Superconducting properties of Tl1?yPbyCaSr2Cu2O7: Role of Pb and oxygen stoichiometry

In the Tl1-yPbyCaSr2Cu2O7 system, monophasic superconducting compositions are formed in the range 0.25 < y < 0.60 and the minimum Pb content required to stabilize the tetragonal 1122 phase is about 25%. Maximum Tc is found when y = 0.5, at which composition the hole concentration is optimal. Metallic compositions of Tl1?yPbyCaSr2Cu2O7 (y = 0.25) and Tl0.75Pb0.25Y1?xCaxSr2Cu2O7 (0.80 less-than-or-equals, slant X less-than-or-equals, slant 1.0) become superconducting on decreasing the oxygen content by vacuum annealing.

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a vertical heated plate

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a heated vertical plate is studied for high Rayleigh numbers. Similarity solutions are obtained within the frame work of boundary layer theory for a power law variation in surface temperature,T Wpropx lambda and surface injectionv Wpropx(lambda–1/2). The analysis incorporates the expression connecting porosity and permeability and also the expression connecting porosity and effective thermal diffusivity. The influence of thermal dispersion on the flow and heat transfer characteristics are also analysed in detail. The results of the present analysis document the fact that variable porosity enhances heat transfer rate and the magnitude of velocity near the wall. The governing equations are solved using an implicit finite difference scheme for both the Darcy flow model and Forchheimer flow model, the latter analysis being confined to an isothermal surface and an impermeable vertical plate. The influence of the intertial terms in the Forchheimer model is to decrease the heat transfer and flow rates and the influence of thermal dispersion is to increase the heat transfer rate.

Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

Sliding wear of YTZP ceramic against steel: observations on ceramic transfer and wear transition

Sliding tests were conducted, in air, of YTZP ceramic pins against steel discs at an applied pressure of 15.5 MPa over a speed range of 0.3 to 4.0 ms(-1). Pin wear was not detectable until 2.0 m s(-1), after which a finite but small wear rate was observed at 3.0 m s(-1), accompanied by a red glow at the contacting surface. A transition in wear behaviour and friction (mu) occurred at 4.0 ms(-1), increasing the former by over two orders of magnitude. Both mu and wear behaviour changed with time at 4.0 m s(-1). During initial periods mu was high and wear rate increased steadily with time accompanied by ceramic transfer onto the disc, which increased with time. When disc coverage exceeds a certain threshold value, mu decreased rapidly and the wear rate stabilized at a very high value. Metal transfer was not observed at any speed. High surface temperatures brought about significant adhesion between TZP and steel and this together with enhanced plastic deformation brought about a transition in wear behaviour.

Synthesis and structure of oxygen-deficient La2NiCoO5 and LaSrCo2O5 phases

The La2NiCoO5 and LaSrCo2O5 phases have been synthesized by the temperature-programmed reduction (TPR) of the parent mixed perovskites LaNi0.5Co0.5O3 and La0.5Sr0.5CoO3, respectively, under an ammonia atmosphere. While La2NiCoO5 adopts a structure similar to the vacancy-ordered La2Ni2O5, LaSrCo2O5 crystallized in a brownmillerite-like structure. The reactivity of the perovskite oxides towards reduction by ammonia and the structure of the product oxides are found to be guided by factors such as the coordination and oxidation state of the transition-metal cations.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.

Gas-phase controlled mass transfer in a foam-bed reactor

Gas-phase controlled absorption of ammonia in foams made of solutions of sulphuric acid has been studied experimentally. Effects of gas-phase concentration of ammonia and type of surfactant on the performance of the foam-bed reactor are investigated. Gas-phase controlled absorption from a spherical bubble is anaylzed using the asymptotic value of Sherwood number (Sh = 6.58), for both negligible as well as significant changes in the volume of the bubble. The experimental data are shown to be in good agreement with the single-stage model of the foam-bed reactor using these asymptotic sub-models, as well as the diffusion-in-sphere analysis available in literature. Influence of effective diffusivity on the time dependence of fractional gas absorption has been found to be unimportant for foam columns with large times of contact. The asymptotic sub-models have been compared and use of the rigid-sphere asymptotic sub-model is recommended for foam columns of practical relevence.

Electronic conduction in LaNiO3-delta: the dependence on the oxygen stoichiometry delta

We report a systematic study of the electronic transport properties of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14). The electrical resistivity, magnetoresistance, susceptibility, Hall effect and thermopower have been studied, All of the transport coefficients are dependent on the value of delta. The resistivity increases almost exponentially as delta increases. We relate this increase in rho to the creation of Ni2+ with square-planar coordination. We find that there is a distinct T-1.5-contribution to the resistivity over the whole temperature range. The thermopower is negative, as expected for systems with electrons as the carrier, but the Hall coefficient is positive. We have given a qualitative and quantitative explanation for the different quantities observed and their systematic variation with the stoichiometry delta.

