Preparation, Characterisation and Catalytic Behaviour of a New TeVMoO Crystalline Phase

TeM_xMo_1.7O mixed oxides (M = V and/or Nb; x = 0-1.7) have been prepared by calcination of the corresponding salts at 600 °C in an atmosphere of N₂. A new crystalline phase, with a Te/V/Mo atomic ratio of 1/0.2-1.5/1.7, has been isolated and characterised by XRD and IR spectroscopy. This phase is observed in the TeVMo or TeVNbMo mixed oxide but not in the TeNbMo mixed oxide. The new crystalline phase shows an XRD pattern similar to Sb₄Mo₁₀O₃₁ and probably corresponds to the M1 phase recently proposed by Aouine et al. (Chem. Commun. 1180, 2001) to be present in the active and selective MoVTeNbO catalysts. Although these catalysts present a very low activity in the propane oxidation, they are active and selective in the oxidation of propene to acrolein and/or acrylic acid. However, the product distribution depends on the catalyst composition. Acrolein or acrylic acid can be selectively obtained from propene on Nb-free or Nb-containing TeVMo catalysts, respectively. The presence of both V and Nb, in addition to Mo and Te, appears to be important in the formation of acrylic acid from propene.     

Comparison of supports for the direct synthesis of hydrogen peroxide from H2 and O2 using Au–Pd catalysts

The direct synthesis of hydrogen peroxide from H₂ and O₂ using a range of supported Au–Pd alloy catalysts is compared for different supports using conditions previously identified as being optimal for hydrogen peroxide synthesis, i.e. low temperature (2 °C) using a water–methanol solvent mixture and short reaction time. Five supports are compared and contrasted, namely Al₂O₃, -Fe₂O₃, TiO₂, SiO₂ and carbon. For all catalysts the addition of Pd to the Au only catalyst increases the rate of hydrogen peroxide synthesis as well as the concentration of hydrogen peroxide formed. Of the materials evaluated, the carbon-supported Au–Pd alloy catalysts give the highest reactivity. The results show that the support can have an important influence on the synthesis of hydrogen peroxide from the direct reaction. The effect of the methanol–water solvent is studied in detail for the 2.5 wt% Au–2.5 wt% Pd/TiO₂ catalyst and the ratio of methanol to water is found to have a major effect on the rate of hydrogen peroxide synthesis. The optimum mixture for this solvent system is 80 vol.% methanol with 20 vol.% water. However, the use of water alone is still effective albeit at a decreased rate. The effect of catalyst mass was therefore also investigated for the water and water–methanol solvents and the observed effect on the hydrogen peroxide productivity using water as a solvent is not considered to be due to mass transfer limitations. These results are of importance with respect to the industrial application of these Au–Pd catalysts.     

Solving identity delegation problem in the e-government environment

At present, many countries allow citizens or entities to interact with the government outside the telematic environment through a legal representative who is granted powers of representation. However, if the interaction takes place through the Internet, only primitive mechanisms of representation are available, and these are mainly based on non-dynamic offline processes that do not enable quick and easy identity delegation. This paper proposes a system of dynamic delegation of identity between two generic entities that can solve the problem of delegated access to the telematic services provided by public authorities. The solution herein is based on the generation of a delegation token created from a proxy certificate that allows the delegating entity to delegate identity to another on the basis of a subset of its attributes as delegator, while also establishing in the delegation token itself restrictions on the services accessible to the delegated entity and the validity period of delegation. Further, the paper presents the mechanisms needed to either revoke a delegation token or to check whether a delegation token has been revoked. Implications for theory and practice and suggestions for future research are discussed.     

