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Inductive plasmas are simulated by using a one-dimensional particle-in-cell simulation including Monte Carlo collision techniques (pic/mcc). To model inductive heating, a non-uniform radio-frequency (rf) electric field, perpendicular to the electron motion is included into the classical particle-in-cell scheme. The inductive plasma pic simulation is used to confirm recent experimental results that electric double layers can form in current-free plasmas. These results differ from previous experimental or simulation systems where the double layers are driven by a current or by imposed potential differences. The formation of a super-sonic ion beam, resulting from the ions accelerated through the potential drop of the double layer and predicted by the pic simulation is confirmed with nonperturbative laser-induced fluorescence measurements of ion flow. It is shown that at low pressure, where the electron mean free path is of the order of, or greater than the system length, the electron energy distribution function (eedf) is close to Maxwellian, except for its tail which is depleted at energies higher than the plasma potential. Evidence supporting that this depletion is mostly due to the high-energy electrons escaping to the walls is given. ¶ A new hybrid simulation scheme (particle ions and Boltzmann/particle electrons), accounting for non-Maxwellian eedf and self-consistently simulating low-pressure high-density plasmas at low computational cost is proposed. Results obtained with the “improved” hybrid model are in much better agreement with the full pic simulation than the classical non self-consistent hybrid model. This model is used to simulate electronegative plasmas and to provide evidence supporting the fact that propagating double layers may spontaneously form in electronegative plasmas. It is shown that critical parameters of the simulation were very much aligned with critical parameters of the experiment.

Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / by Frank Glenroy Smith, III. / Sc.D.

The application of composite action ushered a new era in the use of double-layer spaceframes as efficient floor systems in addition to their competitiveness as roof coveringstructural systems. Earlier research on space frames demonstrated large improvementsin their static behaviour caused by the introduction of composite action. Theseimprovements included an increase in ductility to avoid progressive collapse, a largeincrease in load-carrying capacity and a considerable reduction in materialconsumption.In this work, the effect of introducing composite action in changing the dynamiccharacteristics of space frames, in particular the natural frequencies and damping ratioswas presented. The study was expanded to determine the effect of composite action inchanging the response to dynamic excitations. The measured responses included thelateral displacements and changes in the internal member force distribution undershaking table vibrations.Three aluminium space frame models of the square on square (SOS) configuration weremanufactured. The first model was non-composite, while composite action was appliedto the other two models with a top aluminium deck and a timber deck, respectively.Two common cases of support conditions were used in connecting the models to theloading frame, which was the platform of the shaking table.Initial displacement method (snap test) was used to determine the frequency of vibrationand the damping ratio of test models in the vertical and horizontal directions usinglogarithmic decrement method. All models were then exposed to shaking tablevibrations to determine the changes in dynamic responses between different models.These tests were repeated for the three models after the successive removal of panelsfrom one direction to identify the changes to their characteristics and behaviour withdifferent aspect ratios.The second part of the study was carried out numerically by using the finite elementpackage ABAQUS. It started by selecting a valid finite element model from nineproposed models using experimental test results on physical structures. A parametricstudy was conducted using the validated finite element model to expand the study toinclude two common space frame configurations; the square on large square (SOLS)and square on diagonal (SOD), and two other cases of support configurations, namely,fully edge-supported and supports at corners and middle edges of models.Based on the work done in this study, it can be concluded that composite actionchanged the dynamic characteristics of space frames, which was clear in the increase oftheir vibration frequencies in all directions as a result of the increase in stiffness.Furthermore, the increase in stiffness resulted in a general reduction in the dampingratio of space frames covered with aluminium deck, while the high friction with topjoints and the nature of timber as a good energy absorbent material resulted in a variableeffect on the damping ratio associated with the increase in aspect ratio.The effect of composite action was clear in reducing the lateral displacement ofcomposite models by more than 50% compared to the non-composite case. Moreover,composite action resulted in changing the distribution of internal forces in diagonal andlower chord members such that forces became more concentrated at corners and edgesparallel to the direction of vibrations in both cases of corner and edge-supportedmodels.

