Instabilities and Waves in Thin Films of Living Fluids

We formulate the thin-film hydrodynamics of a suspension of polar self-driven particles and show that it is prone to several instabilities through the interplay of activity, polarity, and the existence of a free surface. Our approach extends, to self-propelling systems, the work of Ben Amar and Cummings [Phys. Fluids 13 1160 (2001)] on thin-film nematics. Based on our estimates the instabilities should be seen in bacterial suspensions and the lamellipodium, and are potentially relevant to the morphology of biofilms. We suggest several experimental tests of our theory.

Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh2)(2)N(R) (R = Pr-i, H, Ph and -CH2-C6H4-CH=CH2) complexes at 40 degrees C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = Pr-i > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile "copper-olefin" complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper-phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism. (C) 2008 Elsevier B. V. All rights reserved.

Supercapacitor studies of electrochemically deposited PEDOT on stainless steel substrate

There has been increasing interest on various properties and applications of electronically conducting polymers. Polyethylenedioxythiophene (PEDOT) is an interesting polymer of this type as it exhibits very high ionic conductivity. In the present study, PEDOT has been electrochemically deposited on stainless steel (SS) substrate for supercapacitor studies. PEDOT/SS electrodes prepared in 0.1M H2SO4 in presence of a surfactant, sodium dodecylsulphate (SDS), have been found to yield higher specific capacitance (SC) than the electrodes prepared from neutral aqueous electrolyte. The effects of concentration of H(2)SO4(,) concentration of SDS, potential of deposition, and nature of supporting electrolytes used for capacitor studies on SC of the PEDOT/SS electrodes have been studied. SC values as high as 250 F/g in 1M oxalic acid have been obtained during the initial stages of cycling. However, there is a rapid decrease in SC on repeated charge-discharge cycling. Spectroscopic data reflect structural changes in PEDOT on extended cycling. (C) 2007 Wiley Periodicals, Inc.

Aspects of tautomerism. Part IV. A kinetic study of the dimerization reaction of pseudo-acid chlorides

The kinetics of dimerization of 4-substituted- and unsubstituted o-benzoylbenzoyl chlorides, with iodide ion can be described by the expression, rate =k2[acid chloride][iodide]. The value for the reaction in dimethylformamide solution is –0·38. The entropy of activation for the reaction is –34·2 cal mol–1 K–1 and the activation energy is 10·7 kcal mol–1. These results have been interpreted as evidence for the formation of pseudo-iodide in the rate-determining step and its fast decomposition to radicals which combine to give a mixture of stereoisomeric dilactones.

Aspects of tautomerism. Part V. Solvent, substituent, and steric effects on the ring–chain tautomerism of o-benzoylbenzamides

Ring-chain tautomeric equilibria of o-benzoylbenzamides in 95% ethanol, chloroform, dioxan, and acetonitrile have been estimated using u.v. spectroscopy. Unlike the case of acids, solvent polarity has only a small effect. In ethanol the cyclic form is favoured. Electron-withdrawing groups in the amide-bearing ring disfavour the cyclic form. Substitution of methyl, ethyl, and phenyl groups on the nitrogen atom of the amide function results in increase of the proportion of the cyclic form in the first two cases and decrease in the last.

Ferroelectric properties of Bi2VO5.5 thin films on LaAlO3 and SiO2/Si substrates with LaNiO3 base electrode

Ferroelectric bismuth vanadate Bi2VO5.5 (BVO) thin films have been grown on LaAlO3 (LAO) and SiO2/Si substrates with LaNiO3 (LNO) base electrodes by the pulsed laser deposition technique. The effect of substrate temperature on the ferroelectric properties of BVO thin films, has been studied by depositing the thin films at different temperatures. The BVO thin films grown on LNO/LAO were textured whereas the thin films grown on LNO/SiO2/Si were polycrystalline. The BVO thin films grown at 450?°C exhibited good ferroelectric properties indicating that LNO acts as a good electrode material. The remanent polarization Pr and coercive field Ec obtained for the BVO thin films grown at 450?°C on LNO/LAO and LNO/SiO2/Si were 2.5 ?C/cm2, 37 kV/cm and 4.6?C/cm2, 93 kV/cm, respectively. © 1995 American Institute of Physics.

