A DMFC with Methanol-Tolerant-Carbon-Supported-Pt-Pd-Alloy Cathode

Methanol-tolerant Pt-Pd alloy catalysts supported on to carbon with varying Pt:Pd atomic ratios of 1:1, 2:1 and 3:1 are prepared by a novel wet-chemical method and characterized using powder XRD, XPS, FESEM, EDAX and TEM techniques. The optimum atomic weight ratio for Pt to Pd in the carbon-supported alloy catalyst as established by linear-sweep voltammetry (LSV) and cell polarization studies is found to be 2:1. A direct methanol fuel cell (DMFC) employing carbon-supported Pt-Pd (2:1) alloy (Pt-Pd/C) catalyst as the cathode catalyst delivers a peak-power density of 115 mW/cm(2) at 70 degrees C as compared to peak-power density of 60 mW/cm(2) obtained with the DMFC employing carbon-supported Pt (Pt/C) catalyst operating under similar conditions. In the literature, DMFCs operating with Pt-TiO2 (2:1)/C and Pt-Au (2:1)/C methanol-tolerant cathodes are reported to exhibit maximum ORR activity among the group of these methanol-tolerant cathodes with varying catalysts compositions. Accordingly, the present study also provides an effective route to design methanol-tolerant-oxygen-reduction catalysts for DMFCs. (C) 2011 The Electrochemical Society. DOI: 10.1149/1.3596542] All rights reserved.

Icosahedral quasicrystalline and hexagonal approximant phases in the Al-Mn-Be alloy system

We report the formation of a primitive icosahedral quasicrystal with increased stability in Al Mn-Be alloys close to the compound Al15Mn13Be2, by melt spinning and injection casting. The crystal structure of this compound was unknown. We show that in as-cast as well as heat treated condition the intermetallic phase H1 has a hexagonal structure with lattice parameters a = 1.2295 run and c = 2.4634 nm. The space group is P6(3)/mmc In the injection-cast samples, the quasicrystal coexists with another closely related hexagonal phase H2 with a = 1.2295 nm and c = 1.2317 nm with a possible space group of P6/mmm. This phase exhibits specific orientation relationships with the icosahedral quasicrystal given by [0001](hex)//2f(QC) and [01 (1) over bar0](hex)//5f(QC) where 2f(QC) and 5f(QC) represent twofold and fivefold axes respectively. Electron diffraction patterns from both phases exhibit a close resemblance to the quasicrystalline phase. It is shown that the H1 phase is closely related to mu-Al4Mn with the same e parameter while the a parameter is reduced by tau. Following Kreiner and Franzen, it is postulated that both structures (H1 and H2) can be understood by a simple hexagonal packing of I13 clusters.

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

MOCVD of aluminium oxide films using aluminiurn beta-diketonates as precursors

Deposition of Al2O3 coatings by CVD is of importance because they are often used as abrading material in cemented carbide cutting tools. The conventionally used CVD process for Al2O3 involves the corrosive reactant AlCl3. In this paper, we report on the thermal characterisation of the metalorganic precursors namely aluminium tristetramethyl-heptanedionate [Al(thd)(3)] and aluminium tris-acetylacetonate [Al(acac)(3)] and their application to the CVD of Al2O3 films. Crystalline Al2O3 films were deposited by MOCVD at low temperatures by the pyrolysis of Al(thd)(3) and Al(acac)(3). The films were deposited on a TiN-coated tungsten carbide (TiN/WC) and Si(100) substrates in the temperature range 500-1100degreesC. The as-deposited films were characterised by x-ray diffraction, optical microscopy, scanning and transmission electron microscopy, Auger electron spectroscopy. The observed crystallinity of films grown at low temperatures, their microstructure, and composition may be interpreted in terms of a growth process that involves the melting of the metalorganic precursor on the hot growth surface.

