The response of porous Al2O3 probed to nanoindentation

The response of porous Al2O3 to nanoindentation was investigated at microscopic scales (nm-mu m) and under ultra-low loads from 5 to 90 mN with special attention paid to the dependence of the load-depth behaviour to sample porosity. It was found that the load-depth curves manifest local responses typical of the various porous structures investigated. This is particularly clear for the residual deformation after load removal. Similarly, the limited mean pressure of the sample containing small grains and interconnected pores is consistent with its porous structure. By comparison, the samples with larger grain size and various porous structures exhibit higher pressures and smaller residual deformations that can be attributed to the mechanical response of the solid phase. (C) 2007 Elsevier B.V. All rights reserved.

Comparisons of static, quasi-static and dynamic 3D porous media scale network models for two-phase immiscible flow in porous media

A dynamic 3D pore-scale network model is formulated for investigating the effect of interfacial tension and oil-water viscosity during chemical flooding. The model takes into account both viscous and capillary forces in analyzing the impact of chemical properties on flow behavior or displacement configuration, while the static model with conventional invasion percolation algorithm incorporates the capillary pressure only. From comparisons of simulation results from these models. it indicates that the static pore scale network model can be used successfully when the capillary number is low. With the capillary increases due to the enhancement of water viscosity or decrease of interfacial tension, only the quasi-static and dynamic model can give insight into the displacement mechanisms.

Stimulation discomfort comparison of asynchronous and synchronous methods with multi-field electrodes

Functional Electrical Stimulation (FES) is a technique that consists on applying electrical current pulses to artificially activate motor nerve fibers and produce muscle contractions to achieve functional movements. The main applications of FES are within the rehabilitation field, in which this technique is used to aid recovery or to restore lost motor functions. People that benefit of FES are usually patients with neurological disorders which result in motor dysfunctions; most common patients include stroke and spinal cord injury (SCI). Neuroprosthesis are devices that have their basis in FES technique, and their aim is to bridge interrupted or damaged neural paths between the brain and upper or lower limbs. One of the aims of neuroprosthesis is to artificially generate muscle contractions that produce functional movements, and therefore, assist impaired people by making them able to perform activities of daily living (ADL). FES applies current pulses and stimulates nerve fibers by means of electrodes, which can be either implanted or surface electrodes. Both of them have advantages and disadvantages. Implanted electrodes need open surgery to place them next to the nerve root, so these electrodes carry many disadvantages that are produced by the use of invasive techniques. In return, as the electrodes are attached to the nerve, they make it easier to achieve selective functional movements. On the contrary, surface electrodes are not invasive and are easily attached or detached on the skin. Main disadvantages of surface electrodes are the difficulty of selectively stimulating nerve fibers and uncomfortable feeling perceived by users due to sensory nerves located in the skin. Electrical stimulation surface electrode technology has improved significantly through the years and recently, multi-field electrodes have been suggested. This multi-field or matrix electrode approach brings many advantages to FES; among them it is the possibility of easily applying different stimulation methods and techniques. The main goal of this thesis is therefore, to test two stimulation methods, which are asynchronous and synchronous stimulation, in the upper limb with multi-field electrodes. To this end, a purpose-built wrist torque measuring system and a graphic user interface were developed to measure wrist torque produced with each of the methods and to efficiently carry out the experiments. Then, both methods were tested on 15 healthy subjects and sensitivity results were analyzed for different cases. Results show that there are significant differences between methods regarding sensation in some cases, which can affect effectiveness or success of FES.

A CE/SE Scheme for Flows in Porous Media and Its Applications

In this paper, a new computational scheme for solving flows in porous media was proposed. The scheme was based on an improved CE/SE method (the space-time Conservation Element and Solution Element method). We described porous flows by adopting DFB (Brinkman-Forchheimer extended Darcy) equation. The comparison between our computational results and Ghia's confirmed the high accuracy, resolution, and efficiency of our CE/SE scheme. The proposed first-order CE/SE scheme is a new reliable way for numerical simulations of flows in porous media. After investigation of effects of Darcy number on porous flow, it shows that Darcy number has dominant influence on porous flow for the Reynolds number and porosity considered.

