A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the Surface of carbon black, by chemically introducing polymeric chains (Nafion (R) like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface call be prevented. The proton conduction between the active electrocatalyst site and the Nafion (R) ionomer membrane should be enhanced, thus diminishing the ohmic drop ill the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H(2)/air(PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm(-2) gmetal(-1) power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization Curves results clearly show that the main Cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer. (C) 2009 Elsevier B.V. All rights reserved.

Offline Detection, Identification, and Correction of Branch Parameter Errors Based on Several Measurement Snapshots

This paper proposes a three-stage offline approach to detect, identify, and correct series and shunt branch parameter errors. In Stage 1 the branches suspected of having parameter errors are identified through an Identification Index (II). The II of a branch is the ratio between the number of measurements adjacent to that branch, whose normalized residuals are higher than a specified threshold value, and the total number of measurements adjacent to that branch. Using several measurement snapshots, in Stage 2 the suspicious parameters are estimated, in a simultaneous multiple-state-and-parameter estimation, via an augmented state and parameter estimator which increases the V - theta state vector for the inclusion of suspicious parameters. Stage 3 enables the validation of the estimation obtained in Stage 2, and is performed via a conventional weighted least squares estimator. Several simulation results (with IEEE bus systems) have demonstrated the reliability of the proposed approach to deal with single and multiple parameter errors in adjacent and non-adjacent branches, as well as in parallel transmission lines with series compensation. Finally the proposed approach is confirmed on tests performed on the Hydro-Quebec TransEnergie network.

Blocked diisocyanates as reactive coupling agents: Application to pine fiber-polypropylene composites

In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

Volumetric reconstruction of the mean flow around circular cylinders fitted with strakes

The volumetric reconstruction technique presented in this paper employs a two-camera stereoscopic particle image velocimetry (SPIV) system in order to reconstruct the mean flow behind a fixed cylinder fitted with helical strakes, which are commonly used to suppress vortex-induced vibrations (VIV). The technique is based on the measurement of velocity fields at equivalent adjacent planes that results in pseudo volumetric fields. The main advantage over proper volumetric techniques is the avoidance of additional equipment and complexity. The averaged velocity fields behind the straked cylinders and the geometrical periodicity of the three-start configuration are used to further simplify the reconstruction process. Two straked cylindrical models with the same pitch (p = 10d) and two different heights (h = 0.1 and 0.2d) are tested. The reconstructed flow shows that the strakes introduce in the wake flow a well-defined wavelength of one-third of the pitch. Measurements of hydrodynamic forces, fluctuating velocity, vortex formation length, and vortex shedding frequency show the interdependence of the wake parameters. The vortex formation length is increased by the strakes, which is an important effect for the suppression of vortex-induced vibrations. The results presented complement previous investigations concerning the effectiveness of strakes as VIV suppressors and provide a basis of comparison to numerical simulations.

Modelling grain boundary migration during geometric dynamic recrystallization

High-angle grain boundary migration is predicted during geometric dynamic recrystallization (GDRX) by two types of mathematical models. Both models consider the driving pressure due to curvature and a sinusoidal driving pressure owing to subgrain walls connected to the grain boundary. One model is based on the finite difference solution of a kinetic equation, and the other, on a numerical technique in which the boundary is subdivided into linear segments. The models show that an initially flat boundary becomes serrated, with the peak and valley migrating into both adjacent grains, as observed during GDRX. When the sinusoidal driving pressure amplitude is smaller than 2 pi, the boundary stops migrating, reaching an equilibrium shape. Otherwise, when the amplitude is larger than 2 pi, equilibrium is never reached and the boundary migrates indefinitely, which would cause the protrusions of two serrated parallel boundaries to impinge on each other, creating smaller equiaxed grains.

Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

Novel blue emitters based on pi-conjugated block copolymers

A series of new phenyl-based conjugated copolymers has been synthesized and investigated by vibrational and photoluminescence spectroscopy (PL). The materials are: poly( 1,4-phenylene-alt-3,6-pyridazine) (COP-PIR), poly(9,9-dioctylfluorene)-co-quaterphenylene (COP-PPP) and poly[(1,4-phenylene-alt-3,6-pyridazine)-co-(1,4-phenylene-alt-9,9-dioctylfluorene)] (COP-PIR-FLUOR), with 3.5% of fluorene. COP-PPP and COP-PIR-FLUOR have high fluorescence quantum yields in solution. Infrared and Raman spectra were used to check the chemical structure of the compounds. The copolymers exhibit blue emission ranging front 2.8 to 3.6 eV when excited at E(exc)=4.13 eV. Stokes-shift Values were estimated on pristine samples in their condensed state from steady-state PL-emission and PL-excitation spectra. They suggest a difference in the torsional angle between the molecular configuration of the polymer blocks at the absorption and PL transitions and also in the photoexcitation diffusion. Additionally, the time-resolved PL of these materials has been investigated by using 100 fs laser pulses at E(exc)=4.64 eV and a streak camera. Results show very fast biexponential kinetics for the two fluorene-based polymers with decay times below 300 ps indicating both intramolecular, fast radiative recombination and migration of photogenerated electron-hole pairs. By contrast, the PL of COP-PIR is less intense and longer lived, indicating that excitons are confined to the chains in this polymer. (C) 2008 Elsevier B.V. All rights reserved.

Ipolamiide and fulvoipolarniide from Stachytarpheta glabra (Verbenaceae): A structural and spectroscopic characterization

The phenylethanoid glycoside acteoside and the iridoids ipolamiide and 4-methoxycarbonyl-7-methylcyclopenta[c]pyran (fulvoipolamiide) were isolated from the leaves of Stachytarpheta glabra. The solid state structure of fulvoipolamiide was confirmed by X-ray diffraction studies. The molecules of fulvoipolamiide are displayed in layers parallel to the crystallographic axis a. This molecule is planar with electron delocalization in the fused ring system and the pyran rings of adjacent layers in the solid state structure are involved in a pi-pi stacking interaction. Raman spectroscopy has also been used to characterize the most important bands present in the spectra of fulvoipolamiide and ipolamiide, and comparison made with literature allows the assignment of some key markers, specially the bands in the 1600-1700 cm(-1) range. (C) 2007 Elsevier B.V. All rights reserved.

An extension of the Pitzer equation for the excess Gibbs energy of aqueous electrolyte systems to aqueous polyelectrolyte solutions

Pitzer`s equation for the excess Gibbs energy of aqueous solutions of low-molecular electrolytes is extended to aqueous solutions of polyelectrolytes. The model retains the original form of Pitzer`s model (combining a long-range term, based on the Debye-Huckel equation, with a short-range term similar to the virial equation where the second osmotic virial coefficient depends on the ionic strength). The extension consists of two parts: at first, it is assumed that a constant fraction of the monomer units of the polyelectrolyte is dissociated, i.e., that fraction does not depend on the concentration of the polyelectrolyte, and at second, a modified expression for the ionic strength (wherein each charged monomer group is taken into account individually) is introduced. This modification is to account for the presence of charged polyelectrolyte chains, which cannot be regarded as punctual charges. The resulting equation was used to correlate osmotic coefficient data of aqueous solutions of a single polyelectrolyte as well as of binary mixtures of a single polyelectrolyte and a salt with low-molecular weight. It was additionally applied to correlate liquid-liquid equilibrium data of some aqueous two-phase systems that might form when a polyelectrolyte and another hydrophilic but neutral polymer are simultaneously dissolved in water. A good agreement between the experimental data and the correlation result is observed for all investigated systems. (c) 2008 Elsevier B.V. All rights reserved.

Collaboration intensity in the Brazilian supermarket retail chain

Purpose - This paper seeks to identify collaboration elements and evaluate their intensity in the Brazilian supermarket retail chain, especially the manufacturer-retailer channel. Design/methodology/approach - A structured questionnaire was elaborated and applied to 125 representatives from suppliers of large supermarket chains. Statistical methods including multivariate analysis were employed. Variables were grouped and composed into five indicators (joint actions, information sharing, interpersonal integration, gains and cost sharing, and strategic integration) to assess the degree of collaboration. Findings - The analyses showed that the interviewees considered interpersonal integration to be of greater importance to collaboration intensity than the other integration factors, such as gain or cost sharing or even strategic integration. Research limitations/implications - The research was conducted solely from the point of view of the industries that supply the large retail networks. The interviews were not conducted in pairs; that is, there was no application of one questionnaire to the retail network and another to the partner industry. Practical implications - Companies should invest in conducting periodic meetings with their partners to increase collaboration intensity, and should carry out technical visits to learn about their partners` logistic reality and thus make better operational decisions. Originality/value - The paper reveals which indicators produce greater collaboration intensity, and thus those that are more relevant to more efficient logistics management.

