Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.

The Role of Tool Design in Influencing the Mechanism for the Formation of Friction Stir Welds in Aluminum Alloy 7020

Design of the required tool is a key and important parameter in the technique of friction stir welding (FSW). This is so because tool design does exert a close control over the quality of the weld. In an attempt to optimize tool design and its selection, it is essential and desirable to understand the mechanisms governing the formation of the weld. In this research study, few experiments were conducted to systematically analyze the intrinsic mechanisms governing the formation of the weld and to effectively utilize the analysis to establish a logical basis for design of the tool. For this purpose, the experiments were conducted using different geometries of the shoulder and pin of the rotating tool in such a way that only tool geometry had an intrinsic influence on formation of the weld. The results revealed that for a particular diameter of the pin there is an optimum diameter of the shoulder. Below this optimum shoulder diameter, the weld does not form while above the optimum diameter the overall symmetry of the weld is lost. Based on experimental results, a mechanism for the formation of friction stir weld is proposed. A synergism of the experimental results with the proposed mechanism is helpful in establishing the set of welding parameters for a given material.

Temperature dependent photoemission spectroscopy on lightly-doped sodium tungsten bronze

Temperature dependent photoemission studies on lightly doped (x = 0.025) sodium tungsten bronzes, NaxWO3 have been investigated by high-resolution photoemission spectroscopy. The experimental results show evidence for polaron formation at the valence band edge and the photoemission spectra taken in different modes of the electron analyzer suggest that the density of states at the valence band edge gradually moves to other k-points in the Brillouin zone with increasing temperature and explain the dynamics of polarons in the insulating disordered sodium tungsten bronzes. (C) 2012 Elsevier Ltd. All rights reserved.

Microstructure and texture evolution during beta extrusion of boron modified Ti-6A1-4V alloy

Boron addition to conventional titanium alloys below the eutectic limit refines the cast microstructure and improves mechanical properties. The present work explores the influence of hypoeutectic boron addition on the microstructure and texture evolution in Ti-6Al-4V alloy under beta extrusion. The beta extruded microstructure of Ti-6Al-4V is characterized by shear bands parallel to the extrusion direction. In contrast, the extruded Ti-6Al-4V-0.1B alloy shows a regular beta worked microstructure consisting of fine prior beta grains and acicular alpha-lamellae with no signs of the microstructural instability. Crystallographic texture after extrusion was almost identical for the two alloys indicating the similarity in their transformation behavior, which is attributed to complete dynamic recrystallization during beta processing. Microstructural features as well as crystallographic texture indicate dominant grain boundary related deformation processes for the boron modified alloy that leads to homogeneous deformation without instability formation. The absence of shear bands has significant technological importance as far as the secondary processing of boron added alloys in (alpha + beta)-phase field are concerned. (C) 2012 Elsevier B.V. All rights reserved.

Effect of carrier concentration of InN on the transport behavior of InN/GaN heterostructure based Schottky junctions

We present the study involving the dependence of carrier concentration of InN films, grown on GaN templates using the plasma assisted molecular beam epitaxy system, on growth temperature. The influence of InN carrier concentration on the electrical transport behavior of InN/GaN heterostructure based Schottky junctions is also discussed. The optical absorption edge of InN film was found to be strongly dependent on carrier concentration, and was described by Kane's k.p model, with non-parabolic dispersion relation for carrier in the conduction band. The position of the Fermi-level in InN films was modulated by the carrier concentration in the InN films. The barrier height of the heterojunctions as estimated from I-V characteristic was also found to be dependent on the carrier concentration of InN. (C) 2012 Elsevier Ltd. All rights reserved.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Curcumin reduces the antimicrobial activity of ciprofloxacin against Salmonella Typhimurium and Salmonella Typhi