A geostatistical algorithm to reproduce lateral gradual facies transitions: Description and implementation

Valid representations of geological heterogeneity are fundamental inputs for quantitative models used in managing subsurface activities. Consequently, the simulation of realistic facies distributions is a significant aim. Realistic facies distributions are typically obtained by pixel-based, object-based or process-based methods. This work presents a pixel-based geostatistical algorithm suitable for reproducing lateral gradual facies transitions (LGFT) between two adjacent sedimentary bodies. Lateral contact (i.e. interfingering) between distinct depositional facies is a widespread geometric relationship that occurs at different scales in any depositional system. The algorithm is based on the truncation of the sum of a linear expectation trend and a random Gaussian field, and can be conditioned to well data. The implementation introduced herein also includes subroutines to clean and geometrically characterize the obtained LGFT. The cleaned sedimentary body transition provides a more appropriate and realistic facies distribution for some depositional settings. The geometric measures of the LGFT yield an intuitive measure of the morphology of the sedimentary body boundary, which can be compared to analogue data. An example of a LGFT obtained by the algorithm presented herein is also flow simulated, quantitatively demonstrating the importance of realistically reproducing them in subsurface models, if further flow-related accurate predictions are to be made.     

Game theoretical pattern recognition: application to imperfect noncooperative learning and to multiclass classification

This paper studies in theory, and gives a solution to, the following concerns which may eventually be simultaneous: 1) obtain alternative classification decisions, ranked by some decreasing order of class membership probabilities; 2) imperfect teacher at the learning stage, or effects of labeling errors due to unsupervised learning by clustering; 3) noncooperative teacher, manipulating the a priori class probabilities; 4) unknown a priori class probabilities. These requirements are taken into account by considering a game between the recognition system and the teacher, in a game theoretical framework. Both players will ultimately select ``mixed strategies,' which are probability distributions over the set of N alternative pattern classes, determined for each feature vector to be classified. This solution concept is interpreted in terms of the requirements 1)-4); numerical algorithms, as well as numerical examples are given with their solutions.     

Mechanical sensorless speed control of permanent-magnet AC motors driving an unknown load

A new sensorless scheme for high-performance speed control of permanent-magnet ac motors (PMACMs) driving an unknown load is proposed. This scheme uses an extended nonlinear reduced-order observer to estimate the induced electromotive force (EMF) and load torque. From the estimated variables, the rotor position, the rotor speed, and the position derivative of flux are calculated and are used to close the control loop. In order to improve the drive performance, the estimated load torque is incorporated as a feedforward signal in the closed control loop. In addition, the proposed sensorless PMACM drive allows the torque-ripple and copper-loss minimization for motors with an arbitrary EMF waveform. Simulation and experimental results to validate the proposal are presented in this paper.     

Feedback linearization via state transformation using estimated states

This paper deals with the exact feedback linearization of nonlinear plants using estimated states. Under appropriate hypotheses, exact linearization can be achieved through transformation of states and feedback. We assume that the states cannot be measured so that a nonlinear observer, with exponential convergence, is included in the loop. We establish sufficient conditions to guarantee that the overall system trajectories asymptotically converge to those obtained with feedback linearization utilizing the true states. We apply our results to control an electrical drive using a permanent-magnet synchronous motor without mechanical and optical sensors. The behaviour of our control scheme is illustrated by simulations.     

Analyzing locality over a P2P computing architecture

A characteristic of Peer-to-Peer (P2P) computing networks is their huge number of different computational resources scattered across the Internet. Gathering peers into markets according to their multi-attribute computational resources makes it easier to manage these environments. This solution is known as market overlay. In this context, the closeness of the markets with similar resources, known as locality, is a key feature for ensuring good P2P resource management. Thus, the locality feature over a market overlay allows a lack of resources in a given market to be compensated quickly by any other market with similar resources, whenever these are close to each other. Consequently, locality becomes an essential challenge.This paper addresses the analysis of the locality of P2P market over-lays. According to this, a new procedure for measuring locality is applied together with an extensive analysis of some well-known structured P2P overlays. Based on this analysis, a new P2P computing architecture, named DisCoP, oriented towards optimizing locality is proposed. Our proposal gathers the peers into markets according to their computational resources. A Hilbert function is used to arrange multi-attribute markets in an ordered and mono-dimensional space and the markets are linked by means of a Bruijn graph. In order to maintain the DisCoP locality whenever the overlay is not completed, a solution based on the virtualization of markets is also proposed. Finally, the DisCoP locality is tested together with the proposed virtualization method for approximate searches over uncompleted overlays. The simulation results show that approximate searches exploit the DisCoP locality efficiently.