Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q(10) of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Complex Oscillatory Response of a PEM Fuel Cell Fed with H(2)/CO and Oxygen

Oscillatory kinetics is commonly observed in the electrocatalytic oxidation of most species that can be used in fuel cell devices. Examples include formic acid, methanol, ethanol, ethylene glycol, and hydrogen/carbon monoxide mixtures, and most papers refer to half-cell experiments. We report in this paper the experimental investigation of the oscillatory dynamics in a proton exchange membrane (PEM) fuel cell at 30 degrees C. The system consists of a Pt/C cathode fed with oxygen and a PtRu (1:1)/C anode fed with H(2) mixed with 100 ppm of CO, and was studied at different cell currents and anode flow rates. Many different states including periodic and nonperiodic series were observed as a function of the cell current and the H(2)/CO flow rate. In general, aperiodic/chaotic states were favored at high currents and low flow rates. The dynamics was further characterized in terms of the relationship between the oscillation amplitude and the subsequent time required for the anode to get poisoned by carbon monoxide. Results are discussed in terms of the mechanistic aspects of the carbon monoxide adsorption and oxidation. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3463725] All rights reserved.

LEARNING A COMPLEX MOTOR SKILL FROM VIDEO AND POINT-LIGHT DEMONSTRATIONS

The aim of this Study was to compare the learning process of a highly complex ballet skill following demonstrations of point light and video models 16 participants divided into point light and video groups (ns = 8) performed 160 trials of a pirouette equally distributed in blocks of 20 trials alternating periods of demonstration and practice with a retention test a day later Measures of head and trunk oscillation coordination d1 parity from the model and movement time difference showed similarities between video and point light groups ballet experts evaluations indicated superiority of performance in the video over the point light group Results are discussed in terms of the task requirements of dissociation between head and trunk rotations focusing on the hypothesis of sufficiency and higher relevance of information contained in biological motion models applied to learning of complex motor skills

Experimental study of a Tollmien-Schlichting wave interacting with a shallow 3D roughness element

The paper is devoted to an experimental study of the effect of a shallow 3D roughness element on the evolution of a 2D Tollmien-Schlichting wave in a Blasius boundary layer. The experiments were carried out under controlled disturbance conditions on an airfoil section which could provide a long run with zero pressure gradient flow. A pneumatically driven slit source was used to introduce the Tollmien-Schilichting wave upstream of the lower branch of the neutral stability curve. A few wavelengths downstream, the T-S wave interacts with a cylindrical roughness element. The height of the roughness was slowly oscillating in time, which allows a continuous measurement of the T-S wave response downstream the roughness. The oscillation frequency was approximately 1500 times lower than the frequency of the studied Tollmien-Schlichting wave and therefore, behaved as a steady roughness with respect to the T-S wave. Hot wire anemometry was used to measure wall normal profiles and spanwise scans close to the maximum of the eigenfunction of the T-S wave. The oscillation of the roughness and the synchronization of all-equipments permitted the use of ensemble average techniques. Two different amplitudes of T-S waves with a non-dimensional frequency of F120E-06 were studied. They show a strong amplification of the disturbances in a small spanwise wave number range. The analysis of the wall normal T-S profiles suggests the growth of oblique modes.

Experimental investigation on the dynamic behaviour of a railway vehicle travelling through a turnout

Track critical locations with respect to the railway vehicle safety are the passages through the turnouts. The purpose of this investigation is to evaluate the safety of a railway vehicle crossing a turnout. In this study, the topography of a track turnout lay-out has been experimentally measured, and its geometric properties were synthesised. Results show that a constant wavelength vehicle oscillation occurs on the switches in the turnout and that the maximum lateral force at 65 km/h is almost 65% greater than those at low speeds (under 30 km/h).

Experimental investigation of flow-induced vibration on isolated and tandem circular cylinders fitted with strakes

The effect of varying the geometric parameters of helical strakes on vortex-induced vibration (VIV) is investigated in this paper. The degree of oscillation attenuation or even suppression is analysed for isolated circular cylinder cases. How a cylinder fitted with strakes behaves when immersed in the wake of another cylinder in tandem arrangement is also investigated and these results are compared to those with a single straked cylinder. The experimental tests are conducted at a circulating water channel facility and the cylindrical models are mounted on a low-damping air bearing elastic base with one degree-of-freedom, restricted to oscillate in the transverse direction to the channel flow. Three strake pitches (p) and heights (h) are tested: p = 5, 10, 15d, and h = 0.1, 0.2, 0.25d. The mass ratio is 1.8 for all models. The Reynolds number range is from 1000 to 10000, and the reduced velocity varies up to 21. The cases with h = 0.1d strakes reduce the amplitude response when compared to the isolated plain cylinder, however the oscillation still persists. On the other hand, the cases with h = 0.2, 0.25d strakes almost completely suppress VIV. Spanwise vorticity fields, obtained through stereoscopic digital particle image velocimetry (SDPIV), show an alternating vortex wake for the p = 10d and h = 0.1d straked cylinder. The p = 10d and h = 0.2d cylinder wake has separated shear layers with constant width and no roll-up close to the body. The strakes do not increase the magnitude of the out-of-plane velocity compared to the isolated plain cylinder. However, they deflect the flow in the out-of-plane direction in a controlled way, which can prevent the vortex shedding correlation along the span. In order to investigate the wake interference effect on the strake efficiency, an experimental arrangement with two cylinders in tandem is employed. The centre-to-centre distance for the tandem arrangement varies from 2 to 6. When the downstream p = 10d and h = 0.2d cylinder is immersed in the wake of an upstream fixed plain cylinder, it loses its effectiveness compared with the isolated case. Although the oscillations have significant amplitude, they are limited, which is a different behaviour from that of a tandem configuration with two plain cylinders. For this particular case, the amplitude response monotonically increases for all gaps, except one, a trait usually found in galloping-like oscillations. SDPIV results for the tandem arrangements show alternating vortex shedding and oscillatory wake. (C) 2010 Elsevier Ltd. All rights reserved.

