Physical chemistry of mixed conducting zirconia ceramics

Suivant la pression partielle d'oxygène, la zircone peut être conducteur ionique ou électronique. Mise au point de méthodes de mesures de f.é.m. permettant de s'affranchir des sources d'erreur introduites par ces propriétés.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

The radiation resistance of off-set series slots in microstrip line

The radiation resistance of off-set series slots has been calculated for microstrip lines using the method proposed by Breithaupt for strip lines. A suitable transformation is made to allow for the difference in structure. Curves relating the slot resistance to the microstrip length, width and off-set distance have been obtained. Microstrip slot antenna arrays are becoming important in applications where size and weight are of significance. The radiation resistance is a very significant parameter is the design of such arrays. Oliner first calculated the radiation conductance of centered series slots in strip transmission lines and that analysis was extended by Breithaupt to the off-set series slots in stripline. The radiation resistance of off-set series slots in microstrip lines is calculated in this paper and data are obtained for different slot lengths, slot widths and off-set values. An example of the use of these data in array antenna design in shown.

Variation of the gas and radiation content in the sub-Keplerian accretion disk around black holes and its impact to the solutions

We investigate the variation of the gas and the radiation pressure in accretion disks during the infall of matter to the black hole and its effect to the flow. While the flow far away from the black hole might be non-relativistic, in the vicinity of the black hole it is expected to be relativistic behaving more like radiation. Therefore, the ratio of gas pressure to total pressure (beta) and the underlying polytropic index (gamma) should not be constant throughout the flow. We obtain that accretion flows exhibit significant variation of beta and then gamma, which affects solutions described in the standard literature based on constant beta. Certain solutions for a particular set of initial parameters with a constant beta do not exist when the variation of beta is incorporated appropriately. We model the viscous sub-Keplerian accretion disk with a nonzero component of advection and pressure gradient around black holes by preserving the conservations of mass, momentum, energy, supplemented by the evolution of beta. By solving the set of five coupled differential equations, we obtain the thermo-hydrodynamical properties of the flow. We show that during infall, beta of the flow could vary up to similar to 300%, while gamma up to similar to 20%. This might have a significant impact to the disk solutions in explaining observed data, e.g. super-luminal jets from disks, luminosity, and then extracting fundamental properties from them. Hence any conclusion based on constant gamma and beta should be taken with caution and corrected. (C) 2011 Elsevier B.V. All rights reserved.

Nanocatalysis and Prospects of Green Chemistry

Designing and developing ideal catalyst paves the way to green chemistry. The fields of catalysis and nanoscience have been inextricably linked to each other for a long time. Thanks to the recent advances in characterization techniques, the old technology has been revisited with a new scope. The last decade has witnessed a flood of research activity in the field of nanocatalysis, with most of the studies focusing on the effect of size on catalytic properties. This led to the development of much greener catalysts with higher activity, selectivity and greater ease of separation from the reaction medium. This Minireview describes the emerging trends in the field of nanocatalysis with implications towards green chemistry and sustainability.

Validation of a Modified Eddy Dissipation Concept Model for Stationary and Nonstationary Turbulent Diffusion Flames

A transient flame simulation tool based on unsteady Reynolds average Navier Stokes (RANS) is characterized for stationary and nonstationary flame applications with a motivation of performing computationally affordable flame stability studies. Specifically, the KIVA-3V code is utilized with incorporation of a recently proposed modified eddy dissipation concept for simulating turbulence-chemistry interaction along with a model for radiation loss. Detailed comparison of velocities, turbulent kinetic energies, temperature, and species are made with the experimental data of the turbulent, non-premixed DLR_A CH4/H-2/N-2 jet flame. The comparison shows that the model is able to predict flame structure very well. The effect of some of the modeling assumptions is assessed, and strategies to model a stationary diffusion flame are recommended. Unsteady flame simulation capabilities of the numerical model are assessed by simulating an acoustically excited, experimental, oscillatory H-2-air diffusion flame. Comparisons are made with oscillatory velocity field and OH plots, and the numerical code is observed to predict transient flame structure well.

Chemistry and biology of DNA-binding small molecules

Regulation of the transcription machinery is one of the many ways to achieve control of gene expression. This has been done either at the transcription initiation stage or at the elongation stage. Different methodologies are known to inhibit transcription initiation via targeting of double-stranded (ds) DNA by: (i) synthetic oligonucleotides, (ii) ds-DNA-specific, sequenceselective minor-groove binders (distamycin A), intercalators (daunomycin) combilexins and (iii) small molecule (peptide or intercalator)-oligonucleotide conjugates. In some cases, instead of ds-DNA, higher order G-quadruplex structures are formed at the start site of transcription. In this regard G-quadruplex DNA-specific small molecules play a significant role towards inhibition of the transcription machinery. Different types of designer DNA-binding agents act as powerful sequence-specific gene modulators, by exerting their effect from transcription regulation to gene modification. But most of these chemotherapeutic agents have serious side effects. Accordingly, there is always a challenge to design such DNA-binding molecules that should not only achieve maximum specific DNA-binding affinity, and cellular and nuclear transport activity, but also would not interfere with the functions of normal cells.

Structure and Photocatalytic Activity of Ti 1- x M x O 2±δ (M = W, V, Ce, Zr, Fe, and Cu) Synthesized by Solution Combustion Method

The W, V, Ce, Zr, Fe, and Cu metal ion substituted nanocrystalline anatase TiO2 was prepared by solution combustion method and characterized by XRD, Raman, BET, EPR, XPS, IR TGA, UV absorption, and photoluminescence measurements. The structural studies indicate that the solid solution formation was limited to a narrow range of concentrations of the dopant ions. The photocatalytic degradation of 4-nitrophenol under UV and solar exposure was investigated with Ti1-xMxO2±δ. The degradation rates of 4-nitrophenol with these catalysts were lesser than the degradation rates of 4-nitrophenol with undoped TiO2 both with UV exposure and solar radiation. However, the photocatalytic activities of most metal ion doped TiO2 are higher than the activity of the commercial TiO2, Degussa P25. The decrease in photocatalytic activity is correlated with decrease in photoluminescence due to electron states of metal ions within the band gap of TiO2.

Synthesis, structure and photocatalytic activity of nano TiO2 and nano Ti1-xMxO2-delta (M = Cu, Fe, Pt, Pd, V, W, Ce, Zr)

We have synthesized 5-7 nm size, highly crystalline TiO2 which absorbs radiation in the visible region of solar spectrum. The material shows higher photocatalytic activity both in UV and visible region of the solar radiation compared to commercial Degussa P25 TiO2. Transition metal ion substitution for Ti4+ creates mid-gap, states which act as recombination centers for electron-hole induced by photons thus reducing photocatalytic activity. However, Pt, Pd and Cu ion substituted TiO2 are excellent CO oxidation and NO reduction catalysts at temperatures less than 100 degrees C.

Strong electron correlation of Re 5d electrons in Ca2FeReO6

We have investigated the electronic structure of a double perovskite Ca2FeReO6 using photoemission spectroscopy and LDA+U bandstructure calculations. Small spectral weight at the Fermi level observed above the metal–insulator transition temperature, gradually disappears with decreasing T, forming a small (≤50 meV) energy gap. To reproduce this small energy gap, we require a very large effective U (Ueff) for Re (4 eV) in addition to Ueff of 4 eV for Fe. From simple calculations in terms of the ionic radii, we demonstrate that the Fe–Re bandwidth is smaller than that of Fe–Mo in Ca2FeMoO6, which should yield a strong electron correlation in the Re 5d bands.