Pt-RuO(2) electrodes prepared by thermal decomposition of polymeric precursors as catalysts for direct methanol fuel cell applications

The electrocatalytic activity of Pt and RuO(2) mixed electrodes of different compositions towards methanol oxidation was investigated. The catalysts were prepared by thermal decomposition of polymeric precursors and characterized by energy dispersive X-ray, scanning electronic microscopy, X-ray diffraction and cyclic voltammetry. This preparation method allowed obtaining uniform films with controlled stoichiometry and high surface area. Cyclic voltammetry experiments in the presence of methanol showed that mixed electrodes decreased the potential peak of methanol oxidation by approximately 100 mV (RHE) when compared to the electrode containing only Pt. In addition, voltammetric experiments indicated that the Pt(0.6)Ru(0.4)O(y) electrode led to higher oxidation current densities at lower potentials. Chronoamperometry experiments confirmed the contribution of RuO(2) to the catalytic activity as well as the better performance of the Pt(0.6)Ru(0.4)O(y) electrode composition. Formic acid and CO(2) were identified as being the reaction products formed in the electrolysis performed at 400 and 600 mV. The relative formation of CO(2) was favored in the electrolysis performed at 400 mV (RHE) with the Pt(0.6)Ru(0.4)O(y) electrode. The presence of RuO(2) in Pt-Ru-based electrodes is important for improving the catalytic activity towards methanol electrooxidation. Moreover, the thermal decomposition of polymeric precursors seems to be a promising route for the production of catalysts applicable to DMFC. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Morphological and electrochemical investigation of RuO(2)-Ta(2)O(5) oxide films prepared by the Pechini-Adams method

Preparation methods can profoundly affect the structural and electrochemical properties of electrocatalytic coatings. In this investigation, RuO(2)-Ta(2)O(5) thin films containing between 10 and 90 at.% Ru were prepared by the Pechini-Adams method. These coatings were electrochemically and physically characterized by cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The composition and morphology of the oxide were investigated before and after accelerated life tests (ALT) by EDX and SEM. SEM results indicate typical mud-flat-cracking morphology for the majority of the films. High resolution SEMs reveal that pure oxide phases exhibit nanoporosity while binary compositions display a very compact structure. EDX analyses reveal considerable amounts of Ru in the coating even after total deactivation. XRD indicated a rutile-type structure for RuO(2) and orthorhombic structure for Ta(2)O(5). XPS data demonstrate that the binding energy of Ta is affected by Ru addition in the thin films, but the binding energy of Ru is not likewise influenced by Ta. The stability of the electrodes was evaluated by ALT performed at 750 mA cm(-2) in 80 degrees C 0.5 mol dm(-3) H(2)SO(4). The performance of electrodes prepared by the Pechini-Adams method is 100% better than that of electrodes prepared by standard thermal decomposition.

Effect of Ni on Pt/C and PtSn/C prepared by the Pechini method

Different compositions of Pt, PtNi, PtSn, and PtSnNi electrocatalysts supported on carbon Vulcan XC-72 were prepared through thermal decomposition of polymeric precursors. The nanoparticles were characterized by morphological and structural analyses (XRD, TEM, and EDX). XRD results revealed a face-centered cubic structure for platinum, and there was evidence that Ni and Sn atoms are incorporated into the Pt structure. The electrochemical investigation was carried out in slightly acidic medium (H(2)SO(4) 0.05 mol L(-1)), in the absence and in the presence of ethanol. Addition of Ni to Pt/C and PtSn/C catalysts significantly shifted the onset of ethanol and CO oxidations toward lower potentials, thus enhancing the catalytic activity, especially in the case of the ternary PtSnNi/C composition. Electrolysis of ethanol solutions at 0.4 V us. RHE allowed for determination of acetaldehyde and acetic acid as the reaction products, as detected by HPLC analysis. Due to the high concentration of ethanol employed in the electrolysis experiments (1.0 mol L(-1)), no formation of CO(2) was observed. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Petri net model decomposition - a model based approach supporting distributed execution

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Electrotécnica, Especialidade de Sistemas Digitais, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Calibration Method for Underwater Visual Ground-Truth System

