The role of HBF(4) in electro-catalysis: Arsenic contamination and anion adsorption

We present in this work a comprehensive investigation of the role played by dissolved tetrafluoroboric acid on the electrochemical response of a polycrystalline platinum electrode in acidic media. HBF(4) from two different suppliers was employed and characterized in terms of the amount of arsenic contamination by Inductively Coupled Plasma-Optical Emission Spectroscopy. The effect of different amounts of HBF(4) on the voltammetric profile of the Pt vertical bar HClO(4)(aq) interface was investigated by means of electrochemical quartz crystal nanobalance (EQCN). Despite the comparable cyclic voltammograms, the presence of arsenic in one of the two HBF(4) used resulted in dramatic variations in the mass change profile, which evidences the deposition/dissolution of arsenic prior to the surface oxidation. For the arsenic-free HBF(4), its effect on the mass change profile was mainly associated to anion adsorption. The impact of dissolved HBF(4) on the electro-oxidation of formic acid was rationalized in terms of two contributions: current enhancement at low potentials due to the arsenic-assisted formic acid electro-oxidation and inhibition at high potentials due to anion adsorption. (C) 2011 Elsevier B.V. All rights reserved.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response. (C) 2009 Elsevier Ltd. All rights reserved.

Ascorbate electro-oxidation by modified electrodes: Polypyrrole and polypyrrole/Ni(OH)(2) composite thin films

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Emprego de redes neurais artificiais supervisionadas e não supervisionadas no estudo de parâmetros reológicos de excipientes farmacêuticos sólidos

In this paper artificial neural network (ANN) based on supervised and unsupervised algorithms were investigated for use in the study of rheological parameters of solid pharmaceutical excipients, in order to develop computational tools for manufacturing solid dosage forms. Among four supervised neural networks investigated, the best learning performance was achieved by a feedfoward multilayer perceptron whose architectures was composed by eight neurons in the input layer, sixteen neurons in the hidden layer and one neuron in the output layer. Learning and predictive performance relative to repose angle was poor while to Carr index and Hausner ratio (CI and HR, respectively) showed very good fitting capacity and learning, therefore HR and CI were considered suitable descriptors for the next stage of development of supervised ANNs. Clustering capacity was evaluated for five unsupervised strategies. Network based on purely unsupervised competitive strategies, classic "Winner-Take-All", "Frequency-Sensitive Competitive Learning" and "Rival-Penalize Competitive Learning" (WTA, FSCL and RPCL, respectively) were able to perform clustering from database, however this classification was very poor, showing severe classification errors by grouping data with conflicting properties into the same cluster or even the same neuron. On the other hand it could not be established what was the criteria adopted by the neural network for those clustering. Self-Organizing Maps (SOM) and Neural Gas (NG) networks showed better clustering capacity. Both have recognized the two major groupings of data corresponding to lactose (LAC) and cellulose (CEL). However, SOM showed some errors in classify data from minority excipients, magnesium stearate (EMG) , talc (TLC) and attapulgite (ATP). NG network in turn performed a very consistent classification of data and solve the misclassification of SOM, being the most appropriate network for classifying data of the study. The use of NG network in pharmaceutical technology was still unpublished. NG therefore has great potential for use in the development of software for use in automated classification systems of pharmaceutical powders and as a new tool for mining and clustering data in drug development

Heterodyne Interferometry Applied to the Characterization of Acousto-Electro-Optic Light Modulators

When the electro-optic and acousto-optic effects are combined into a single device, the resulting acousto-electro-optic (AEO) modulator shows improved flexibility to overcome some limitations of the individual modulators or their cascade combinations. By using optical interferometry, it is possible to investigate the AEO modulator behavior as a function of this applied voltage. By this way, a lithium niobate AEO modulator is positioned in one of the arms of a Mach-Zehnder interferometer and operates at 62 MHz frequency, which constitutes the intermediate frequency of the heterodyne interferometer. Operating the AEO modulator in the acousto-optic small diffraction efficiency regime, the photodetected signal amplitude and phase are analyzed, and the induced phase shift, transmission curve and linearity response are obtained. The experimental results show good agreement with that expected from the coupled-mode theory. The possibility of linear control of the optical phase shift by the external voltage, from 0 to 2 p radians, is demonstrated.