Scaling analysis of momentum, heat, and mass transfer in binary alloy solidification problems

A systematic approach is developed for scaling analysis of momentum, heat and species conservation equations pertaining to the case of solidification of a binary mixture. The problem formulation and description of boundary conditions are kept fairly general, so that a large class of problems can be addressed. Analysis of the momentum equations coupled with phase change considerations leads to the establishment of an advection velocity scale. Analysis of the energy equation leads to an estimation of the solid layer thickness. Different regimes corresponding to different dominant modes of transport are simultaneously identified. A comparative study involving several cases of possible thermal boundary conditions is also performed. Finally, a scaling analysis of the species conservation equation is carried out, revealing the effect of a non-equilibrium solidification model on solute segregation and species distribution. It is shown that non-equilibrium effects result in an enhanced macrosegregation compared with the case of an equilibrium model. For the sake of assessment of the scaling analysis, the predictions are validated against corresponding computational results.

Structural model for the Cu-B site of dopamine beta-hydroxylase: Crystal structure of a copper(II) complex showing N3OS coordination with an axial sulfur ligation

A copper(II) complex containing a NSO-donor Schiff base and NN-donor 2,2'-bipyridine has been prepared and structurally characterized. The square pyramidal complex with an axial sulfur ligation is a structural model for the CUB site of dopamine-hydroxylase in its oxidized form. The copper(II) complex is catalytically active in the oxidation of ascorbic acid by dioxygen mediated by a copper(I) species which is proposed to have a four-coordinate structure with a N3S coordination geometry.

Influence of temperature and strain rate on the flow stress of an FeAl alloy

The deformation behavior of an FeAl alloy processed by hot extrusion of water atomized powder has been investigated. Compression tests are performed in the temperature range 1073–1423 K and in the strain rate range 0.001–100 s−1 up to a true plastic strain of 0.5. The flow stress has been found to be strongly dependent on temperature as well as strain rate. The stress exponent in the power law rate equation is estimated to be in the range 7.0–4.0, decreasing with temperature. The activation energy for plastic flow in the range 1073–1373 K varies from 430 kJ mol−1 at low stresses to 340 kJ mol−1 at high stresses. However, it is fairly independent of strain rate and strain. The activation area has similarly shown a stress dependence and lies in the range 160–45b2. At 1423 K and at strain rates lower than 0.1 s−1 a strain rate sensitivity of 0.3 is observed with an associated activation energy of 375 kJ mol−1. The plastic flow in the entire range of temperature and strain rate investigated appears to be controlled by a diffusion mechanism. The results have revealed that it is possible to process the alloy by superplastic forming in the range 1373–1423 K at strain rates lower than 0.1 s−1.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part I-Experimental Studies

Experimental studies were performed to investigate the role and influence of grain movement on macrosegregation and microstructure evolution during equiaxed solidification. Casting experiments were performed with a grain-refined Al-Cu alloy in a rectangular sand mold. For the aluminum alloy studied, the equiaxed grains are lighter than the bulk melt and thus float up. Experiments were designed to investigate floatation phenomena of equiaxed grains in the presence of thermosolutal convection. Cooling curves were recorded at key locations in both the casting and the chill. Quantitative image analysis and spatial chemical analysis were performed on the solidified casting to observe the chemical and microstructural inhomogeneity created by the melt convection and solid floatation. Several notable features that can be attributed to grain movement were observed in temperature histories, macrosegregation patterns, and microstructures. In our experiments, the floatation of grains influences the thermal conditions and the overall flow direction in the casting cavity. In some cases, the induced flow resulting from the grain movement caused a flow reversal. This in turn influences the solidification direction, microstructure evolution, and the overall macrosegregation behavior.