This work presents an automatic calibration method for a vision based external underwater ground-truth positioning system. These systems are a relevant tool in benchmarking and assessing the quality of research in underwater robotics applications. A stereo vision system can in suitable environments such as test tanks or in clear water conditions provide accurate position with low cost and flexible operation. In this work we present a two step extrinsic camera parameter calibration procedure in order to reduce the setup time and provide accurate results. The proposed method uses a planar homography decomposition in order to determine the relative camera poses and the determination of vanishing points of detected lines in the image to obtain the global pose of the stereo rig in the reference frame. This method was applied to our external vision based ground-truth at the INESC TEC/Robotics test tank. Results are presented in comparison with an precise calibration performed using points obtained from an accurate 3D LIDAR modelling of the environment.

Development of a new method for the characterisation of bioreactors concerning heat and mass transfer

Since the specific heat transfer coefficient (UA) and the volumetric mass transfer coefficient (kLa) play an important role for the design of biotechnological processes, different techniques were developed in the past for the determination of these parameters. However, these approaches often use imprecise dynamic methods for the description of stationary processes and are limited towards scale and geometry of the bioreactor. Therefore, the aim of this thesis was to develop a new method, which overcomes these restrictions. This new approach is based on a permanent production of heat and oxygen by the constant decomposition of hydrogen peroxide in continuous mode. Since the degradation of H2O2 at standard conditions only takes place by the support of a catalyst, different candidates were investigated for their potential (regarding safety issues and reaction kinetic). Manganese-(IV)-oxide was found to be suitable. To compensate the inactivation of MnO2, a continuous process with repeated feeds of fresh MnO2 was established. Subsequently, a scale-up was successfully carried out from 100 mL to a 5 litre glass bioreactor (UniVessel®)To show the applicability of this new method for the characterisation of bioreactors, it was compared with common approaches. With the newly established technique as well as with a conventional procedure, which is based on an electrical heat source, specific heat transfer coefficients were measured in the range of 17.1 – 24.8 W/K for power inputs of about 50 – 70 W/L. However, a first proof of concept regarding the mass transfer showed no constant kLa for different dilution rates up to 0.04 h-1.Based on this, consecutive studies concerning the mass transfer should be made with higher volume flows, due to more even inflow rates. In addition, further experiments are advisable, to analyse the heat transfer in single-use bioreactors and in larger common systems.

An analysis of strategic paths through the decomposition of total factor productivity: the case of Spanish savings banks

The Spanish savings banks attracted quite a considerable amount of interest within the scientific arena, especially subsequent to the disappearance of the regulatory constraints during the second decade of the 1980s. Nonetheless, a lack of research identified with respect to mainstream paths given by strategic groups, and the analysis of the total factor productivity. Therefore, on the basis of the resource-based view of the firm and cluster analysis, we make use of changes in structure and performance ratios in order to identify the strategic groups extant in the sector. We attain a threeways division, which we link with different input-output specifications defining strategic paths. Consequently, on the basis of these three dissimilar approaches we compute and decompose a Hicks-Moorsteen total factor productivity index. Obtained results put forward an interesting interpretation under a multi-strategic approach, together with the setbacks of employing cluster analysis within a complex strategic environment. Moreover, we also propose an ex-post method of analysing the outcomes of the decomposed total factor productivity index that could be merged with non-traditional techniques of forming strategic groups, such as cognitive approaches.

Comparison between computational alanine scanning and per-residue binding free energy decomposition for protein-protein association using MM-GBSA: application to the TCR-p-MHC complex.

