Electro-Oxidation of Borohydride on Rhodium, Iridium, and Rhodium-Iridium Bimetallic Nanoparticles with Implications to Direct Borohydride Fuel Cells

Electrochemical oxidation of borohydride is studied on nanosized rhodium, iridium, and bimetallic rhodium-iridium catalysts supported onto Vulcan XC72R carbon. The catalysts are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy in conjunction with cyclic voltammetry and polarization studies. The studies reveal that a 20 wt % bimetallic Rh-Ir catalyst supported onto carbon (Rh-Ir/C) is quite effective for the oxidation of borohydride. Direct borohydride fuel cell with Rh-Ir/C as the anode catalyst and Pt/C as the cathode catalyst exhibits a peak power density of 270 mW/cm(2) at a load current density of 290 mA/cm(2) as against 200 mW/cm(2) at 225 mA/cm(2) for Rh/C and 140 mW/cm(2) at 165 mA/cm(2) for Ir/C while operating at 80 degrees C. The synergistic catalytic activity for the bimetallic Rh-Ir nanoparticles toward borohydride oxidation is corroborated by density-functional theory calculations using electron-localization function. (C) 2010 The Electrochemical Society. [DOI:10.1149/1.3442372] All rights reserved.

Direct Writing of Copper Film Patterns by Laser-Induced Decomposition of Copper Acetate

Direct writing of patterns is being widely attempted in the field of microelectronic circuit/device manufacture. Use of this technique eliminates the need for employing photolithographic process. Laser induced direct writing can be achieved by (i) Photochemical reaction [i] , (ii) Evaporation from target material [2], and (iii) decomposition.Micron size features of palladium and copper through decomposition of palladium acetate and copper formate respectively on quartz and silicon using Argon ion laser have been reported [3,4] .In this commuication we report a technique for both single line and large area depositon of copper through decomposition of copper acetate,(CH3COO)2Cu, on alumina substrates.Nd:YAG laser known for its reliability and low maintenance cost as compared to excimer and other gas lasers is used. This technique offers an attractive and economical alternative for manufacture of thin film microcircuits.

Modified-Pore-Filled-PVDF-Membrane Electrolytes for Direct Methanol Fuel Cells

The polyvinylidene fluoride (PVDF) membrane is modified by the chemical etchant-route employing a sodium naphthalene charge-transfer complex followed by impregnation with Nafion ionomer or polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) polymeric blend solutions by a dip-coating technique to form pore-filled-membrane electrolytes for application in direct methanol fuel cells (DMFCs). The number of coatings on the surface-modified PVDF membrane is varied between 5 and 15 and is found to be optimum at 10 layers both for Nafion and PVA-PSSA impregnations for effective DMFC performance. Hydrophilicity of the modified-membrane electrolytes is studied by determining average contact angle and surface-wetting energy. Morphology of the membranes is analyzed by a cross-sectional scanning electron microscope. The modified PVDF membrane electrolytes are characterized for their water-methanol sorption in conjunction with their mechanical properties, proton conductivity, and DMFC performance. Air permeability for the modified membranes is studied by a capillary-flow porometer. Methanol crossover flux across modified-PVDF-membrane electrolytes is studied by measuring the mass balance of methanol using a density meter. DMFCs employing membrane electrode assemblies with the modified PVDF membranes exhibit a peak power-density of 83 mW/cm(2) with Nafion impregnation and 59 mW/cm(2) for PVA-PSSA impregnation, respectively. Among the membranes studied here, stabilities of modified-pore-filled PVDF-Nafion and PVDF-PVA-PSSA membranes with 10-layers coat are promising for application in DMFCs. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3518774] All rights reserved.

Modeling of concrete cracking-A hybrid technique of using displacement discontinuity element method and direct boundary element method

This paper presents a new approach by making use of a hybrid method of using the displacement discontinuity element method and direct boundary element method to model concrete cracking by incorporating fictitious crack model. Fracture mechanics approach is followed using the Hillerborg's fictitious crack model. A boundary element based substructure method and a hybrid technique of using displacement discontinuity element method and direct boundary element method are compared in this paper. In order to represent the process zone ahead of the crack, closing forces are assumed to act in such a way that they obey a linear normal stress-crack opening displacement law. Plain concrete beams with and without initial crack under three-point loading were analyzed by both the methods. The numerical results obtained were shown to agree well with the results from existing finite element method. The model is capable of reproducing the whole range of load-deflection response including strain-softening and snap-back behavior as illustrated in the numerical examples. (C) 2011 Elsevier Ltd. All rights reserved.