Typhoidal and non-typhoidal infection by Salmonella is a serious threat to human health. Ciprofloxacin is the last drug of choice to clear the infection. Ciprofloxacin, a gyrase inhibitor, kills bacteria by inducing chromosome fragmentation, SOS response and reactive oxygen species (ROS) in the bacterial cell. Curcumin, an active ingredient from turmeric, is a major dietary molecule among Asians and possesses medicinal properties. Our research aimed at investigating whether curcumin modulates the action of ciprofloxacin. We investigated the role of curcumin in interfering with the antibacterial action of ciprofloxacin in vitro and in vivo. RTPCR, DNA fragmentation and confocal microscopy were used to investigate the modulation of ciprofloxacin-induced SOS response, DNA damage and subsequent filamentation by curcumin. Chemiluminescence and nitroblue tetrazolium reduction assays were performed to assess the interference of curcumin with ciprofloxacin-induced ROS. DNA binding and cleavage assays were done to understand the rescue of ciprofloxacin-mediated gyrase inhibition by curcumin. Curcumin interferes with the action of ciprofloxacin thereby increasing the proliferation of Salmonella Typhi and Salmonella Typhimurium in macrophages. In a murine model of typhoid fever, mice fed with curcumin had an increased bacterial burden in the reticuloendothelial system and succumbed to death faster. This was brought about by the inhibition of ciprofloxacin-mediated downstream signalling by curcumin. The antioxidant property of curcumin is crucial in protecting Salmonella against the oxidative burst induced by ciprofloxacin or interferon (IFN), a pro-inflammatory cytokine. However, curcumin is unable to rescue ciprofloxacin-induced gyrase inhibition. Curcumins ability to hinder the bactericidal action of ciprofloxacin and IFN might significantly augment Salmonella pathogenesis.

Diffusion in tungsten silicides

Experiments are conducted in the W-Si system to understand the diffusion mechanism of the species. The activation energies from integrated diffusion coefficients are calculated as 152 +/- 7 and 301 +/- 40 kJ/mol in the WSi2 and W5Si3 phases, respectively. In both the phases, Si has a much higher diffusion rate compared to W. This is not surprising to find in the WSi2 phase, if we consider the number of nearest neighbors for both the elements in the crystal. The diffusion of W in this phase indicates the presence of W antisites. The faster diffusion rate of Si in the W5Si3 phase indicates the presence of higher concentration of vacancies on the Si sublattice compared to W sublattice.

Decode-and-forward relay beamforming for secrecy with finite-alphabet input

In this letter, we compute the secrecy rate of decode-and-forward (DF) relay beamforming with finite input alphabet of size M. Source and relays operate under a total power constraint. First, we observe that the secrecy rate with finite-alphabet input can go to zero as the total power increases, when we use the source power and the relay weights obtained assuming Gaussian input. This is because the capacity of an eavesdropper can approach the finite-alphabet capacity of 1/2 log(2) M with increasing total power, due to the inability to completely null in the direction of the eavesdropper. We then propose a transmit power control scheme where the optimum source power and relay weights are obtained by carrying out transmit power (source power plus relay power) control on DF with Gaussian input using semi-definite programming, and then obtaining the corresponding source power and relay weights which maximize the secrecy rate for DF with finite-alphabet input. The proposed power control scheme is shown to achieve increasing secrecy rates with increasing total power with a saturation behavior at high total powers.

Structural, iono and thermoluminescence properties of heavy ion (100 MeV Si7+) bombarded Zn2SiO4:Sm3+ nanophosphor

Structural, iono (IL) and thermoluminescence (TL) studies of Zn2SiO4:Sm3+ (1-5 mol%) nanophosphor bombarded with swift heavy ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) cm(-2) have been carried out. The average crystallite sizes for pristine and ion irradiated for 3.91 x 10(12) ions cm(-2) and 21.48 x 10(12) ions cm(-2) were found to be 34, 26 and 20 nm. With increase of ion fluence, the intensity of XRD peaks decreases and FWHM increases. The peak broadening indicates the stress induced point/clusters defects produced due to heavy ion irradiation. IL studies were carried out for different Sm3+ concentrations in Zn2SiO4 by irradiating with ion fluence of 15.62 x 10(12) ions cm(-2). The characteristic emission peaks at similar to 562, 599, 646 and 701 nm were recorded by exciting Si7+ ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). These peaks were attributed to (4)G(5/2)-> H-6(5/2) (562 nm), (4)G(5/2)-> H-6(7/2) (599 nm), (4)G(5/2)-> H-6(9/2) (646 nm), and (4)G(5/2)-> H-6(5/2) (701 nm) transitions of Sm3+. The highest emission was recorded at 3 mol% of Sm3+ doped Zn2SiO4. TL studies were carried out for 3 mol% Sm3+ concentration in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). Two U glow peaks at 152 and 223 degrees C were recorded. The kinetic parameters (E, b, and s), were estimated using Chen's peak shape method. Simple glow curve structure (223 degrees C), highly resistive, increase in TL. intensity up to 19.53 x 10(12) ions cm(-2), simple trap distribution makes Zn2SiO4:Sm3+ (3 mol%) phosphor highly useful in radiation dosimetry.