Recognition by the T-cell receptor (TCR) of immunogenic peptides (p) presented by Class I major histocompatibility complexes (MHC) is the key event in the immune response against virus-infected cells or tumor cells. A study of the 2C TCR/SIYR/H-2K(b) system using a computational alanine scanning and a much faster binding free energy decomposition based on the Molecular Mechanics-Generalized Born Surface Area (MM-GBSA) method is presented. The results show that the TCR-p-MHC binding free energy decomposition using this approach and including entropic terms provides a detailed and reliable description of the interactions between the molecules at an atomistic level. Comparison of the decomposition results with experimentally determined activity differences for alanine mutants yields a correlation of 0.67 when the entropy is neglected and 0.72 when the entropy is taken into account. Similarly, comparison of experimental activities with variations in binding free energies determined by computational alanine scanning yields correlations of 0.72 and 0.74 when the entropy is neglected or taken into account, respectively. Some key interactions for the TCR-p-MHC binding are analyzed and some possible side chains replacements are proposed in the context of TCR protein engineering. In addition, a comparison of the two theoretical approaches for estimating the role of each side chain in the complexation is given, and a new ad hoc approach to decompose the vibrational entropy term into atomic contributions, the linear decomposition of the vibrational entropy (LDVE), is introduced. The latter allows the rapid calculation of the entropic contribution of interesting side chains to the binding. This new method is based on the idea that the most important contributions to the vibrational entropy of a molecule originate from residues that contribute most to the vibrational amplitude of the normal modes. The LDVE approach is shown to provide results very similar to those of the exact but highly computationally demanding method.

Allowing for heterogeneity in the decomposition of measures of inequality in health

This paper shows how recently developed regression-based methods for the decomposition ofhealth inequality can be extended to incorporate heterogeneity in the responses of health to the explanatory variables. We illustrate our method with an application to the GHQ measure of psychological well-being taken from the British Household Panel Survey. The results suggest that there is an important degree of heterogeneity in the association of health to explanatory variables across birth cohorts and genders which, in turn, accounts for a substantial percentage of the inequality in observed health.

Optimization of multiclass queueing networks with changeover times via the achievable region method: Part II, the multi-station case

We address the problem of scheduling a multi-station multiclassqueueing network (MQNET) with server changeover times to minimizesteady-state mean job holding costs. We present new lower boundson the best achievable cost that emerge as the values ofmathematical programming problems (linear, semidefinite, andconvex) over relaxed formulations of the system's achievableperformance region. The constraints on achievable performancedefining these formulations are obtained by formulatingsystem's equilibrium relations. Our contributions include: (1) aflow conservation interpretation and closed formulae for theconstraints previously derived by the potential function method;(2) new work decomposition laws for MQNETs; (3) new constraints(linear, convex, and semidefinite) on the performance region offirst and second moments of queue lengths for MQNETs; (4) a fastbound for a MQNET with N customer classes computed in N steps; (5)two heuristic scheduling policies: a priority-index policy, anda policy extracted from the solution of a linear programmingrelaxation.

The importance of individual heterogeneity in the decomposition of measures of socioeconomic inequality in health: An approach based on quantile regression

This paper shows how recently developed regression-based methods for thedecomposition of health inequality can be extended to incorporateindividual heterogeneity in the responses of health to the explanatoryvariables. We illustrate our method with an application to the CanadianNPHS of 1994. Our strategy for the estimation of heterogeneous responsesis based on the quantile regression model. The results suggest that thereis an important degree of heterogeneity in the association of health toexplanatory variables which, in turn, accounts for a substantial percentageof inequality in observed health. A particularly interesting finding isthat the marginal response of health to income is zero for healthyindividuals but positive and significant for unhealthy individuals. Theheterogeneity in the income response reduces both overall health inequalityand income related health inequality.

Multiresolution-based image fusion with additive wavelet decomposition

The standard data fusion methods may not be satisfactory to merge a high-resolution panchromatic image and a low-resolution multispectral image because they can distort the spectral characteristics of the multispectral data. The authors developed a technique, based on multiresolution wavelet decomposition, for the merging and data fusion of such images. The method presented consists of adding the wavelet coefficients of the high-resolution image to the multispectral (low-resolution) data. They have studied several possibilities concluding that the method which produces the best results consists in adding the high order coefficients of the wavelet transform of the panchromatic image to the intensity component (defined as L=(R+G+B)/3) of the multispectral image. The method is, thus, an improvement on standard intensity-hue-saturation (IHS or LHS) mergers. They used the ¿a trous¿ algorithm which allows the use of a dyadic wavelet to merge nondyadic data in a simple and efficient scheme. They used the method to merge SPOT and LANDSATTM images. The technique presented is clearly better than the IHS and LHS mergers in preserving both spectral and spatial information.

