Molecular simulation of temperature-programmed desorption

We use accelerated molecular dynamics to probe the thermal desorption of n-alkanes from the Au(1 1 1) and C(0 0 0 1) surfaces. Studying an alkane series ranging from CH₄ to C₁₆H₃₄, we find that the desorption prefactor increases with increasing chain length for the short chains until a certain chain length is reached when it becomes essentially constant and independent of chain length. We can understand the dependence of the preexponential factor on alkane chain length in terms of conformational changes within the alkane molecules. For the shorter molecules, the desorption temperatures probed in experimental temperature-programmed desorption studies lie below those for which torsional motion is activated. Thus, the short alkanes can be treated as rigid rods, and the loss in translational and rotational entropy upon adsorption leads to a preexponential factor that increases with increasing chain length. As the alkane chain length increases, the binding energy and the experimental desorption temperatures also increase. Thus, torsional motion is activated to an extent that increases with increasing chain length. This torsional activation increases the entropy of adsorption and counteracts the entropy decrease due to a loss of translation and rotation. This leads to a virtually constant prefactor for sufficiently long chains. Our findings are consistent with experimental data for the thermal desorption of alkanes from the Au(1 1 1), Pt(1 1 1), MgO(1 0 0) and C(0 0 0 1) surfaces.     

On application of input data partitioning to Bayesian weighted averaging of biomedical signals

Averaging in the time domain may be used for noise attenuation in case of biomedical signals with a quasi‐cyclical character. Traditional arithmetic averaging technique assumes the constancy of the noise power cycle‐wise, however, most types of noise are not stationary and the variability of noise power is observed. It constitutes a motivation for using methods of weighted averaging, in particular Bayesian weighted averaging. This paper presents the computational study of Bayesian weighted averaging with traditional (sharp) and fuzzy partition of the input data in the presence of non‐stationary noise. There is presented the known empirical Bayesian weighted averaging method (EBWA), with the parameter p describing the probabilistic model, and its modification NBWA which eliminates the parameter. Both methods can be extended by partitioning of the input data. The performance of presented methods is experimentally evaluated for an analytical signal as well as a real ECG signal and compared with traditional arithmetic averaging method. However, the methods can be applied to any signal with a quasi‐cyclical character. The aim of the paper is to show the influence of the type of partition as well as the number of parts on the quality of the averaged signal.     

Synthetic adipic complex tetraesters as eco‐friendly lubricants

The paper presents results concerning the synthesis and characterisation as lubricants with biodegradability potential of some complex tetraesters realised on the basis of adipic acid and different glycols such as (mono) ethylene, 1,3‐propylene, 1,4‐butylene, 1,5‐pentamethylene, 1,6‐hexamethylene, diethylene and triethylene glycol, respectively, along with oleic acid used, considered as an end, final segment or as a capping element. On the basis of a regular alternation or successive distribution principle of the polar and nonpolar chemical functions equally distributed, shared out on the length of a sufficient, satisfactorily long, large molecule, valuable synthetic complex tetraester lubricants considered as eco‐friendly base oils with biodegradability potential were performed. These products showed very good tribological properties, such as high viscosity indices and high flash points, and also very good lubricity features. Copyright © 2013 John Wiley & Sons, Ltd.     

An investigation into the surface fatigue of materials and thin layers using a sliding diamond spherical segment

Methods for testing the surface fatigue of materials or thin layers normally involve configurations with two or more rolling balls or discs. Such equipment and test specimens are quite complicated, and for a large number of experiments, costly. Testing could be considerably simplified if the stressing of the material surface were performed with a sliding natural diamond spherical segment. A diamond on steel (or any different material) friction pair has the particular attribute that sliding wear is absent. Under these circumstances, after a certain number of strain cycles, fatigue failure of the investigated surface or layers appears. A particularly relevant application is investigation of the adhesion of a DLC layer.     