Control Design Applied to a Micro Electro Mechanical System: MEMS Comb drive

This paper presents the linear optimal control technique for reducing the chaotic movement of the micro-electro-mechanical Comb Drive system to a small periodic orbit. We analyze the non-linear dynamics in a micro-electro-mechanical Comb Drive and demonstrated that this model has a chaotic behavior. Chaos control problems consist of attempts to stabilize a chaotic system to an equilibrium point, a periodic orbit, or more general, about a given reference trajectory. This technique is applied in analyzes the nonlinear dynamics in an MEMS Comb drive. The simulation results show the identification by linear optimal control is very effective.

A reducing of a chaotic movement to a periodic orbit, of a micro-electro-mechanical system, by using an optimal linear control design

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On an Non-Ideal Global and Local Energy Transfer, Using an Electro-Magneto and Magneto-Rheological Dampers

In this paper, we investigated the nonlinear vibrations of a Non-ideal (NIS) electromechanical absorber (NEVA), taking into account a modified mathematical model of (MR) Damper. We observed the presence of the Sornmerfeld effect (it is the steady state frequencies of the DC motor, which it will usually increasing as more power (Voltage) is given to it, in a step-by-step fashion. When a resonance condition it is reached, the better part of this energy it is consumed to generate large amplitude vibrations of the foundation, without sensible change of the motor frequency). The obtained results, by using numerical and analytical simulations, were discussed, in details.

On a Nonideal (MRD) Damper-Electro-mechanical Absorber Dynamics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Harmonical oscillator and electro-mechanical analogy: an interdiscinary experiment to high precision mass variation measurements

De forma geral, os cursos de física clássica oferecidos nas universidades carecem de exemplos de aplicações nas áreas de química e biologia, o que por vezes desmotivam os alunos de graduação destas áreas a estudarem os conceitos físicos desenvolvidos em sala de aula. Neste texto, a analogia entre os osciladores elétrico e mecânico é explorada visando possívies aplicações em química e biologia, mostrando-se de grande valia devido ao seu uso em técnicas de medição de variação de massa com alta precisão, tanto de forma direta como indireta. Estas técnicas são conhecidas como técnicas eletrogravimétricas e são de especial importância em aplicações que envolvem biossensores. Desta forma, o texto explora o estudo da analogia eletromecânica de forma interdisciplinar envolvendo as áreas de física, química e biologia. Baseado nessa analogia é proposto um experimento que permite a sua aplicação em diferentes níveis conceituais dessas disciplinas, tanto em abordagem básica como mais profunda.

Chaotic vibrations of a nonideal electro-mechanical system

Nonideal systems are those in which one takes account of the influence of the oscillatory system on the energy supply with a limited power (Kononenko, 1969). In this paper, a particular nonideal system is investigated, consisting of a pendulum whose support point is vibrated along a horizontal guide by a two bar linkage driven by a DC motor, considered to be a limited power supply. Under these conditions, the oscillations of the pendulum are analyzed through the variation of a control parameter. The voltage supply of the motor is considered to be a reliable control parameter. Each simulation starts from zero speed and reaches a steady-state condition when the motor oscillates around a medium speed. Near the fundamental resonance region, the system presents some interesting nonlinear phenomena, including multi-periodic, quasiperiodic, and chaotic motion. The loss of stability of the system occurs through a saddle-node bifurcation, where there is a collision of a stable orbit with an unstable one, which is approximately located close to the value of the pendulum's angular displacement given by alpha (C)= pi /2. The aims of this study are to better understand nonideal systems using numerical simulation, to identify the bifurcations that occur in the system, and to report the existence of a chaotic attractor near the fundamental resonance. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Electro-optical properties of Er-doped SnO2 thin films

Photoconductivity of SnO2 sol-gel films is excited, at low temperature, by using a 266 nm line-fourth harmonic-of a Nd:YAG laser. This line has above bandgap energy and promotes generation of electron-hole pairs, which recombines with oxygen adsorbed at grain boundary. The conductivity increases up to 40 times. After removing the illumination on an undoped SnO2 film, the conductivity remains unchanged, as long as the temperature is kept constant. Adsorbed oxygen ions recombine with photogenerated holes and are continuously evacuated from the system, leaving a net concentration of free electrons into the material, responsible for the increase in the conductivity. For Er doped SnO2, the excitation of conductivity by the laser line has similar behavior, however after removing illumination, the conductivity decreases with exponential-like decay. (C) 2003 Elsevier Ltd. All rights reserved.