Parameter estimation for a morphochemical reaction-diffusion model of electrochemical pattern formation

The process of electrodeposition can be described in terms of a reaction-diffusion partial differential equation (PDE) system that models the dynamics of the morphology profile and the chemical composition. Here we fit such a model to the different patterns present in a range of electrodeposited and electrochemically modified alloys using PDE constrained optimization. Experiments with simulated data show how the parameter space of the model can be divided into zones corresponding to the different physical patterns by examining the structure of an appropriate cost function. We then use real data to demonstrate how numerical optimization of the cost function can allow the model to fit the rich variety of patterns arising in experiments. The computational technique developed provides a potential tool for tuning experimental parameters to produce desired patterns.     

A simple model for deep dynamic stall conditions

The present study is focused on modeling of dynamic stall behavior of a pitching airfoil. The deep stall regime is in particular considered. A model is proposed, which has a low implementation and computational complexity but yet is able to deal with different types of dynamic stall conditions, including those characterized by multiple vortex shedding at the airfoil leading edge. The proposed model is appraised against an extensive data set of experimental (α,C_L) curves for NACA0012. The results of an existing widely used model, having comparable complexity, are also shown for comparison. The proposed model is able to well reproduce not only the classic curves of deep dynamic stall but also the curves characterized by lift oscillations at high angles of attack due to the shedding of multiple vortices. Furthermore, the model appears to be robust to variations of its parameters from the optimal values and of the airfoil geometry. Finally, the model is successfully implemented in a commercial CFD software and applied to the simulation of a vertical axis wind turbine within the actuator cylinder approach. The accuracy of the prediction of the turbine power coefficient in the whole rotation cycle is very good for the optimal working condition of the turbine, for which the model parameters were calibrated. Fairly good accuracy is also obtained in significantly different working conditions without any further calibration.     

QoS assessment of 3G video-phone calls by tracing watermarking exploiting the new colour space `YST?

Tracing watermarking has been recently proposed as a technique to provide a blind measure of the quality of service of the communication link, focusing on multimedia communication scenarios. 3G communication scenarios, where each customer transmits both voice and MPEG-4 video sequences in real time, have been considered. Typical video-phone call consists of close shots of speakers, framing their face in the foreground. For such particular application, a novel colour space (YST) is adopted to minimise the perceptual distortions on face coding introduced by watermarking. In the YST space, the luminance component (Y) is the same as in conventional YUV space, whereas the vectors S and T lie within the chrominance (UV) plane. The S (skin) component is a linear combination of U and V obtained as the 'average' chrominance estimated from an assorted set human faces to achieve a reasonable generalisation. The third component, T, is defined as orthogonal to the YS plane. The results show the benefits obtained in digital watermarking by the new representation against the conventional approach. In fact, the sensitivity of the YST representation outperforms the conventional one in terms of objective (mean square error, peak signal-to-noise ratio) and subjective (video-quality metrics) indicators.     

A comparison of the shake test, optical density, L/S ratio (planimetric and stechiometric) and PG for the assessment of fetal lung maturity

Our aim was to determine the diagnostic accuracy and reliability of four tests for the assessment of fetal lung maturity (FLM): shake test, optical density at 650 nm (OD650), lecithin to sphingomyelin ratio (L/S) by planimetry and stechiometry, and presence of phosphatydylglycerol. Amniotic fluid was obtained from 74 patients at various gestational ages. The shake test and the OD650 were performed according to published methods L/S was determined by TLC (thin-layer chromatography) and the ratio assessed by planimetry and stechiometrically by measurement of organic phosphorus from the chromatographic spots. PG was assessed similarly by TLC. When correlated with gestational age at amniocentesis, all tests correlated positively: shake test (r = 0.46, p < 0.005); OD650 (r = 0.31, p < 0.005); planimetric L/S (r = 0.77, p < 0.005); stechiometric L/S (r = 0.52, p < 0.005) and PG (r = 0.54, p < 0.005). The diagnostic accuracy of each test was as follows: the shake test and the OD650 had a sensitivity of 50%, while the steciometric L/S had a sensitivity of 75%, the planimetric L/S and the presence of PG were 100%. All four tests demonstrated a specificity greater than 64%, the highest for the PG presence being (83%) and the shake test (86%). Predictive negative values for lung maturity were > 93% for all tests, with the highest for the planimetric L/S and presence of PG being (100%). The study confirms that the determination of L/S ratio is still superior to other tests in terms of overall diagnostic accuracy. In addition, it was found that presence of PG was highly associated with the absence of respiratory complications in the newborn.     

The effect of support morphology on the reaction of oxidative dehydrogenation of ethane to ethylene at short contact times

The oxidative dehydrogenation of ethane is carried out in short contact time reactors over Pt and LaMnO₃ based catalysts supported on a large number of different ceramic substrates (45, 60 and 80 ppi foam monoliths and 200, 400, 600, 900 and 1200 cpsi honeycomb monoliths). Experimental results, obtained under the same conditions at varying the C₂H₆/O₂ ratio, showed that the highest performance in terms of ethylene selectivity and yield is always attained on LaMnO₃ catalysts. Furthermore, the results are significantly influenced by the morphology and cell density of the support, with 45 and 60 ppi foams and 400 and 600 cpsi honeycombs giving the best performance. The experimental results are explained by means of geometrical and fluid dynamic considerations on the support, and by means of a 2D mathematical model, which clearly indicates an optimal intermediate cell density for maximising ethylene selectivity and yield.     

SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

Necessary conditions for asymptotic tracking in nonlinear systems

In the literature, it has been shown that if a single-input single-output analytic nonlinear plant 1) has a well-defined relative degree and 2) is minimum-phase, it is possible to achieve asymptotic tracking for an open set of output trajectories containing the origin in C^N [0, ∞), the space of N-times continuously differentiable functions taking values in R. When either of these sufficient conditions is not met, various authors have investigated approximate analytic solutions, discontinuous solutions and solutions for restricted sets of trajectories. In this paper, it is shown that conditions 1) and 2) are necessary for the existence of an analytic compensator which yields asymptotic tracking for an open set of output trajectories. Analogous results are established for multi-input multi-output systems     

On the observation of inductive high-frequency impedance behaviour during the electrodeposition of Au—Sn alloys

Inductive high-frequency impedance behaviour is often observed in metal electrodeposition systems. This behaviour is typically attributed to equipment limitations or non-idealities in the cell set-up and electrical connections. Such instrumental artefacts would nevertheless be relevant to a frequency range which is expected to be well above that in which inductive behaviour is in fact observed (down to a few tens of Hz). In this paper some results on an acidic Au—Sn electrodeposition system are reported. Electrochemical impedance and potentiostatic transients were measured. These results suggest that the high-frequency inductive behaviour may be related to metal nucleation processes. A correlation is proposed between the pseudo-inductive potentiostatic nucleation transients and the pseudo-inductive behaviour of the impedance spectra.     

Precipitation from glassy polymer solutions

Solid solutions of general-purpose polystyrene containing crystalline tetrabromoxylene, tetrachloroxylene, or tetrachlorobenzene were prepared. The effects of the low molecular weight crystalline additive concentration and the thermal history on the thermal properties of the system have been studied. The system solubility, rejection of solute, etc., were characterized by such techniques as rheology, thermal analysis (DSC), and Vicat softening point.