Bio-Composite Membrane Electrolytes for Direct Methanol Fuel Cells

A new class of bio-composite polymer electrolyte membranes comprising chitosan (CS) and certain biomolecules in particular, plant hormones such as 3-indole acetic acid (IAA), 4-chlorophenoxy acetic acid (CAA) and 1-naphthalene acetic acid (NAA) are explored to realize proton-conducting bio-composite membranes for application in direct methanol fuel cells (DMFCs). The sorption capability, proton conductivity and ion-exchange capacity of the membranes are characterized in conjunction with their thermal and mechanical behaviour. A novel approach to measure the permeability of the membranes to both water and methanol is also reported, employing NMR imaging and volume localized NMR spectroscopy, using a two compartment permeability cell. A DMFC using CS-IAA composite membrane, operating with 2M aqueous methanol and air at 70 degrees C delivers a peak power density of 25 mW/cm(2) at a load current density of 150 mA/cm(2). The study opens up the use of bio-compatible membranes in polymer-electrolyte-membrane fuel cells. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.030111jes] All rights reserved.

Semiconductor to metal transition in bilayer phosphorene under normal compressive strain

Phosphorene, a two-dimensional analog of black phosphorous, has been a subject of immense interest recently, due to its high carrier mobilities and a tunable bandgap. So far, tunability has been predicted to be obtained with very high compressive/tensile in-plane strains, and vertical electric field, which are difficult to achieve experimentally. Here, we show using density functional theory based calculations the possibility of tuning electronic properties by applying normal compressive strain in bilayer phosphorene. A complete and fully reversible semiconductor to metal transition has been observed at similar to 13.35% strain, which can be easily realized experimentally. Furthermore, a direct to indirect bandgap transition has also been observed at similar to 3% strain, which is a signature of unique band-gap modulation pattern in this material. The absence of negative frequencies in phonon spectra as a function of strain demonstrates the structural integrity of the sheets at relatively higher strain range. The carrier mobilities and effective masses also do not change significantly as a function of strain, keeping the transport properties nearly unchanged. This inherent ease of tunability of electronic properties without affecting the excellent transport properties of phosphorene sheets is expected to pave way for further fundamental research leading to phosphorene-based multi-physics devices.

Direct Measurement of Three-Dimensional Forces in Atomic Force Microscopy

Direct measurement of three-dimensional (3-D) forces between an atomic force microscope (AFM) probe and the sample benefits diverse applications of AFM, including force spectroscopy, nanometrology, and manipulation. This paper presents the design and evaluation of a measurement system, wherein the deflection of the AFM probe is obtained at two points to enable direct measurement of all the three components of 3-D tip-sample forces in real time. The optimal locations for measurement of deflection on the probe are derived for a conventional AFM probe. Further, a new optimal geometry is proposed for the probe that enables measurement of 3-D forces with identical sensitivity and nearly identical resolution along all three axes. Subsequently, the designed measurement system and the optimized AFM probe are both fabricated and evaluated. The evaluation demonstrates accurate measurement of tip-sample forces with minimal cross-sensitivities. Finally, the real-time measurement system is employed as part of a feedback control system to regulate the normal component of the interaction force, and to perform force-controlled scribing of a groove on the surface of polymethyl methacrylate.

Direct Numerical Simulation Of Hypersonic Boundary-Layer Transition Over A Blunt Cone

Direct numerical simulation of transition How over a blunt cone with a freestream Mach number of 6, Reynolds number of 10,000 based on the nose radius, and a 1-deg angle of attack is performed by using a seventh-order weighted essentially nonoscillatory scheme for the convection terms of the Navier-Stokes equations, together with an eighth-order central finite difference scheme for the viscous terms. The wall blow-and-suction perturbations, including random perturbation and multifrequency perturbation, are used to trigger the transition. The maximum amplitude of the wall-normal velocity disturbance is set to 1% of the freestream velocity. The obtained transition locations on the cone surface agree well with each other far both cases. Transition onset is located at about 500 times the nose radius in the leeward section and 750 times the nose radius in the windward section. The frequency spectrum of velocity and pressure fluctuations at different streamwise locations are analyzed and compared with the linear stability theory. The second-mode disturbance wave is deemed to be the dominating disturbance because the growth rate of the second mode is much higher than the first mode. The reason why transition in the leeward section occurs earlier than that in the windward section is analyzed. It is not because of higher local growth rate of disturbance waves in the leeward section, but because the growth start location of the dominating second-mode wave in the leeward section is much earlier than that in the windward section.