On the SIG-dimension of trees under the L (a)-metric

Let where be a set of points in d-dimensional space with a given metric rho. For a point let r (p) be the distance of p with respect to rho from its nearest neighbor in Let B(p,r (p) ) be the open ball with respect to rho centered at p and having the radius r (p) . We define the sphere-of-influence graph (SIG) of as the intersection graph of the family of sets Given a graph G, a set of points in d-dimensional space with the metric rho is called a d-dimensional SIG-representation of G, if G is isomorphic to the SIG of It is known that the absence of isolated vertices is a necessary and sufficient condition for a graph to have a SIG-representation under the L (a)-metric in some space of finite dimension. The SIG-dimension under the L (a)-metric of a graph G without isolated vertices is defined to be the minimum positive integer d such that G has a d-dimensional SIG-representation under the L (a)-metric. It is denoted by SIG (a)(G). We study the SIG-dimension of trees under the L (a)-metric and almost completely answer an open problem posed by Michael and Quint (Discrete Appl Math 127:447-460, 2003). Let T be a tree with at least two vertices. For each let leaf-degree(v) denote the number of neighbors of v that are leaves. We define the maximum leaf-degree as leaf-degree(x). Let leaf-degree{(v) = alpha}. If |S| = 1, we define beta(T) = alpha(T) - 1. Otherwise define beta(T) = alpha(T). We show that for a tree where beta = beta (T), provided beta is not of the form 2 (k) - 1, for some positive integer k a parts per thousand yen 1. If beta = 2 (k) - 1, then We show that both values are possible.

Climatic variability in Central Indian Himalaya during the last similar to 1800 years: Evidence from a high resolution speleothem record

Stable isotopes from a U/Th dated aragonite stalagmite from the Central Kumaun Himalaya provide evidence of variation in climatic conditions in the last similar to 1800 years. The delta O-18 and delta C-13 values vary from -4.3 parts per thousand to -7.6 parts per thousand and -3.4 parts per thousand to -9.1 parts per thousand respectively, although the stalagmite was not grown in isotopic equilibrium with cave drip water, a clear palaeoclimatic signal in stalagmite delta O-18 values is evident based on the regional climate data. The stalagmite showed a rapid growth rate during 830-910 AD, most likely the lower part of Medieval Warm Period (MWP), and 1600-1640 AD, the middle part of Little Ice Age (LIA). Two distinct phases of reduced precipitation are marked by a 2 parts per thousand shift in 8180 values towards the end of MWP (similar to 1080-1160 AD) and after its termination from similar to 1210 to 1440 AD. The LIA (similar to 1440-1880 AD) is represented by sub-tropical climate similar to modern conditions, whereas the post-LIA was comparatively drier. The Inter Tropical Convergence Zone (ITCZ) was located over the cave location during wetter/warmer conditions. When it shifted southward, precipitation over the study area decreased. A prominent drop in delta O-18 and delta C-13 values during the post-LIA period may also have been additionally influenced by anthropogenic activity in the area. (C) 2013 Elsevier Ltd and INQUA. All rights reserved.

Bilinear tension softening diagrams of concrete mixes corresponding to their size-independent specific fracture energy

The study of the fracture behaviour of concrete structures using the fictitious crack model requires two fracture properties of the concrete mix, namely, the size-independent specific fracture energy G(F). and the corresponding tension softening relation sigma(w) between the residual stress carrying capacity sigma and the crack opening w in the fracture process zone ahead of a real crack. In this paper, bi-linear tension softening diagrams of three different concrete mixes, ranging in compressive strength from 57 to 122 MPa whose size-independent specific fracture energy has been previously determined, have been constructed in an inverse manner based on the concept of a non-linear hinge from the load-crack mouth opening plots of notched three-point bend beams. (C) 2013 Elsevier Ltd. All rights reserved.

Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal zeta-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the zeta-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the zeta-phase. A complete solid solution of Ag with a grain size of similar to 8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of zeta-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and zeta-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

Life Estimation of Electrothermally Stressed Epoxy Nanocomposites

Accelerated electrothermal aging tests were conducted at a constant temperature of 60 degrees C and at different stress levels of 6 kV/mm, 7 kV/mm and 8 kV/mm on unfilled epoxy and epoxy filled with 5 wt% of nano alumina. The leakage current through the samples were continuously monitored and the variation in tan delta values with aging duration was monitored to predict the impending failure and the time to failure of the samples. It is observed that the time to failure of epoxy alumina nanocomposite samples is significantly higher as compared to the unfilled epoxy. Data from the experiments has been analyzed graphically by plotting the Weibull probability and theoretically by the linear least square regression analysis. The characteristic life obtained from the least square regression analysis has been used to plot the inverse power law curve. From the inverse power law curve, the life of the epoxy insulation with and without nanofiller loading at a stress level of 3 kV/mm, i.e. within the midrange of the design stress level of rotating machine insulation, has been obtained by extrapolation. It is observed that the life of epoxy alumina nanocomposite of 5 wt% filler loading is nine times higher than that of the unfilled epoxy.