A comparison of three turbulence models for the prediction of parallel lobed jets in perforated panel optimization

The general context of the present study is the design of high induction HVAC air diffusers by means of passive jet control. When the diffuser is a perforated panel with lobed orifices (Meslem et al. 2010), the optimization of jet induction consists in improving the orifice’s geometry, the spacing between orifices and their arrangement on the panel. In this study, the flow field of a turbulent twin cross-shaped jet is investigated numerically using the standard k-ε model, the Shear Stress Transport (SST) k-ω model and the Reynolds Stress Model (RSM). The results are compared with PIV measurements. The objective is to assess their capability and limitations to predict the significant features of twin jet flow when the flow is numerically resolved through a lobed diffuser. It is shown that the k-ε and RSM models are more appropriate for predicting potential jet core length, the change in jet centreline streamwise velocity, and flow expansion in the symmetry plane of the twin jet flow. However, these models overestimate the overall flow expansion and the jet volumetric flow rate. The SST k-ω model seems more appropriate for the prediction of such dynamic integral quantities. A high level of turbulent kinetic energy predicted by the k-ε and RSM models in the near field of jets is probably the reason for this overestimation of jet induction. The SST k-ω model would appear to be the most appropriate tool for optimizing orifice design, orifice to orifice spacing and relative orifice orientation on a perforated panel diffuser.     

Urban spatial pattern as self-organizing system: An empirical evaluation of firm location decisions in Cleveland–Akron PMSA,Ohio

Economic models of urban spatial patterns have largely ignored complexity as an attribute of urban systems. Complexity theorists on the other hand have not made sufficiently serious and sustained attempts to verify empirically the relevance of complex systems models for urban spatial patterns. This research bridges this gap by simulating the evolution of an urban employment pattern as a self-organizing complex system and seeking its empirical validation. It estimates the model’s parameters by using firm data aggregated to the level of municipalities in Cleveland-Akron Consolidated Metropolitan Statistical Area in Ohio. The interaction among four parameters, forces of attraction and dispersion and their respective rates of dissipation with distance, are modeled as a two-dimensional complex system. The research compares the states of the modeled system with empirical data to present viable methods for verification, calibration and validation of such models.

---

     

Improved Management of the Existing Stock - The Case of Poland

This paper traces the changes which have occurred in housing provision and management in Poland during the period of transition to the market system. It suggests that the changes that have occurred have been greatly influenced by the environment within which the reforms have taken place. It claims that changes in housing management are restricted by historic attitudes yet have proceeded due to financial constraints imposed as part of the government's policy for restructuring the economy in the early 1990s. At the same time these restrictions have worked against the developmentof the housing market and investment in the existing housing stock. While the planned programmaticand legislative tasks in the reform of Polish housing are concluded, there is still a need for major shifts in the attitudes of consumers and providers to effect these changes.     

Acetylcholinesterase voltammetric biosensors based on carbon nanostructure-chitosan composite material for organophosphate pesticides

A sensitive biosensor for chloropyrifos (CPF), an organophosphorus pesticide, was developed by immobilizing acetylcholinesterase (AChE) through covalent bonding to an oxidized exfoliated graphite nanoplatelet (xGnPs)–chitosan cross-linked composite. Because of the increased surface area and the conductive properties of the nanomaterial, AChE developed a high affinity for acetylthiocholine (ATCI) and formed thiocholine with a fast response. The response of the sensor was a linear function of ATCI concentration in two segments, one from 0.005 to 0.039 mM and the second from 0.064 mM to 0.258 mM. The corresponding equation for the first range was i_p(A) = 2.26 × 10^? 5c + 4.39 × 10^? 7 (R² = 0.992) and the equation for the second was i_p(A) = 6.80 × 10^? 6c + 1.30 × 10^? 6 (R² = 1.000), with a detection limit of 1.58 × 10^? 10 M. The fabrication of the sensor was simple, the response was fast and the stability acceptable. This sensor has many potential applications, the foremost being in organophosphorus pesticides.