Two-Phase Flow In Anode Flow Field Of A Small Direct Methanol Fuel Cell In Different Gravities

An in-situ visualization of two-phase flow inside anode flow bed of a small liquid fed direct methanol fuel cells in normal and reduced gravity has been conducted in a drop tower. The anode flow bed consists of 11 parallel straight channels. The length, width and depth of single channel, which had rectangular cross section, are 48.0, 2.5 and 2.0 mm, respectively. The rib width was 2.0 mm. The experimental results indicated that when the fuel cell orientation is vertical, two-phase flow pattern in anode channels can evolve from bubbly flow in normal gravity into slug flow in microgravity. The size of bubbles in the reduced gravity is also bigger. In microgravity, the bubbles rising speed in vertical channels is obviously slower than that in normal gravity. When the fuel cell orientation is horizontal, the slug flow in the reduced gravity has almost the same characteristic with that in normal gravity. It implies that the effect of gravity on two-phase flow is small and the bubbles removal is governed by viscous drag. When the gas slugs or gas columns occupy channels, the performance of liquid fed direct methanol fuel cells is failing rapidly. It infers that in long-term microgravity, flow bed and operating condition should be optimized to avoid concentration polarization of fuel cells.

Kinetic theory of normal quantum fluids

Close to equilibrium, a normal Bose or Fermi fluid can be described by an exact kinetic equation whose kernel is nonlocal in space and time. The general expression derived for the kernel is evaluated to second order in the interparticle potential. The result is a wavevector- and frequency-dependent generalization of the linear Uehling-Uhlenbeck kernel with the Born approximation cross section.

The theory is formulated in terms of second-quantized phase space operators whose equilibrium averages are the n-particle Wigner distribution functions. Convenient expressions for the commutators and anticommutators of the phase space operators are obtained. The two-particle equilibrium distribution function is analyzed in terms of momentum-dependent quantum generalizations of the classical pair distribution function h(k) and direct correlation function c(k). The kinetic equation is presented as the equation of motion of a two -particle correlation function, the phase space density-density anticommutator, and is derived by a formal closure of the quantum BBGKY hierarchy. An alternative derivation using a projection operator is also given. It is shown that the method used for approximating the kernel by a second order expansion preserves all the sum rules to the same order, and that the second-order kernel satisfies the appropriate positivity and symmetry conditions.

Direct numerical simulation of turbulent flows over superhydrophobic surfaces with gas pockets using linearized boundary conditions

Superhydrophobic surfaces are shown to be effective for surface drag reduction under laminar regime by both experiments and simulations (see for example, Ou and Rothstein, Phys. Fluids 17:103606, 2005). However, such drag reduction for fully developed turbulent flow maintaining the Cassie-Baxter state remains an open problem due to high shear rates and flow unsteadiness of turbulent boundary layer. Our work aims to develop an understanding of mechanisms leading to interface breaking and loss of gas pockets due to interactions with turbulent boundary layers. We take advantage of direct numerical simulation of turbulence with slip and no-slip patterned boundary conditions mimicking the superhydrophobic surface. In addition, we capture the dynamics of gas-water interface, by deriving a proper linearized boundary condition taking into account the surface tension of the interface and kinematic matching of interface deformation and normal velocity conditions on the wall. We will show results from our simulations predicting the dynamical behavior of gas pocket interfaces over a wide range of dimensionless surface tensions.