Role of TGF-beta beta and BMP7 in the pathogenesis of oral submucous fibrosis

To understand the molecular pathogenesis of oral submucous fibrosis (OSF), which is a chronic inflammatory disease, gene expression profiling was performed in 10 OSF tissues against 8 pooled normal tissues using oligonucleotide arrays. Microarray results revealed differential expression of 5288 genes (P < a parts per thousand currency sign 0.05 and fold change >= a parts per thousand yen 1.5). Among these, 2884 are upregulated and 2404 are downregulated. Validation employing quantitative real-time PCR and immunohistochemistry confirmed upregulation of transforming growth factor-beta beta 1 (TGF-beta beta 1), TGFBIp, THBS1, SPP1, and TIG1 and downregulation of bone morphogenic protein 7 (BMP7) in OSF tissues. Furthermore, activation of TGF-beta beta pathway was evident in OSF as demonstrated by pSMAD2 strong immunoreactivity. Treatment of keratinocytes and oral fibroblasts by TGF-beta beta confirmed the regulation of few genes identified in microarray including upregulation of connective tissue growth factor, TGM2, THBS1, and downregulation of BMP7, which is a known negative modulator of fibrosis. Taken together, these data suggest activation of TGF-beta beta signaling and suppression of BMP7 expression in the manifestation of OSF.

Evolution of crystallographic texture during deformation of submicron grain size titanium

Evolution of deformation texture in commercially pure titanium with submicron grain size (SMG) was studied using x-ray diffraction (XRD) and electron back scatter diffraction (EBSD) methods. The material was deformed by rolling at room temperature. The deformation mechanism was found to be slip dominated with a pyramidal slip system facilitating plastic deformation. No evidence of tensile or compressive twinning was detected, as generally seen in the case of titanium with conventional microcrystalline grain size. The absence of twinning and the propensity of the pyramidal slip system in the SMG Ti is attributed to the lack of coordinated motion of zonal partial dislocations that leads to twinning.

Characterization of Ni-Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni-Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H2SO4 medium. Electronic absorption spectrum of bath solution containing Ni2+ Pd2+ ions and EDA indicated the formation of a four coordinate square planar metal-ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd-Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm(-2)). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H2SO4 medium is found to be promoted on Ni-Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni-Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times. (C) 2003 Elsevier Science B.V. All rights reserved.

Thin Films of Titanium Dioxide Prepared by Chemical Routes using Novel Precursors

Novel, volatile, stable, oxo-β-ketoesterate complexes of titanium, whose synthesis requires only an inert atmosphere, as opposed to a glove box, have been developed. Using one of the complexes as the precursor, thin films of TiO2 have been deposited on glass substrates by metalorganic chemical vapor deposition (MOCVD) at temperatures ranging from 400°C to 525°C and characterized by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. All the films grown in this temperature range are very smooth; those grown above 480°C consist of nearly monodisperse, nanocrystals of the anatase phase. Optical studies show the bandgaps in the range 3.4–3.7 eV for films grown at different temperatures. Thin films of anatase TiO2 have also been grown by spin-coating technique using another ketoesterate complex of titanium, demonstrating that the newly developed complexes can be successfully used for thin film growth by various chemical routes.

Texture evolution in an Al-Cu alloy during equal channel angular pressing: the effect of starting microstructure

In this article, the effect of initial microstructure on the texture evolution in 2014 Al alloy during equal channel angular pressing (ECAP) through route A has been reported. Three heat treatment conditions were chosen to generate the initial microstructures, namely (i) the recrystallization anneal (as-received), (ii) solution treatment at 768 K for 1 h, and (iii) solution treatment (768 K for 1 h) plus aging at 468 K for 5 h. Texture analyses were performed using orientation distribution function (ODF) method. The texture strength after ECAP processing was different for the three samples in the order, solutionised > solutionised plus aged condition > as-received. The prominent texture components were A (E) /(A) over bar (E) and B(E)/(B) over bar (E) in addition to several weaker components for the three materials. The strong texture evolution in solutionised condition has been attributed to higher strain hardening of the matrix due to higher amount of solute. In case of the as-received as well as solutionised plus aged alloy, the weaker texture could be due to the strain scattering from extensive precipitate fragmentation and dissolution during ECAP.