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.

Mechanism and model of the oscillatory electro-oxidation of methanol

A mechanism for the kinetic instabilities observed in the galvanostatic electro-oxidation of methanol is suggested and a model developed. The model is investigated using stoichiometric network analysis as well as concepts from algebraic geometry (polynomial rings and ideal theory) revealing the occurrence of a Hopf and a saddle-node bifurcation. These analytical solutions are confirmed by numerical integration of the system of differential equations. (C) 2010 American Institute of Physics

Topology Optimized Design, Microfabrication and Characterization of Electro-Thermally Driven Microgripper

This article presents a systematic and logical study of the topology optimized design, microfabrication, and static/dynamic performance characterization of an electro-thermo-mechanical microgripper. The microgripper is designed using a topology optimization algorithm based on a spatial filtering technique and considering different penalization coefficients for different material properties during the optimization cycle. The microgripper design has a symmetric monolithic 2D structure which consists of a complex combination of rigid links integrating both the actuating and gripping mechanisms. The numerical simulation is performed by studying the effects of convective heat transfer, thermal boundary conditions at the fixed anchors, and microgripper performance considering temperature-dependent and independent material properties. The microgripper is fabricated from a 25 mm thick nickel foil using laser microfabrication technology and its static/dynamic performance is experimentally evaluated. The static and dynamic electro-mechanical characteristics are analyzed as step response functions with respect to tweezing/actuating displacements, applied current/power, and actual electric resistance. A microgripper prototype having overall dimensions of 1mm (L) X 2.5mm (W) is able to deliver the maximum tweezing and actuating displacements of 25.5 mm and 33.2 mm along X and Y axes, respectively, under an applied power of 2.32 W. Experimental performance is compared with finite element modeling simulation results.

Electro-optically sensitive diamond-like carbon thin films deposited by reactive magnetron sputtering for electronic device applications

The goal of this work is to study and relate electrical and optical properties of diamond-like carbon (DLC) thin films for applications in electronic devices. DLC films were deposited in a reactive RF magnetron sputtering system on p-type silicon and glass substrates. The target was a 99.9999% pure, 6 in. diameter graphite plate and methane was used as processing gas. Eight DLC films were produced for each substrate, varying deposition time, the reactor pressure between 5 mTorr and 10 mTorr while the RF power was applied at 13.56 MHz and varied between 100, 150, 200 and 250W. After deposition, the films were analyzed by I-V and C-V measurements (Cheng et al. (2004) [1]) in order to determine the electric resistivity, photo-current response and dielectric constant, optical transmittance, used to find the optical gap by the Tauc method; and by photoluminescence analysis to determine the photoemission and confirm the optical band gap. These characteristics are compared and the influence of the deposition parameters is discussed. (C) 2011 Published by Elsevier B.V.

Development and fabrication of an optimized thermo-electro-optic device using a Mach-Zehnder interferometer

The development and fabrication of a thermo-electro-optic sensor using a Mach-Zehnder interferometer and a resistive micro-heater placed in one of the device`s arms is presented. The Mach-Zehnder structure was fabricated on a single crystal silicon substrate using silicon oxynitride and amorphous hydrogenated silicon carbide films to form an anti-resonant reflective optical waveguide. The materials were deposited by Plasma enhanced chemical vapor deposition technique at low temperatures (similar to 320 degrees C). To optimize the heat transfer and increase the device response with current variation, part of the Mach-Zehnder sensor arm was suspended through front-side bulk micromachining of the silicon substrate in a KOH solution. With the temperature variation caused by the micro-heater, the refractive index of the core layer of the optical waveguide changes due to the thermo-optic effect. Since this variation occurs only in one of the Mach-Zehnder`s arm, a phase difference between the arms is produced, leading to electromagnetic interference. In this way, the current applied to the micro-resistor can control the device output optical power. Further, reactive ion etching technique was used in this work to define the device`s geometry, and a study of SF6 based etching rates on different composition of silicon oxynitride films is also presented. (C) 2007 Elsevier B.V. All rights reserved.

