Photoluminescence emission behavior on the reduced band gap of Fe doping in CeO2-SiO2 nanocomposite and photophysical properties

Fe/CeO₂-SiO₂ nanocomposite was synthesized via hydrothermal method. Bond length of nanocomposite was determined through FTIR analysis, while Raman analysis showed lattice relaxation of CeO₂ phase in Fe/CeO₂-SiO₂. TEM, XRD and DLS-PSA revealed an increase in size of Fe/CeO₂-SiO₂ as compared to CeO₂-SiO₂ which was attributed to have more oxygen vacancies in CeO₂ after doping of iron. Lattice contraction was also observed in some phases of CeO₂ in Fe/CeO₂-SiO₂ nanocomposite as compared to CeO₂-SiO₂ nanocomposite. This contraction was used for determination of Fe content incorporated in CeO₂ [1 1 1] phase. The band gap values of Fe/CeO₂-SiO₂ nanocomposite were found reduced after doping of Fe by factors of 0.62 and 0.55 eV, respectively. Photoluminescence study of the materials was carried out to study the different type of transitions occurring after absorption of electromagnetic radiation. Photoluminescence intensity at 2.12 eV was found enhanced after doping of Fe due to increased oxygen vacancy. Photocatalytic activity of the nanocomposites was studied with the degradation of chlorpyrifos pesticide.     

Wetting on the microscale: shape of a liquid drop on a microstructured surface at different length scales

Describing wetting of a liquid on a rough or structured surface is a challenge because of the wide range of involved length scales. Nano- and micrometer-sized textures cause pinning of the contact line, reflected in a hysteresis of the contact angle. To investigate contact angles at different length scales, we imaged water drops on arrays of 5 μm high poly(dimethylsiloxane) micropillars. The drops were imaged by laser scanning confocal microscopy (LSCM), which allowed us to quantitatively analyze the local and large-scale drop profile simultaneously. Deviations of the shape of drops from a sphere decay at two different length scales. Close to the pillars, the amplitude of deviations decays exponentially within 1-2 μm. The drop profile approached a sphere at a length scale 1 order of magnitude larger than the pillars' height. The height and position dependence of the contact angles can be understood from the interplay of pinning of the contact line, the principal curvatures set by the topography of the substrate, and the minimization of the air-water interfaces.     

Using direct electrochemistry to probe rate limiting events during nitrate reductase turnover

Protein film voltammetry of NarGH catalysing nitrate reduction under steady state conditions provides information on events occurring within the enzyme during the catalytic cycle. In this discussion we have focused on exploring the ability of two simple catalytic schemes to reproduce the voltammetric response of NarGH; electron transfer to the enzyme's active site being described either by interfacial electron exchange (Scheme 1) or intramolecular electron delivery via the operation of an electron relay centre (Scheme 2). When the two electron reduced, catalytically competent active site of the enzyme is generated from the oxidised form in 'rapid', non-rate limiting steps of the catalytic cycle, the voltammetric behaviour of NarGH cannot be reproduced. Rather under all the conditions investigated, one electron reduction of the active site from a semi-reduced to a fully-reduced state is found to be crucial to progression through the enzyme's catalytic cycle. The catalytically relevant semi- and fully-reduced oxidation states of the NarGH active site are most likely to correspond to the Mo(V) and Mo(IV) states of the Mo(MGD)2 centre, respectively, although it is not possible to rule out the possibility that they correspond to molybdopterin based oxidation states as observed in other enzymes. We suggest that the rate of either conformational rearrangement within the semi-reduced active site or intramolecular electron delivery to the active site constitutes a defining feature in the catalytic cycle of NarGH and results in the napp approximately 1 appearance of the catalytic waveform.     

Mössbauer study of the corrosion of mild steel due to prolonged immersion in deionized water

The corrosion of mild steel as a result of 3 years of immersion in deionized water, using Mössbauer results, indicates that -FeOOH, -FeOOH and Fe₃O₄ are formed as corrosion products. This study shows that purified water will produce -FeOOH only when the exposure time is long. It is proposed that ferrihydrite, which is formed as an intermediate corrosion product, is converted to -FeOOH, which in turn is converted to -FeOOH and Fe₃O₄.     

Correlation between work hardening and stress relaxation in polycrystalline nickel

Stress-relaxation rates at a constant strain in A-grade nickel polycrystals has been reported to depend in a peculiar manner on the initial stress levelσ ₀ at which relaxation is allowed to start. For large grains (D>75μm),s varies withσ ₀ linearly over the entire stress strain curve. For small grains (D<75μm),s-σ ₀ curve undergoes a change in its slope at a critical value of plastic strainɛ, which decreases as grain size increases. The observation referred to are found to correlate well with the work-hardening behaviour of the nickel polycrystals.     

Low-temperature anomalies in the plastic response of crystalline materials

The non-uniform, wavy, temperature-dependence of the yield-stress and of the rate of logarithmic creep frequently observed in metals, alloys and non-metallic crystalline solids at low temperature, is shown to be largely a consequence of the progressive inhibition of dynamic recovery processes as T → 0 K. Plastic deformation becomes increasingly localised, resulting in high stress-concentrations. On allowing for this increase in the usual equations of the deformation kineties, the anomalies are very well accounted for.     

Fast dynamic wetting of polymer surfaces by miscible and immiscible liquids

The initial stages of spontaneous spreading of a solvent drop (toluene) on the surface of a soluble polymer (polystyrene) have been studied with a high-speed camera. For drops of 1–4 μL volume, the increase in contact radius r can be described by a power law r μ t^a r propto {t^{alpha }} , with the spreading exponent α = 0.50 and for the first ≈8 ms. Thereafter, the three-phase contact line was pinned leading to a macroscopic static contact angle of Θ₀ = 12–15°. The insoluble liquids ethanol (α = 0.47, Θ₀ = 0) and water (α = 0.35, Θ₀ = 90°) showed a slower spreading. We attribute the fast spreading of toluene to the strong interaction with the polymer, like in reactive wetting. The finite macroscopic contact angle indicates the formation of a ridge by softening of polystyrene due to permeated toluene and the subsequent plastic deformation by the surface tension of the liquid. This interpretation is supported by experiments on polymers grafted from a silicon wafer. Toluene completely wets polymer brush surfaces. Transport of toluene through the vapor phase plays a significant role.     

Motion by mean curvature by scaling a nonlocal equation: Convergence at all times in the two-dimensional case

The convergence to a motion by mean curvature by diffusively scaling a nonlocal evolution equation, describing the macroscopic behavior of a ferromagnetic spin system with Kac interaction and Glauber dynamics has recently been proved. The convergence is proven up to the times when the motion by curvature is regular. Here we show the convergence at all times in the two-dimensional case. Since, in this case, the only singularity is the shrinking to a point of a closed curve, we verify that the curve actually disappears past the singularity.     

中低变质程度煤显微组分结构的13 C-NMR研究

利用13C-NMR核磁共振技术对中低变质程度煤显微组分（镜质组和惰质组）的分子结构进行了研究,计算了5种煤9个显微组分的13C-NMR结构参数,获得了样品的结构特征及变化规律。结果表明,惰质组结构中芳构化程度要高于镜质组;脂碳数量则少于镜质组,芳环上的烷烃侧链也没有镜质组长;随着煤变质程度的提高,煤分子中芳构化程度不断提高,但惰质组的芳香度随变质程度变化的规律明显不如镜质组;在中低变质阶段,对煤化进程起主导作用的的是芳构化作用而不是环缩合作用,但在惰质组中脂碳断裂形成芳环的现象不明显。惰质组中含氧官能团的总量要低于同等变质程度的镜质组。