplanar gas-discharge display

1. The electric field strength between coplanar electrodes is calculated employing "conformal transformations." The electron multiplication factor is then computed in the nonuniform field region. These calculations have been made for different gap lengths, voltages, and also for different gases and gas pressures. The configuration results in a curved discharge path. It is found that the electron multiplication is maximum along a particular flux line and the prebreakdown discharge is expected to follow this flux line. Experimental tubes incorporating several coplanar gaps have been fabricated. Breakdown voltages have been measured for various discharge gaps and also for various gases such as xenon, helium, neon, argon, and neon-argon mixture (99.5:0.5) at different filling pressures. The variation of breakdown voltage with pressure and gap length is discussed. The observed discharge paths are curved and this is in agreement with theoretical results. A few experimental single-digit coplanar gas-discharge displays (CGDD's) with digit height of 5 cm have been fabricated and dependence of their characteristics on various parameters, including spacing between top glass plate and bottom substrate, have been studied.

Statistical Optimization of Iron Electrodes for Alkaline Storage Batteries

A pressed-plate Fe electrode for alkalines storage batteries, designed using a statistical method (fractional factorial technique), is described. Parameters such as the configuration of the base grid, electrode compaction temperature and pressure, binder composition, mixing time, etc. have been optimised using this method. The optimised electrodes have a capacity of 300 plus /minus 5 mA h/g of active material (mixture of Fe and magnetite) at 7 h rate to a cut-off voltage of 8.86V vs. Hg/HgO, OH exp 17 ref.

Helix-coil stability constants for amino acids in nonaqueous solvents. Studies of random poly(-benzyl-L-glutamate-co-L-alanine) and poly(-benzyl-L-glutamate-co-L-leucine) in a mixed solvent

The host-guest technique has been applied to the determination of the helix-coil stability constants of two naturally occurring amino acids, L-alanine and L-leucine, in a nonaqueous solvent system. Random copolymers containing L-alanine and L-leucine, respectively, as guest residues and -benzyl-L-glutamate as the host residue were synthesized. The polymers were fractionated and characterized for their amino acid content, molecular weight, and helix-coil transition behavior in a dichloroacetic acid (DCA)-1,2-dichloroethane (DCE) mixture. Two types of helix-coil transitions were carried out on the copolymers: solvent-induced transitions in DCA-DCE mixtures at 25°C and thermally induced transitions in a 82:18 (wt %) DCA-DCE mixture. The thermally induced transitions were analyzed by statistical mechanical methods to determine the Zimm-Bragg parameters, and s, of the guest residues. The experimental data indicate that, in the nonaqueous solvent, the L-alanine residue stabilizes the -helical conformation more than the L-leucine residue does. This is in contrast to their behavior in aqueous solution, where the reverse is true. The implications of this finding for the analysis of helical structures in globular proteins are discussed.

Evidence for H2O2 as the product of reduction of oxygen by alternative oxidase in mitochondria from potato tubers

Oxygen Consumption by alternative oxidase (AOX), present in mitochondria of many angiosperms, is known to be cyanide-resistant in contrast to cytochrome oxidase. Its activity in potato tuber (Solarium tuberosum L.) was induced following chilling treatment at 4 degrees C.About half of the total O-2 consumption of succinate oxidation in such mitochondria was found to be sensitive to SHAM, a known inhibitor of AOX activity. Addition of catalase to the reaction mixture of AOX during the reaction decreased the rate of SHAM-sensitive oxygen consumption by nearly half, and addition at the end of the reaction released nearly half of the consumed oxygen by AOX, both typical of catalase action on H2O2. These findings with catalase suggest that the product of reduction of AOX is H2O2 and not H2O, as previously Surmised. In potatoes Subjected to chill stress (4 degrees C) for periods of 3, 5 and >= 8 days the activity of AOX in mitochondria increased progressively with a corresponding increase in the AOX protein detected by immunoblot of the protein.

Electron attachment in binary mixtures of electronegative and buffer gases

The ratio of the electron attachment coefficient eta to the gas pressure p (reduced to 0 degrees C) evaluated from the Townsend current growth curves in binary mixtures of electronegative gases (SF6, CCl2F2, CO2) and buffer gases (N2, Ar, air) clearly indicate that the eta /p ratios do not scale as the partial pressure of electronegative gas in the mixture. Extensive calculations carried out using data experimentally obtained have shown that the attachment coefficient of the mixture eta mix can be expressed as eta mix= eta (1-exp- beta F/(100-F)) where eta is the attachment coefficient of the 100% electronegative gas, F is the percentage of the electronegative gas in the mixture and beta is a constant. The results of this analysis explain to a high degree of accuracy the data obtained in various mixtures and are in very good agreement with the data deduced by Itoh and co-workers (1980) using the Boltzmann equation method.

Behaviour of methylmethacrylate-acrylonitrile random copolymers in dilute solution

Studies on the dilute solution properties of methylmethacrylate-acrylonitrile random copolymers of three different compositions, 0.236, 0.5 and 0.74 mole fraction (m.f.) of acrylonitrile (AN) designated as MAa, MAb and MAc, respectively, have been made in good solvents and theta solvents. MAa has been studied in benzene (Bz) and ethylacetate (EAc). MAb in acetonitrile (MeCN), dimethyl sulphoxide (DMSO) and a binary solvent mixture of Bz and dimentyl formamide (DMF) in the volume ratio 6.5:1 designated as BM1 and MAc in MeCN, DMSO and Bz + DMF in the volume ratio 1.667:1 designated as BM2. The Mark-Houwink exponent ‘a’ reveals that Bz is a theta solvent for MAa at 20°C. For MAb and MAc, BM1 and BM2, respectively have ‘a’ values of 0.5 at all three temperatures studied (30°, 40° and 50°C). It is not clear whether they represent theta states or preferential adsorption plays a role complicating the behaviour in solution. The values of A2 are very low in MeCN considering that it is a very good solvent for the copolymer, ‘a’ values for MAb and MAc being 0.75 and 0.7, respectively.

Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.