Diseño hidráulico de vertedores escalonados con pendientes moderadas: Metodología basada en un estudio experimental

Durante las últimas tres décadas el interés y diversidad en el uso de canales escalonados han aumentado debido al desarrollo de nuevas técnicas y materiales que permiten su construcción de manera rápida y económica (Concreto compactado con rodillo CCR, Gaviones, etc.). Actualmente, los canales escalonados se usan como vertedores y/o canales para peces en presas y diques, como disipadores de energía en canales y ríos, o como aireadores en plantas de tratamiento y torrentes contaminados. Diversos investigadores han estudiado el flujo en vertedores escalonados, enfocándose en estructuras de gran pendiente (  45o) por lo que a la fecha, el comportamiento del flujo sobre vertedores con pendientes moderadas (  15 a 30o) no ha sido totalmente comprendido. El presente artículo comprende un estudio experimental de las propiedades físicas del flujo aire-agua sobre canales escalonados con pendientes moderadas, típicas en presas de materiales sueltos. Un extenso rango de gastos en condiciones de flujo rasante se investigó en dos modelos experimentales a gran escala (Le = 3 a 6): Un canal con pendiente 3.5H:1V (  16o) y dos alturas de escalón distintas (h = 0.1 y 0.05 m) y un canal con pendiente 2.5H:1V (  22o) y una altura de escalón de h = 0.1 m. Los resultados incluyen un análisis detallado de las propiedades del flujo en vertedores escalonados con pendientes moderadas y un nuevo criterio de diseño hidráulico, el cual está basado en los resultados experimentales obtenidos. English abstract: Stepped chutes have been used as hydraulic structures since antiquity, they can be found acting as spillways and fish ladders in dams and weirs, as energy dissipators in artificial channels, gutters and rivers, and as aeration enhancers in water treatment plants and polluted streams. In recent years, new construction techniques and materials (Roller Compacted Concrete RCC, rip-rap gabions, etc.) together with the development of the abovementioned new applications have allowed cheaper construction methods, increasing the interest in stepped chute design. During the last three decades, research in stepped spillways has been very active. However, studies prior to 1993 neglected the effect of free-surface aeration. A number of studies have focused since on steep stepped chutes (  45o) but the hydraulic performance of moderate-slope stepped channels is not yet totally understood. This study details an experimental investigation of physical air-water flow properties down moderate slope stepped spillways conducted in two laboratory models: the first model was a 3.15 m long stepped chute with a 15.9o slope comprising two interchangeable step heights (h = 0.1 m and h = 0.05 m); the second model was a 3.3 m long, stepped channel with a 21.8o slope (h = 0.1 m). A broad range of discharges within transition and skimming flow regimes was investigated. Measurements were conducted using a double tip conductivity probe. The study provides new, original insights into air-water stepped chute flows not foreseen in prior studies and presents a new design criterion for chutes with moderate slopes based on the experimental results.

Large amplitude vibration of thermo-electro-mechanically stressed FGM laminated plates

This paper presents a large amplitude vibration analysis of pre-stressed functionally graded material (FGM) laminated plates that are composed of a shear deformable functionally graded layer and two surface-mounted piezoelectric actuator layers. Nonlinear governing equations of motion are derived within the context of Reddy's higher-order shear deformation plate theory to account for transverse shear strain and rotary inertia. Due to the bending and stretching coupling effect, a nonlinear static problem is solved first to determine the initial stress state and pre-vibration deformations of the plate that is subjected to uniform temperature change, in-plane forces and applied actuator voltage. By adding an incremental dynamic state to the pre-vibration state, the differential equations that govern the nonlinear vibration behavior of pre-stressed FGM laminated plates are derived. A semi-analytical method that is based on one-dimensional differential quadrature and Galerkin technique is proposed to predict the large amplitude vibration behavior of the laminated rectangular plates with two opposite clamped edges. Linear vibration frequencies and nonlinear normalized frequencies are presented in both tabular and graphical forms, showing that the normalized frequency of the FGM laminated plate is very sensitive to vibration amplitude, out-of-plane boundary support, temperature change, in-plane compression and the side-to-thickness ratio. The CSCF and CFCF plates even change the inherent hard-spring characteristic to soft-spring behavior at large vibration amplitudes. (C) 2003 Elsevier B.V. All rights reserved.