Instabilities of a liquid film flowing down an inclined porous plane

The problem of a film flowing down an inclined porous layer is considered. The fully developed basic flow is driven by gravitation. A careful linear instability analysis is carried out. We use Darcy's law to describe the porous layer and solve the coupling equations of the fluid and the porous medium rather than the decoupled equations of the one-sided model used in previous works. The eigenvalue problem is solved by means of a Chebyshev collocation method. We compare the instability of the two-sided model with the results of the one-sided model. The result reveals a porous mode instability which is completely neglected in previous works. For a falling film on an inclined porous plane there are three instability modes, i.e., the surface mode, the shear mode, and the porous mode. We also study the influences of the depth ratio d, the Darcy number delta, and the Beavers-Joseph coefficient alpha(BJ) on the instability of the system.

Electro-optic integration of embedded electrodes and waveguides in LiNbO3 using a femtosecond laser

We describe the fabrication of a Mach-Zehnder optical modulator in LiNbO3 by femtosecond laser micormachining, which is composed of optical waveguides inscripted by a femtosecond laser and embedded microelectrodes subsequently using femtosecond laser ablation and selective electroless plating. A half-wave voltage close to 19 V is achieved at a wavelength of 632.8 nm with an interaction length of 2.6 mm. This simple and cost-effective technique opens up new opportunities for fabricating integrated electro-optic devices. (C) 2008 Optical Society of America

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Development of Metalloenzyme Dioxygen Reduction Cathodes

The prime thrust of this dissertation is to advance the development of fuel cell dioxygen reduction cathodes that employ some variant of multicopper oxidase enzymes as the catalyst. The low earth-abundance of platinum metal and its correspondingly high market cost has prompted a general search amongst chemists and materials scientists for reasonable alternatives to this metal for facilitating catalytic dioxygen reduction chemistry. The multicopper oxidases (MCOs), which constitute a class of enzyme that naturally catalyze the reaction O₂ + 4H⁺ + 4e^- → 2H₂O, provide a promising set of biochemical contenders for fuel cell cathode catalysts. In MCOs, a substrate reduces a copper atom at the type 1 site, where charge is then transferred to a trinuclear copper cluster consisting of a mononuclear type 2 or “normal copper” site and a binuclear type 3 copper site. Following the reduction of all four copper atoms in the enzyme, dioxygen is then reduced to water in two two-electron steps, upon binding to the trinuclear copper cluster. We identified an MCO, a laccase from the hyperthermophilic bacterium Thermus thermophilus strain HB27, as a promising candidate for cathodic fuel cell catalysis. This protein demonstrates resilience at high temperatures, exhibiting no denaturing transition at temperatures high as 95°C, conditions relevant to typical polymer electrolyte fuel cell operation.

In Chapter I of this thesis, we discuss initial efforts to physically characterize the enzyme when operating as a heterogeneous cathode catalyst. Following this, in Chapter II we then outline the development of a model capable of describing the observed electrochemical behavior of this enzyme when operating on porous carbon electrodes. Developing a rigorous mathematical framework with which to describe this system had the potential to improve our understanding of MCO electrokinetics, while also providing a level of predictive power that might guide any future efforts to fabricate MCO cathodes with optimized electrochemical performance. In Chapter III we detail efforts to reduce electrode overpotentials through site-directed mutagenesis of the inner and outer-sphere ligands of the Cu sites in laccase, using electrochemical methods and electronic spectroscopy to try and understand the resultant behavior of our mutant constructs. Finally, in Chapter IV, we examine future work concerning the fabrication of enhanced MCO cathodes, exploring the possibility of new cathode materials and advanced enzyme deposition techniques.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.