206 resultados para Exclusive processes


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The electrochemistry of Pt nanostructured electrodes is investigated using hydrodynamic modulated voltammetry (HMV). Here a liquid crystal templating process is used to produce platinum-modified electrodes with a range of surface areas (roughness factor 42.4-280.8). The electroreduction of molecular oxygen at these nanostructured platinum surfaces is used to demonstrate the ability of HMV to discriminate between faradaic and nonfaradaic electrode reactions. The HMV approach shows that the reduction of molecular oxygen experiences considerable signal loss within the high pseudocapacitive region of the voltammetry. Evidence for the contribution of the double layer to transient mass transfer events is presented. In addition, a model circuit and appropriate theoretical analysis are used to illustrate the transient responses of a time variant faradaic component. This in conjunction with the experimental evidence shows that, far from being a passive component in this system, the double layer can contribute to HMV faradaic reactions under certain conditions.

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Increasingly, the UK’s Private Finance Initiative has created a demand for construction companies to transfer knowledge from one organization or project to another. Knowledge transfer processes in such contexts face many challenges, due to the many resulting discontinuities in the involvement of organisations, personnel and information flow. This paper empirically identifies the barriers and enablers that hinder or enhance the transfer of knowledge in PFI contexts, drawing upon a questionnaire survey of construction firms. The main findings show that knowledge transfer processes in PFIs are hindered by time constraints, lack of trust, and policies, procedures, rules and regulations attached to the projects. Nevertheless, the processes of knowledge transfer are enhanced by emphasising the value and importance of a supportive leadership, participation/commitment from the relevant parties, and good communication between the relevant parties. The findings have considerable relevance to understanding the mechanism of knowledge transfer between organizations, projects and individuals within the PFI contexts in overcoming the barriers and enhancing the enablers. Furthermore, practitioners and managers can use the findings to efficiently design knowledge transfer frameworks that can be used to overcome the barriers encountered while enhancing the enablers to improve knowledge transfer processes.

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Two different ways of performing low-energy electron diffraction (LEED) structure determinations for the p(2 x 2) structure of oxygen on Ni {111} are compared: a conventional LEED-IV structure analysis using integer and fractional-order IV-curves collected at normal incidence and an analysis using only integer-order IV-curves collected at three different angles of incidence. A clear discrimination between different adsorption sites can be achieved by the latter approach as well as the first and the best fit structures of both analyses are within each other's error bars (all less than 0.1 angstrom). The conventional analysis is more sensitive to the adsorbate coordinates and lateral parameters of the substrate atoms whereas the integer-order-based analysis is more sensitive to the vertical coordinates of substrate atoms. Adsorbate-related contributions to the intensities of integer-order diffraction spots are independent of the state of long-range order in the adsorbate layer. These results show, therefore, that for lattice-gas disordered adsorbate layers, for which only integer-order spots are observed, similar accuracy and reliability can be achieved as for ordered adsorbate layers, provided the data set is large enough.

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A new surface-crossing algorithm suitable for describing bond-breaking and bond-forming processes in molecular dynamics simulations is presented. The method is formulated for two intersecting potential energy manifolds which dissociate to different adiabatic states. During simulations, crossings are detected by monitoring an energy criterion. If fulfilled, the two manifolds are mixed over a finite number of time steps, after which the system is propagated on the second adiabat and the crossing is carried out with probability one. The algorithm is extensively tested (almost 0.5 mu s of total simulation time) for the rebinding of NO to myoglobin. The unbound surface ((FeNO)-N-...) is represented using a standard force field, whereas the bound surface (Fe-NO) is described by an ab initio potential energy surface. The rebinding is found to be nonexponential in time, in agreement with experimental studies, and can be described using two time constants. Depending on the asymptotic energy separation between the manifolds, the short rebinding timescale is between 1 and 9 ps, whereas the longer timescale is about an order of magnitude larger. NO molecules which do not rebind within 1 ns are typically found in the Xenon-4 pocket, indicating the high affinity of NO to this region in the protein.

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The thoughtful construction of molecular switches has led to a gamut of supramolecular systems that can be used in molecular electronics. These include molecules based on thienylethenes, spiropyrans, fulgides, dithienylphenanthrolines, and diazafluorenes. This article reviews the recent developments made in the synthesis and characterization of all these systems, thereby allowing a comparative study to validate the viability of these switchable molecules on a nanoscale. Also, the drawbacks of each class are demonstrated and, at the same time, the remedies for further improvisation are prescribed. We have made an honest attempt to present at? exhaustive account of all the different photochromic switches developed by us hitherto.