Postbuckling of piezoelectric FGM plates subject to thermo-electro-mechanical loading

In this paper, we examine the postbuckling behavior of functionally graded material FGM rectangular plates that are integrated with surface-bonded piezoelectric actuators and are subjected to the combined action of uniform temperature change, in-plane forces, and constant applied actuator voltage. A Galerkin-differential quadrature iteration algorithm is proposed for solution of the non-linear partial differential governing equations. To account for the transverse shear strains, the Reddy higher-order shear deformation plate theory is employed. The bifurcation-type thermo-mechanical buckling of fully clamped plates, and the postbuckling behavior of plates with more general boundary conditions subject to various thermo-electro-mechanical loads, are discussed in detail. Parametric studies are also undertaken, and show the effects of applied actuator voltage, in-plane forces, volume fraction exponents, temperature change, and the character of boundary conditions on the buckling and postbuckling characteristics of the plates. (C) 2003 Elsevier Science Ltd. All rights reserved.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwal carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. Themechanical properties aremainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwall carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. The mechanical properties are mainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Electro-mechanical properties of triblock copolymer styrene-butadiene-styrene / carbon nanotube composites for large deformation sensor applications

Thermoplastic elastomer/carbon nanotube composites are studied for sensor applications due to their excellent mechanical and electrical properties. Piezoresisitive properties of tri-block copolymer styrene-butadiene-styrene (SBS)/ carbon nanotubes (CNT) prepared by solution casting have been investigated. Young modulus of the SBS/CNT composites increases with the amount of CNT filler content present in the samples, without losing the high strain deformation on the polymer matrix (~1500 %). Further, above the percolation threshold these materials are unique for the development of large deformation sensors due to the strong piezoresistive response. Piezoresistive properties evaluated by uniaxial stretching in tensile mode and 4-point bending showed a Gauge Factors up to 120. The excellent linearity obtained between strain and electrical resistance makes these composites interesting for large strain piezoresistive sensors applications.

La Implementación del Cuadro de Mando Integral en Organizaciones Públicas y Privadas Portuguesas: Factores Relacionados con los Sistemas de Información y Gestión

La presente comunicación tiene como objetivo identificar y analizar un conjunto de variables que pueden potencialmente influir en la adopción del Cuadro de Mando Integral (CMI) en las organizaciones públicas y privadas portuguesas. Definimos un conjunto de hipótesis de investigación relativas a variables relacionadas con los sistemas de información y gestión, y para comprobar empíricamente las hipótesis formuladas hemos recurrido a los datos obtenidos mediante la aplicación de un cuestionario postal a 591 organizaciones públicas (ayuntamientos, hospitales, empresas municipales y empresas intermunicipales) y 549 organizaciones privadas (grandes empresas y pequeñas y medianas empresas) portuguesas, con una tasa de respuesta total del 31,3%.

Correlación de la productividad de un forraje con las propiedades físicas de un Ultisol en Aquidauana

Los sistemas de producción de ganadería y de manejo de pastos alteran las propiedades físicas del suelo, reflejados en la productividad y la composición vegetal. El objetivo de este trabajo fue indicar las propiedades físicas del suelo con mejores correlaciones lineales y espaciales para obtener sitios específicos de manejo del suelo. Se analizaron las correlaciones lineales y espaciales entre la productividad de la materia seca del forraje de Brachiaria decumbens (Stapf) y algunas propiedades físicas de un Ultisol en dos profundidades (0,00-0,10 m y 0,10-0,20 m). Para la colecta de los datos fue instalada una red geoestadística con 121 puntos de muestreo. La productividad del forraje varió aleatoriamente y no siguió patrones espaciales, presentando el efecto pepita puro. La resistencia mecánica del suelo a la penetración y la humedad del suelo en la capa de 0,10-0,20 m, son importantes indicadores de la calidad física del suelo. El aumento de estas propiedades en el cultivo del forraje, promovió la reducción de la materia seca del forraje. Por lo tanto, estos indicadores representan confiabilidad para estimar la productividad del forraje.