Floquet stability analysis of the flow around an oscillating cylinder

This investigative work is concerned with the flow around a circular cylinder submitted to forced transverse oscillations. The goal is to investigate how the transition to turbulence is initiated in the wake for cases with different Reynolds numbers (Re) and displacement amplitudes (A). For each Re the motion frequency is kept constant, close to the Strouhal number of the flow around a fixed cylinder at the same Re. Stability analysis of two-dimensional periodic flows around a forced-oscillating cylinder is carried out with respect to three-dimensional infinitesimal perturbations. The procedure consists of performing a Floquet type analysis of time-periodic base flows, computed using the spectral/hp element method. With the results of the Floquet calculations, considerations regarding the stability of the system are drawn, and the form of the instability at its onset is obtained. The critical Reynolds number is observed to change with the amplitude of oscillation. With respect to instabilities, unstable modes with the same symmetry as mode A of a fixed cylinder are observed; however, they present different wavelengths. Also, the instabilities observed for the oscillating cylinder are distinctively stronger in the braid shear layers. Other unstable modes similar to mode B are found. Quasi-periodic modes are observed in the 2S wake, and subharmonic mode occurrences are reported in P + S wakes. (C) 2009 Elsevier Ltd. All rights reserved.

Experimental investigation of Vortex-Induced Vibration on rigid, smooth and inclined cylinders

This paper presents new experimental results of Vortex-Induced Vibration (VIV) on inclined cylinders. Models are mounted on a low damping air-bearing elastic base with one degree-of-freedom, constrained to oscillate only in the transverse direction to a free stream. The Reynolds number varied in the range 2000 less than or similar to Re less than or similar to 8000. New measurements on the dynamic response oscillations of inclined cylinders, due to VIV, are compared with previous experiments of a vertical cylinder. Models with circular and elliptical cross sections have been tested. The purpose of this work is to check the validity of the normal velocity correction of VIV studies of inclined structures. The results show that the reduced velocity range, in which the upper and lower branches of VIV occurs, is similar to the vertical cylinder case if the proper projected velocity is considered. Tests have been conducted to support this observation with inclinations up to 45 degrees. We have also observed that the amplitudes of oscillation of the inclined circular cylinder are comparable, but slightly lower than, to the amplitudes observed in the vertical cylinder experiments. Measured forces and added mass also show similar behaviour. However, for cases with an elliptical cylinder, the amplitudes of oscillation are considerably lower than those observed for a circular cylinder. This difference is explained by the higher added mass of the elliptical cylinder. (C) 2009 Elsevier Ltd. All rights reserved.

Mitigation of Vortex-Induced Motion, (VIM) on a Monocolumn Platform: Forces and Movements

A great deal of works has been developed on the spar vortex-induced motion (VIM) issue. There are, however, very few published works concerning VIM of monocolumn platforms, partly due to the fact that the concept is fairly recent and the first unit was only installed last year. In this context, a meticulous study on VIM for this type of platform concept is presented here. Model test experiments were performed to check the influence of many factors on VIM, such as different headings, wave/current coexistence, different drafts, suppression elements, and the presence of risers. The results of the experiments presented here are motion amplitudes in both in-line and transverse directions, forces and added-mass coefficients, ratios of actual oscillation and natural periods, and motions in the XY plane. This is, therefore, a very extensive and important data set for comparisons and validations of theoretical and numerical models for VIM prediction. [DOI: 10.1115/1.4001440]

Phase-Locked Loop design applied to frequency-modulated atomic force microscope

The atomic force microscope (AFM) introduced the surface investigation with true atomic resolution. In the frequency modulation technique (FM-AFM) both the amplitude and the frequency of oscillation of the micro-cantilever must be kept constant even in the presence of tip-surface interaction forces. For that reason, the proper design of the Phase-Locked Loop (PLL) used in FM-AFM is vital to system performance. Here, the mathematical model of the FM-AFM control system is derived considering high order PLL In addition a method to design stable third-order Phase-Locked Loops is presented. (C) 2010 Elsevier B.V. All rights reserved.