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Symmetrical behaviour of the covariance matrix and the positive-definite criterion are used to simplify identification of single-input/single-output systems using recursive least squares. Simulation results are obtained and these are compared with ordinary recursive least squares. The adaptive nature of the identifier is verified by varying the system parameters on convergence.

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Successful knowledge transfer is an important process which requires continuous improvement in today’s knowledge-intensive economy. However, improving knowledge transfer processes represents a challenge for construction practitioners due to the complexity of knowledge acquisition, codification and sharing. Although knowledge transfer is context based, understanding the critical success factors can lead to improvements in the transfer process. This paper seeks to identify and evaluate the most significant critical factors for improving knowledge transfer processes in Public Private Partnerships/Private Finance Initiatives (PPP/PFI) projects. Drawing upon a questionnaire survey of 52 construction firms located in the UK, data is analysed using Severity Index (SI) and Coefficient of Variation (COV), to examine and identify these factors in PPP/PFI schemes. The findings suggest that a supportive leadership, participation/commitment from the relevant parties, and good communication between the relevant parties are crucial to improving knowledge transfer processes in PFI schemes. Practitioners, managers and researchers can use the findings to efficiently design performance measures for analysing and improving knowledge transfer processes.

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A common problem in many data based modelling algorithms such as associative memory networks is the problem of the curse of dimensionality. In this paper, a new two-stage neurofuzzy system design and construction algorithm (NeuDeC) for nonlinear dynamical processes is introduced to effectively tackle this problem. A new simple preprocessing method is initially derived and applied to reduce the rule base, followed by a fine model detection process based on the reduced rule set by using forward orthogonal least squares model structure detection. In both stages, new A-optimality experimental design-based criteria we used. In the preprocessing stage, a lower bound of the A-optimality design criterion is derived and applied as a subset selection metric, but in the later stage, the A-optimality design criterion is incorporated into a new composite cost function that minimises model prediction error as well as penalises the model parameter variance. The utilisation of NeuDeC leads to unbiased model parameters with low parameter variance and the additional benefit of a parsimonious model structure. Numerical examples are included to demonstrate the effectiveness of this new modelling approach for high dimensional inputs.

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This paper presents a controller design scheme for a priori unknown non-linear dynamical processes that are identified via an operating point neurofuzzy system from process data. Based on a neurofuzzy design and model construction algorithm (NeuDec) for a non-linear dynamical process, a neurofuzzy state-space model of controllable form is initially constructed. The control scheme based on closed-loop pole assignment is then utilized to ensure the time invariance and linearization of the state equations so that the system stability can be guaranteed under some mild assumptions, even in the presence of modelling error. The proposed approach requires a known state vector for the application of pole assignment state feedback. For this purpose, a generalized Kalman filtering algorithm with coloured noise is developed on the basis of the neurofuzzy state-space model to obtain an optimal state vector estimation. The derived controller is applied in typical output tracking problems by minimizing the tracking error. Simulation examples are included to demonstrate the operation and effectiveness of the new approach.

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In 1967 a novel scheme was proposed for controlling processes with large pure time delay (Fellgett et al, 1967) and some of the constituent parts of the scheme were investigated (Swann, 1970; Atkinson et al, 1973). At that time the available computational facilities were inadequate for the scheme to be implemented practically, but with the advent of modern microcomputers the scheme becomes feasible. This paper describes recent work (Mitchell, 1987) in implementing the scheme in a new multi-microprocessor configuration and shows the improved performance it provides compared with conventional three-term controllers.

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The processes that govern the predictability of decadal variations in the North Atlantic meridional overturning circulation (MOC) are investigated in a long control simulation of the ECHO-G coupled atmosphere–ocean model. We elucidate the roles of local stochastic forcing by the atmosphere, and other potential ocean processes, and use our results to build a predictive regression model. The primary influence on MOC variability is found to come from air–sea heat fluxes over the Eastern Labrador Sea. The maximum correlation between such anomalies and the variations in the MOC occurs at a lead time of 2 years, but we demonstrate that the MOC integrates the heat flux variations over a period of 10 years. The corresponding univariate regression model accounts for 74.5% of the interannual variability in the MOC (after the Ekman component has been removed). Dense anomalies to the south of the Greenland-Scotland ridge are also shown to precede the overturning variations by 4–6 years, and provide a second predictor. With the inclusion of this second predictor the resulting regression model explains 82.8% of the total variance of the MOC. This final bivariate model is also tested during large rapid decadal overturning events. The sign of the rapid change is always well represented by the bivariate model, but the magnitude is usually underestimated, suggesting that other processes are also important for these large rapid decadal changes in the MOC.