Understanding the strategies of late-movers in International Manufacturing

This paper analyzes the internationalization of new multinationals from emerging countries. It also focuses on Production`s role in firm internationalization, a subject seldom addressed because the discipline of International Manufacturing is still embryonic, while International Business tends to overlook production. The authors integrate International Business and International Manufacturing concepts and frameworks in order to analyze new multinationals from emerging countries, using the empirical evidence of a survey plus case studies of Brazilian multinationals for understanding late-movers` strategies and competences, with emphasis on production. (C) 2009 Elsevier B.V. All rights reserved.

Backside contact effect on the morphological and optical features of porous silicon photonic crystals

The present work reports on the effect of the type of backside contact used in the electrochemical process and their relation with the structural features and optical responses of the one-dimensional photonic crystal (PC) anodized in simple and double electrochemical cell. The PC, obtained in the single cell, showed to have thicker layers than of the PC obtained in double electrochemical cell. Additionally, the PC obtained in double cell showed highest reflectance in the band gap region than of the PCs obtained in single cell. These results suggest that the interface roughness between adjacent layers in the PC devices obtained in double electrochemical cell is minimized. (C) 2008 Elsevier Ltd. All rights reserved.

Optimized network structure for full-synchronization

A network of Kuramoto oscillators with different natural frequencies is optimized for enhanced synchronizability. All node inputs are normalized by the node connectivity and some important properties of the network Structure are determined in this case: (i) optimized networks present a strong anti-correlation between natural frequencies of adjacent nodes: (ii) this anti-correlation should be as high as possible since the average path length between nodes is maintained as small as in random networks: and (iii) high anti-correlation is obtained without any relation between nodes natural frequencies and the degree of connectivity. We also propose a network construction model with which it is shown that high anti-correlation and small average paths may be achieved by randomly rewiring a fraction of the links of a totally anti-correlated network, and that these networks present optimal synchronization properties. (C) 2008 Elsevier B.V. All rights reserved.

Singular Perturbation for the Discounted Continuous Control of Piecewise Deterministic Markov Processes

This paper deals with the expected discounted continuous control of piecewise deterministic Markov processes (PDMP`s) using a singular perturbation approach for dealing with rapidly oscillating parameters. The state space of the PDMP is written as the product of a finite set and a subset of the Euclidean space a""e (n) . The discrete part of the state, called the regime, characterizes the mode of operation of the physical system under consideration, and is supposed to have a fast (associated to a small parameter epsilon > 0) and a slow behavior. By using a similar approach as developed in Yin and Zhang (Continuous-Time Markov Chains and Applications: A Singular Perturbation Approach, Applications of Mathematics, vol. 37, Springer, New York, 1998, Chaps. 1 and 3) the idea in this paper is to reduce the number of regimes by considering an averaged model in which the regimes within the same class are aggregated through the quasi-stationary distribution so that the different states in this class are replaced by a single one. The main goal is to show that the value function of the control problem for the system driven by the perturbed Markov chain converges to the value function of this limit control problem as epsilon goes to zero. This convergence is obtained by, roughly speaking, showing that the infimum and supremum limits of the value functions satisfy two optimality inequalities as epsilon goes to zero. This enables us to show the result by invoking a uniqueness argument, without needing any kind of Lipschitz continuity condition.

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

This work investigates the formation of self-assembled monolayers (SAMs) of cystamine and cystamine-glutaraldehyde on a screen-printed electrode, and the immobilization of the Tc85 protein (from Trypanosoma cruzi) on these monolayers. The methods used included infrared techniques, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical studies were performed at pH 6.9 in 0.1 mol L(-1) phosphate buffer solution containing Fe(CN)(6)(-3/-4) redox species. The surface coverage (0) of the electrode was 0.10 (cystamine), 0.35 (cystamine-glutaraldehyde) and 0.84 (Tc85). Interpretation of electrochemical impedance spectroscopy results was based on a charge-transfer reaction involving Fe(CN)(6)(-3/-4) species at high frequencies, followed by a diffusion through the monolayers at lower frequencies. Estimates of the electrode surface coverage, active site radius, and distance between two adjacent sites assumed that charge transfer occurred at the active sites, and that there was a planar diffusion of redox species to these sites. (C) 2009 Elsevier B.V. All rights reserved.