A wavelet-based method for the determination of the relative resolution between remotely sensed images

Spatial resolution is a key parameter of all remote sensing satellites and platforms. The nominal spatial resolution of satellites is a well-known characteristic because it is directly related to the area in ground that represents a pixel in the detector. Nevertheless, in practice, the actual resolution of a specific image obtained from a satellite is difficult to know precisely because it depends on many other factors such as atmospheric conditions. However, if one has two or more images of the same region, it is possible to compare their relative resolutions. In this paper, a wavelet-decomposition-based method for the determination of the relative resolution between two remotely sensed images of the same area is proposed. The method can be applied to panchromatic, multispectral, and mixed (one panchromatic and one multispectral) images. As an example, the method was applied to compute the relative resolution between SPOT-3, Landsat-5, and Landsat-7 panchromatic and multispectral images taken under similar as well as under very different conditions. On the other hand, if the true absolute resolution of one of the images of the pair is known, the resolution of the other can be computed. Thus, in the last part of this paper, a spatial calibrator that is designed and constructed to help compute the absolute resolution of a single remotely sensed image is described, and an example of its use is presented.

Microbial biomass and soil fauna during the decomposition of cover crops in no-tillage system

The decomposition of plant residues is a biological process mediated by soil fauna, but few studies have been done evaluating its dynamics in time during the process of disappearance of straw. This study was carried out in Chapecó, in southern Brazil, with the objective of monitoring modifications in soil fauna populations and the C content in the soil microbial biomass (C SMB) during the decomposition of winter cover crop residues in a no-till system. The following treatments were tested: 1) Black oat straw (Avena strigosa Schreb.); 2) Rye straw (Secale cereale L.); 3) Common vetch straw (Vicia sativa L.). The cover crops were grown until full flowering and then cut mechanically with a rolling stalk chopper. The soil fauna and C content in soil microbial biomass (C SMB) were assessed during the period of straw decomposition, from October 2006 to February 2007. To evaluate C SMB by the irradiation-extraction method, soil samples from the 0-10 cm layer were used, collected on eight dates, from before until 100 days after residue chopping. The soil fauna was collected with pitfall traps on seven dates up to 85 days after residue chopping. The phytomass decomposition of common vetch was faster than of black oat and rye residues. The C SMB decreased during the process of straw decomposition, fastest in the treatment with common vetch. In the common vetch treatment, the diversity of the soil fauna was reduced at the end of the decomposition process.

Straw decomposition of nitrogen-fertilized grasses intercropped with irrigated maize in an integrated crop-livestock system

The greatest limitation to the sustainability of no-till systems in Cerrado environments is the low quantity and rapid decomposition of straw left on the soil surface between fall and spring, due to water deficit and high temperatures. In the 2008/2009 growing season, in an area under center pivot irrigation in Selvíria, State of Mato Grosso do Sul, Brazil, this study evaluated the lignin/total N ratio of grass dry matter , and N, P and K deposition on the soil surface and decomposition of straw of Panicum maximum cv. Tanzânia, P. maximum cv. Mombaça, Brachiaria. brizantha cv. Marandu and B. ruziziensis, and the influence of N fertilization in winter/spring grown intercropped with maize, on a dystroferric Red Latosol (Oxisol). The experiment was arranged in a randomized block design in split-plots; the plots were represented by eight maize intercropping systems with grasses (sown together with maize or at the time of N side dressing). Subplots consisted of N rates (0, 200, 400 and 800 kg ha-1 year-1) sidedressed as urea (rates split in four applications at harvests in winter/spring), as well as evaluation of the straw decomposition time by the litter bag method (15, 30, 60, 90, 120, and 180 days after straw chopping). Nitrogen fertilization in winter/spring of P. maximum cv. Tanzânia, P. maximum cv. Mombaça, B. brizantha cv. Marandu and B. ruziziensis after intercropping with irrigated maize in an integrated crop-livestock system under no-tillage proved to be a technically feasible alternative to increase the input of straw and N, P and K left on the soil surface, required for the sustainability of the system, since the low lignin/N ratio of straw combined with high temperatures accelerated straw decomposition, reaching approximately 30 % of the initial amount, 90 days after straw chopping.