Role of outer membrane exopolymers of Acidithiobacillus ferrooxidans in adsorption of cells onto pyrite and chalcopyrite

Bacterial surface polymers play a major role in the adhesion of bacterial cells to solid surfaces. Lipopolysaccharides (LPS) are essential constituents of the cell walls of almost all Gram-negative bacteria. This paper reports the results of the investigations on the role of outer membrane exopolymers (LPS) of the chemolithotroph, Acidithiobacillus ferrooxidans, in adsorption of the cells onto pyrite and chalcopyrite. Optimization of EDTA treatment for removal of LPS from cell surface and the surface characterization of EDTA-treated cells are outlined. There was no change in cell morphology or loss in cell motility upon treatment with upto 0.04 mM EDTA for 1 h. Partial removal of LPS by EDTA treatment resulted in reduced adsorption of the cells on both pyrite and chalcopyrite. The protein profile of the EDTA-extractable fraction showed presence of certain outer membrane proteins indicating that EDTA treatment results in temporary gaps in the outer membrane. Also, specificity towards pyrite compared to chalcopyrite that was exhibited by untreated cells was lost when their exopolymer layers were stripped off, which could be attributed to the role of outer membrane proteins in the mineral-specificity exhibited by the bacteria. (C) 2013 Elsevier B.V. All rights reserved.

Dinuclear zinc bis(thiosemicarbazone) complexes: Synthesis, in vitro anticancer activity, cellular uptake and DNA interaction study

Four dinucleating bis(thiosemicarbazone) ligands and their zinc complexes have been synthesized and characterized by multinuclear NMR (H-1 and C-13), IR, UV-Vis, ESI-MS and fluorescence spectroscopic techniques. Their purity was assessed by elemental analysis. Cytotoxicity was tested against five human cancer cell lines using the sulphorhodamine B (SRB) assay, where one of the complexes, 1,3-bis{biacetyl-2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} propane (6), was found to be quite cytotoxic against MCF-7 (breast cancer) and HepG2 (hepatoma cancer) cell lines, with a potency similar to that of the well known anticancer drug adriamycin. It is evident from the cellular uptake studies that the uptake is same for the active complex 6 and the inactive complex 8 (1,6-bis{biacetyl- 2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} hexane) in MCF-7 and HepG2 cell lines. In vitro DNA binding and cleavage studies revealed that all complexes bind with DNA through electrostatic interaction, and cause no significant cleavage of DNA. (C) 2'13 Elsevier B. V. All rights reserved.

Nitrogen deposition: how important is it for global terrestrial carbon uptake?

Global carbon budget studies indicate that the terrestrial ecosystems have remained a large sink for carbon despite widespread deforestation activities. CO2 fertilization, N deposition and re-growth of mid-latitude forests are believed to be key drivers for land carbon uptake. In this study, we assess the importance of N deposition by performing idealized near-equilibrium simulations using the Community Land Model 4.0 (CLM4). In our equilibrium simulations, only 12-17% of the deposited nitrogen is assimilated into the ecosystem and the corresponding carbon uptake can be inferred from a C : N ratio of 20 : 1. We calculate the sensitivity of the terrestrial biosphere for CO2 fertilization, climate warming and N deposition as changes in total ecosystem carbon for unit changes in global mean atmospheric CO2 concentration, global mean temperature and Tera grams of nitrogen deposition per year, respectively. Based on these sensitivities, it is estimated that about 242 PgC could have been taken up by land due to the CO2 fertilization effect and an additional 175 PgC taken up as a result of the increased N deposition since the pre-industrial period. Because of climate warming, the terrestrial ecosystem could have lost about 152 PgC during the same period. Therefore, since pre-industrial times terrestrial carbon losses due to warming may have been more or less compensated by effects of increased N deposition, whereas the effect of CO2 fertilization is approximately indicative of the current increase in terrestrial carbon stock. Our simulations also suggest that the sensitivity of carbon storage to increased N deposition decreases beyond current levels, indicating that climate warming effects on carbon storage may overwhelm N deposition effects in the future.

The projective plane, J-holomorphic curves and Desargues' theorem

By a theorem of Gromov, for an almost complex structure J on CP2 tamed by the standard symplectic structure, the J-holomorphic curves representing the positive generator of homology form a projective plane. We show that this satisfies the Theorem of Desargues if and only if J is isomorphic to the standard complex structure. This answers a question of Ghys. (C) 2013 Published by Elsevier Masson SAS on behalf of Academie des sciences.