Using bifurcations in the determination of lock-in ranges for third-order phase-locked loops

Transmission and switching in digital telecommunication networks require distribution of precise time signals among the nodes. Commercial systems usually adopt a master-slave (MS) clock distribution strategy building slave nodes with phase-locked loop (PLL) circuits. PLLs are responsible for synchronizing their local oscillations with signals from master nodes, providing reliable clocks in all nodes. The dynamics of a PLL is described by an ordinary nonlinear differential equation, with order one plus the order of its internal linear low-pass filter. Second-order loops are commonly used because their synchronous state is asymptotically stable and the lock-in range and design parameters are expressed by a linear equivalent system [Gardner FM. Phaselock techniques. New York: John Wiley & Sons: 1979]. In spite of being simple and robust, second-order PLLs frequently present double-frequency terms in PD output and it is very difficult to adapt a first-order filter in order to cut off these components [Piqueira JRC, Monteiro LHA. Considering second-harmonic terms in the operation of the phase detector for second order phase-locked loop. IEEE Trans Circuits Syst [2003;50(6):805-9; Piqueira JRC, Monteiro LHA. All-pole phase-locked loops: calculating lock-in range by using Evan`s root-locus. Int J Control 2006;79(7):822-9]. Consequently, higher-order filters are used, resulting in nonlinear loops with order greater than 2. Such systems, due to high order and nonlinear terms, depending on parameters combinations, can present some undesirable behaviors, resulting from bifurcations, as error oscillation and chaos, decreasing synchronization ranges. In this work, we consider a second-order Sallen-Key loop filter [van Valkenburg ME. Analog filter design. New York: Holt, Rinehart & Winston; 1982] implying a third order PLL The resulting lock-in range of the third-order PLL is determined by two bifurcation conditions: a saddle-node and a Hopf. (C) 2008 Elsevier B.V. All rights reserved.

Reachability of the synchronous state in a mutually connected PLL network

Second-order phase locked loops (PLLs) are devices that are able to provide synchronization between the nodes in a network even under severe quality restrictions in the signal propagation. Consequently, they are widely used in telecommunication and control. Conventional master-slave (M-S) clock-distribution systems are being, replaced by mutually connected (MC) ones due to their good potential to be used in new types of application such as wireless sensor networks, distributed computation and communication systems. Here, by using an analytical reasoning, a nonlinear algebraic system of equations is proposed to establish the existence conditions for the synchronous state in an MC PLL network. Numerical experiments confirm the analytical results and provide ideas about how the network parameters affect the reachability of the synchronous state. The phase-difference oscillation amplitudes are related to the node parameters helping to design PLL neural networks. Furthermore, estimation of the acquisition time depending on the node parameters allows the performance evaluation of time distribution systems and neural networks based on phase-locked techniques. (c) 2008 Elsevier GmbH. All rights reserved.

Measuring Dynamic Oscillations of a Small Span Cable-Stayed Footbridge: Case Study Using L1 GPS Receivers

Highly redundant or statically undetermined structures, such as a cable-stayed bridge, have been of particular concern to the engineering community nowadays because of the complex parameters that must be taken into account for healthy monitoring. The purpose of this study was to verify the reliability and practicability of using GPS to characterize dynamic oscillations of small span bridges. The test was carried out on a cable-stayed wood footbridge at Escola de Engenharia de Sao Carlos-Universidade de Sao Paulo, Brazil. Initially a static load trial was carried out to get an idea of the deck amplitude and oscillation frequency. After that, a calibration trial was carried out by applying a well known oscillation on the rover antenna to check the environment detectable limits for the method used. Finally, a dynamic load trial was carried out by using GPS and a displacement transducer to measure the deck oscillation. The displacement transducer was used just to confirm the results obtained by the GPS. The results have shown that the frequencies and amplitude displacements obtained by the GPS are in good agreement with the displacement transducer responses. GPS can be used as a reliable tool to characterize the dynamic behavior of large structures such as cable-stayed footbridges undergoing dynamic loads.

Multiple synchronous states in static delay-free mutually connected PLL networks

In many engineering applications, the time coordination of geographically separated events is of fundamental importance, as in digital telecommunications and integrated digital circuits. Mutually connected (MC) networks are very good candidates for some new types of application, such as wireless sensor networks. This paper presents a study on the behavior of MC networks of digital phase-locked loops (DPLLs). Analytical results are derived showing that, even for static networks without delays, different synchronous states may exist for the network. An upper bound for the number of such states is also presented. Numerical simulations are used to show the following results: (i) the synchronization precision in MC DPLLs networks; (ii) the existence of synchronous states for the network does not guarantee its achievement and (iii) different synchronous states may be achieved for different initial conditions. These results are important in the neural computation context. as in this case, each synchronous state may be associated to a different analog memory information. (C) 2010 Elsevier B.V. All rights reserved.