Direct determination of sialic acids in serum by capillary electrophoresis with UV detection

A novel method for the determination of N-acetylneuraminic acid (NANA) and N-glycolylneuraminic acid (NGNA) has been developed using high-performance capillary electrophoresis with UV detection at 195 nm, without pre or post-column derivatisation. The acids were separated in a 50-cm, fused-silica capillary (50 mu m i.d, 45.5-cm effective length) with Na2B4O7-Na2HPO4 buffer. The detection limit for NANA is a concentration of 9.6 x 10(-6) M or, in terms of mass: 3.879 x 10(-14) mol (39 fmol). This method is applicable to determination of NANA in normal human serum. The results were also compared with those of the colorimetrie method.

Direct deposition and characterization of Langmuir-Blodgett monolayers of soluble polyimides

Langmuir-Blodgett (LB) monolayers of three kinds of soluble polyimides were prepared with the direct deposition method, The monolayer structures were characterized with W-vis absorption spectroscopy, the wide angle X-ray scattering method and electrochemical techniques. The polyimide molecules in the LB monolayers lie orderly on the substrate surfaces with the orientation in which the dianhydride group is normal to the substrate surface and two carbonyl oxygen groups close to the surface. Therefore, the thickness of the three kinds of polyimide LB monolayers are the same because it depends on the distance between the two carbonyl oxygen groups in the same ring. The area of monomeric units are dependent on the length of the diamine group. The model of the molecular packing proposed from the quantomechanical calculation is in good agreement with the experimental results. (C) 1997 Elsevier Science S.A.

Direct electron transfer to cytochrome c oxidase in self-assembled monolayers on gold electrodes

The monolayer of cytochrome c oxidase maintaining physiological activity and attached covalently to the self-assembled monolayers of 3-mercaptopropionic acid (MPA) on a gold electrode was obtained. The results of cyclic voltammetry show that direct electron transfer between cytochrome c oxidase and the electrode surface is a fast and diffusionless process. MPA has a dual role as both electrode modifier and the bridging molecule which: keeps cytochrome c oxidase at an appropriate orientation without denaturation and enables direct electron transfer between the protein and the modified electrode. Immobilized cytochrome c oxidase exhibits biphasic phenomena between the concentration of the electrolyte and the normal potentials; meanwhile its electrochemical behavior is also influenced by the buffer components. The quasi-reversible electron transfer process of cytochrome c oxidase with formal potential 385 mV vs. SHE in 5mM phosphate buffer solution (pH 6.4) corresponds to the redox reaction of cyt a(3) in cytochrome c oxidase, and the heterogeneous electron transfer rate constant obtained is 1.56 s(-1). By cyclic voltammetry measurements, it was observed that oxidation and reduction of cytochrome c in solution were catalyzed by the immobilized cytochrome c oxidase. This cytochrome c oxidase/MPA/Au system provides a good mimetic model to study the physiological functions of membrane-associated enzymes and hopefully to build a third-generation biosensor without using a mediator.

Responses of vegetative gametophytes of Undaria pinnatifida to high irradiance in the process of gametogenesis

The population of Undaria pinnatifida in its ecologic niche sustains itself in high temperature summer in the form of vegetative gametophytes, the haploid stage in its heteromorphic life cycle. Gametogenesis initiates when seawater temperature drops below the threshold levels in autumn in the northern hemisphere. Given that the temperature may fall into the appropriate range for gametogenesis, the level of irradiance determines the final destiny of a gametophytic cell, either undergoing vegetative cell division or initiating gametogenesis. In elucidating how vegetatively propagated gametophytes cope with changes of irradiance in gametogenesis, we carried out a series of culture experiments and found that a direct exposure to irradiance as high as 270 mu mol photons m(-2) s(-1) was lethal to dim-light (7-10 mu mol photons m(-2) s(-1)) adapted male and female gametophytes. This lethal effect was linearly corelated with the exposure time. However, dim-light adapted vegetative gametophytes were shown to be able tolerate as high as 420 mu mol photons m(-2) s(-1) if the irradiance was steadily increased from dim light levels (7-10 mu mol photons m(-2) s(-1)) to 90, 180 and finally 420 mu mol photons m(-2) s(-1), respectively, at a minimum of 1-3 h intervals. Percentage of female gametophytic cells that turned into oogonia and were eventually fertilized was significantly higher if cultured at higher but not lethal irradiances. Findings of this investigation help to understand the dynamic changes of population size of sporophytic plants under different light climates at different site-specific ecologic niches. It may help to establish specific technical details of manipulation of light during mass production of seedlings by use of vegetatively propagated gametophytes.