Ethanol combustion over strontium- and cerium-doped LaCoO3 catalysts

Ce- or Sr-doped LaCoO₃ bulk perovskites were prepared by citric acid method as well as 10 wt.% of LaCoO₃ was deposited on alumina carrier stabilized with lanthanum. Properties of prepared materials were characterized by determination of surface area, acid-basic properties and XRD, XPS, TPDO₂, H₂-TPR measurements as well as catalytic activity and selectivity for ethanol combustion was tested. It was found that substitution of La in LaCoO₃ with either Sr or Ce has only small effect on its activity in ethanol combustion. Strontium inserted into LaCoO₃ structure increases basic character of the perovskite surface as well as selectivity to acetaldehyde (ACA). Substitution of La with cerium has no effect on the concentration of basic sites and does not affect the selectivity to ACA. Activity of LaCoO₃-based catalysts in ethanol combustion and their selectivity to ACA formation can be explained on the basis of the presence of both -oxygen species and sites with basic character on the material surface.

Acid-basic properties of supported LaCoO₃ are dominated by acidic character of the carrier. Results of XPS and H₂-TPR measurements of LaCoO₃ supported on La–Al₂O₃ suggest that perovskite remains in strong interaction with carrier and probably is partially decomposed. Deposition of perovskite on stabilized carrier significantly increases the rate of ethanol combustion.     

Defect structure and chemical diffusion in nickel sulfide β-Ni3S2

The chemical composition, defect structure, and diffusion in nickel sulfide -Ni₃S₂ have been investigated in H₂S-H₂ mixtures containing between 1 and 65% H₂S between 560 and 700°C. Gravimetric, density, and X-ray studies were carried out. In the thermodynamically stable compound the ratio of Ni/S varied between 1.3 and 1.75. The X-ray examination showed a step change in the lattice parameter at the Ni/S ratio 1.4. A linear dependence of the density values (between 5.5 and 6.2 g/cm³) on the composition was observed. On the basis of the chemical composition and density measurements the number of nickel and sulfur atoms in 1 cm³ were determined. It has been shown that the Ni₃S₂ phase is defected in both anion and cation sublattices and that its chemical formula may be described as follows: Ni_3±yS_2x, where y 2x. It has been found that in the mixture containing 10% H₂S the process of defect formation is determined by their diffusion in the sulfide. The temperature dependence of the diffusion coefficient is described by the equation D = 13.15 exp(-30,000/RT) cm²/sec. No dependence of D on the sulfur partial pressure was observed, but this may be due to the relatively large uncertainties in the measurement of the diffusion coefficients.     

Kinetics of copper sulfidation at temperatures 570–1123 K

The kinetics of copper sulfidation have been studied as a function of temperature (570–1120 K) by the use of the modified Wagner's pellet method. It has been found that sulfidation follows a parabolic rate law with different activation energies in the low- and high-temperature ranges: $$k_{p}^{'} = 10.2 exp - (70 \pm 4)[kJ/mole]/RT (570 - 780 K)$$ and $$k_{p}^{'} = 1.69 \times 10^{ - 3} exp - (13 \pm 1.0)[kJ/mole]/RT (780 - 1120 K)$$ Using thermodynamic data as well as interfacial chemical potentials and ionic conductivity, the parabolic rate constants of sulfidation of copper have been calculated with good agreement with experimental results. Parabolic rate constants of sulfidation have been used to calculate average self-diffusion coefficients of copper in Cu₂S, the temperature dependence of which is as follows: $$\bar D_{Cu} = 8.76 \times 10^{ - 4} exp - (22.4 \pm 1)[kJ/mole]/RT$$      

A two‐level detector of short‐term unique changes in time series based on a similarity method

In the paper, a novel two‐level algorithm of time‐series change detection is presented. In the first level, to identify non‐stationary sequences in a processed signal, preliminary detection of events is performed with a short‐term prediction comparison. In the second stage, to confirm the changes detected in the first level, a similarity method aimed at identification of unique changes is employed. The detection of changes in a non‐stationary time series is discussed, implemented algorithms are described and the results produced on a sample four financial time series are shown. General conditions for implementing the proposed algorithm as an immune‐like event detector are discussed.     

Discrete time sliding mode control with reduced switching – a new reaching law approach

In this paper, a novel reaching law for discrete‐time variable structure systems is proposed. It ensures that the representative point (state) of the controlled plant approaches the switching plane in finite time and then crosses it in every subsequent step. Moreover, the proposed reaching law ensures that for the nominal plant the absolute value of the sliding variable asymptotically decreases to zero, and for the perturbed plant, it converges to a smaller interval around zero than with the application of previously proposed reaching laws. The control method proposed in this paper guarantees asymptotic stability of the nominal system and uniform ultimate boundedness of the perturbed one. Furthermore, the method ensures that the sliding variable rate of change (i.e. the difference between its values at any two subsequent sampling instants) is bounded by design parameters, which do not depend on the system initial conditions. This is a highly desirable property, as it results in a priori specified, ‘almost’ constant convergence rate of the sliding variable when the system state is far off the switching plane and helps enforce state constraints in the system. Copyright © 2014 John Wiley & Sons, Ltd.     

INSIGMA: an intelligent transportation system for urban mobility enhancement

Intelligent Transportation Systems (ITS) aim to improve safety, mobility and environmental performance of road transport. The INSIGMA project provides a fresh look at the possible innovations in this field, by enhancing the functionality and accuracy of ITS in urban environments. This paper describes the architecture, sensors, processing algorithms, output modules and advantages of the developed system. A comparison of existing ITS systems has been provided as background. Special attention has been given to performance and privacy issues, as the system includes social aspects such as location monitoring.     

Regular Languages of Thin Trees

An infinite tree is called thin if it contains only countably many infinite branches. Thin trees can be seen as intermediate structures between infinite words and infinite trees. In this work we investigate properties of regular languages of thin trees. Our main tool is an algebra suitable for thin trees. Using this framework we characterize various classes of regular languages: commutative, open in the standard topology, and definable in weak MSO logic among all trees. We also show that in various meanings thin trees are not as rich as all infinite trees. In particular we observe a collapse of the parity index to the level (1, 3) and a collapse of the topological complexity to co-analytic sets. Moreover, a gap property is shown: a regular language of thin trees is either weak MSO-definable among all trees or co-analytic-complete.     

Time and Energy Performance of Parallel Systems with Hierarchical Memory

In this paper we analyze the impact of memory hierarchies on time-energy trade-off in parallel computations. Contemporary computing systems have deep memory hierarchies with significantly different speeds and power consumptions. This results in nonlinear phenomena in the processing time and energy usage emerging when the size of the computation is growing. In this paper the nonlinear dependence of the time and energy on the size of the solved problem is formalized and verified using measurements in practical computer systems. Then it is applied to formulate a problem of minimum time and minimum energy scheduling parallel processing of divisible loads. Divisible load theory is a scheduling and performance model of data-parallel applications. Mathematical programming is exploited to solve the scheduling problem. A trade-off between energy and schedule length is analyzed and again nonlinear relationships between these two criteria are observed. Further performance analysis reveals that energy consumption and schedule length are ruled by a complex interplay between the costs and speeds of on-core and out-of-core computations, communication delays, and activating new machines.