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Variations in the Levels of Aminoacylation and Modified Nucleotide Content Between Total Transfer-RNAS From Chloroplasts and Etioplasts in Cucumber Cotyledons

Total tRNAs isolated from chloroplasts and etioplasts of cucumber cotyledons were compared with respect to amino acid acceptance, isoacceptor distribution and extent of modification. Aminoacylation of the tRNAs with nine different amino acids studied indicated that the relative acceptor activities of chloroplast total tRNAs for four amino acids are significantly higher than etioplast total tRNAs. Two dimensional polyacrylamide gel electrophoresis (2D-PAGE) of chloroplast total tRNAs separated at least 32 spots, while approximately 41 spots were resolved from etioplast total tRNAs. Comparison of the reversed-phase chromatography (RPC-5) profiles of chloroplast and etioplast leucyl-, lysyl-, phenylalanyl-, and valyl-tRNA species showed no qualitative differences in the elution profiles. However, leucyl-, lysyl- and valyl-tRNA species showed quantitative differences in the relative amounts of the isoaccepting species present in chloroplasts and etioplasts. The analysis of modified nucleotides of total tRNAs from the two plastid types indicated that total tRNA from etioplasts was undermodified with respect to ribothymidine, isopentenyladenosine/hydroxy-isopentenyladenosine, 1-methylguanosine and 2-o-methylguanosine. This indicates that illumination may cause de novo synthesis of chloroplast tRNA-modifying enzymes encoded for by nuclear genes leading to the formation of highly modified tRNAs in chloroplasts. Based on these results, we speculate that the observed decrease in levels of aminoacylation, variations in the relative amounts of certain isoacceptors, and differences in the electrophoretic mobilities of some extra tRNA spots in the etioplast total tRNAs as compared to chloroplast total tRNAs could be due to some partially undermodified etioplast tRNAs. Taken together, the data suggested that the light-induced transformation of etioplasts into chloroplasts is accompanied by increases in the relative levels of some functional chloroplast tRNAs by post transcriptional nucleotide modifications.

Non-exponentiality in electron transfer kinetics: Static versus dynamic disorder models

Non-exponential electron transfer kinetics in complex systems are often analyzed in terms of a quenched, static disorder model. In this work we present an alternative analysis in terms of a simple dynamic disorder model where the solvent is characterized by highly non-exponential dynamics. We consider both low and high barrier reactions. For the former, the main result is a simple analytical expression for the survival probability of the reactant. In this case, electron transfer, in the long time, is controlled by the solvent polarization relaxation-in agreement with the analyses of Rips and Jortner and of Nadler and Marcus. The short time dynamics is also non-exponential, but for different reasons. The high barrier reactions, on the other hand, show an interesting dynamic dependence on the electronic coupling element, V-el.

Non-viral ex vivo hepatic gene transfer by in situ lipofection of liver and intraperitoneal transplantation of hepatocytes

Perfusion of liver with plasmid DNA-lipofectin complexes via the portal vein results in efficient accumulation of the vector in hepatocytes. Such hepatocytes, when administered intraperitoneally into a hepatectomized rat, repopulate the liver and express the transgene efficiently. This procedure obviates the need for large-scale hepatocyte culture for ex vivo gene transfer. Further, intraperitoneal transplantation is a simple and cost-effective strategy of introducing genetically modified hepatocytes into liver. Thus, in situ lipofection of liver and intraperitoneal transfer of hepatocytes can be developed into a novel method of non-viral ex vivo gene transfer technique that has applications in the treatment of metabolic disorders of liver and hepatic gene therapy.

Role of silver doping in oxygen incorporation of oxide thin film

A distinctive characteristic of silver in oxygen incorporation of oxide thin films during pulsed laser ablation has been discovered. Optical emission spectroscopy studies of laser-induced plume of Ag-target indicates the presence of AgO species whose concentration increases with an increase in oxygen partial pressure. The formation of AgO in laser-plume has been found to be very useful for the realization of high temperature superconducting YBa2Cu3O7-delta (YBCO) and giant magnetoresistive La0.7MnO3-delta (LMO) thin films with dramatically superior quality if the target materials contained a small amount of silver. The improvement in the quality of these films is brought about by the supply of atomic oxygen to oxide lattices during their formation. This becomes possible due to the fact that Ag, after it is ablated with other constituent materials in the target, gets moderately oxidized in an oxygen atmosphere and the oxidized species dissociate back into Ag and nascent O at the substrate surface. The nascent oxygen is very highly reactive and is easily assimilated into the lattice of these compounds. (C) 1997 Elsevier Science S.A.