The electrochemical double layer (EDL) at the solid–liquid interface is the near surface region where important electrochemical processes (e.g., electrodeposition, corrosion, and heterogeneous catalysis) take place. Subtle changes in the electrode surface material/topography and the nature of the fluid medium can drastically alter interactions between liquid molecules and the solid surface. A better understanding of this interfacial region can help advance numerous applied fields, such as battery technologies, solar cells, double layer capacitors, and carbon dioxide capture/conversion. Ionic liquids (IL) are an emerging class of solvents that could replace traditional aqueous/non-aqueous solvents due to their advantageous physiochemical properties (e.g., wide solvent window, high thermal stability, and excellent solvating power). However, our understanding of the near-surface structure of ILs in the EDL is still being developed. This thesis focuses on the fundamental electrochemical behavior of ILs to help understand its interfacial behavior in three main areas: 1) the nature of capacitance-potential relationships in neat ILs, 2) the role of ‘user-defined’ experimental variables on capacitive electrochemical measurements, and 3) the impact of IL + water mixtures on experimental data. The general shape of capacitance-potential curves can suggest at the broad architecture of the EDL region. Fundamental capacitive studies of the IL EDL show a wide range of results, even for similar electrochemical systems. Theoretical predictions suggest the capacitance-potential curve should exhibit bell- or camel-shaped curvature depending on the nature of the IL. Experimental observations have demonstrated several functional shapes such as U-shaped, bell-shaped, camel-shaped, and relatively featureless responses. Much of the work in this thesis starkly contrasts theoretical expectations by demonstrating capacitive behavior that is analogous to high temperature molten salts and dilute aqueous electrolytes with metallic and non-metallic electrode materials. However, our systematic studies of a model IL electrochemical system reveal that there are several ‘user-defined’ experimental variables (i.e. potential scan direction, data acquisition protocol, experimental technique, and potential range probed) which in some instances can significantly impact the resulting capacitance curvature. Some of these variables are often overlooked in the literature and our efforts are aimed at uniting the scientific community in this area to help better compare and understand results. An additional experimental variable of importance is the sorption of water into ILs, which is nearly impossible to prevent due to their hygroscopic nature. The presence of water is known to have a significant effect on the resulting mixtures’ bulk and interfacial properties. While the interaction between ILs and water can significantly vary depending on the nature of the IL, this thesis demonstrates that within small quantities (e.g., < 5000 ppm) of sorbed water there are only minor changes in spectroscopic and electrochemical responses. Collectively, the work outlined in this thesis helps the scientific community better understand electrochemical measurements in IL solvents by examining key analytical variables associated with capacitive measurements. The fundamental electrochemical studies described in this thesis demonstrate that the solid-liquid interface for IL solvents is response to even subtle changes in surface chemistries. These governing interfacial properties have ramifications in myriad applications from energy storage to lubrication.

In this research the environmental effects related to the position of a redox moiety with the electrochemical double layer were studied. This project was made possible with the synthesis of a series of lengths of ferrocene derived alkanethiols, a series of lengths of ferrocene derived norbornylogous bridges and a series of lengths of anthraquinone derived norbornylogous bridges. The series of ferrocene derived alkanethiols were used to study the effect of gradually varying the polarity of the self-assembled monolayers (SAMs) surface on the standard electron transfer rate constant and formal potential. This was achieved by varying the portion of hydroxyl to methyl terminated alkanethiol diluent in the SAM preparation step. It was found that the formal potential increased with a decreasing proportion of hydroxyl terminated diluent and increasing length of the diluent. For pure hydroxyl terminated diluent the formal potential was relatively independent of length. It was found that the rate constant increased for short alkane chain lengths with decreasing proportion of hydroxyl terminated diluent. However, it decreased in magnitude with long alkane chain lengths for low proportions of hydroxyl terminated diluent. The norbornylogous bridges were shown to stand proud above the diluent with a similar tilt angle as the alkanethiol diluent. The ferrocene derived norbornylogous bridges showed hydroxyl terminated monolayers had a slower rate constant then methyl terminated diluents independent of length and that it is highly probable that an alkane bridged redox moiety is located very close to the surface of the monolayer. SAMs were created with the ferrocene of the ferrocene derived norbornylogous bridges located at various heights above the monolayers surface. This was done by using various lengths of hydroxyl terminated diluent. It was found that the rate constant and the formal potential decreased with height above the surface. Interfacial potential distribution was used to account for this and to estimate a ??true?? formal potential. The anthraquinone derived norbornylogous bridges were tested at various pH values and heights above the surface. It was found that an accurate estimate for the electron transfer mechanism can not be made for surface bound species due to the effects of interfacial potential distribution. They demonstrated a novel technique for estimating the point of zero charge of the electrode.

Electroosmotic flow is a convenient mechanism for transporting polar fluid in a microfluidic device. The flow is generated through the application of an external electric field that acts on the free charges that exists in a thin Debye layer at the channel walls. The charge on the wall is due to the chemistry of the solid-fluid interface, and it can vary along the channel, e.g. due to modification of the wall. This investigation focuses on the simulation of the electroosmotic flow (EOF) profile in a cylindrical microchannel with step change in zeta potential. The modified Navier-Stoke equation governing the velocity field and a non-linear two-dimensional Poisson-Boltzmann equation governing the electrical double-layer (EDL) field distribution are solved numerically using finite control-volume method. Continuities of flow rate and electric current are enforced resulting in a non-uniform electrical field and pressure gradient distribution along the channel. The resulting parabolic velocity distribution at the junction of the step change in zeta potential, which is more typical of a pressure-driven velocity flow profile, is obtained. / Singapore-MIT Alliance (SMA)

The core of any electric vehicle (EV) is the electric drive train, intended as the energy conversion chain from the energy tank (typically some kind of rechargeable battery) to the electric motor that converts the electrical energy into the mechanical energy needed for the vehicle motion. The need for on-board electrical energy storage is the factor that has so far prevented pure electric vehicles from conquering significant market share. In fact electrochemical batteries, which are currently the most suitable device for electrical energy storage, have serious limitations in terms of energy and/or power density, cost and safety. All those characteristics reflect in pure electric vehicles being outperformed by standard internal combustion engine (ICE) based vehicles in terms of driving range, time needed to refuel and purchase cost. Electric vehicles do have their distinctive advantages, being intrinsically much more efficient, operating at zero emissions at the pipe, and offering a higher degree of controllability that can potentially enhance driving safety. No wonder then, that electric energy storage technology has attracted considerable R&amp;D investments, resulting in new traction battery packs that are getting closer and closer to the industrial targets. In this scenario of EV technology gaining momentum, power electronics engineers have to come up with newer solutions allowing for more efficient and more reliable utilization of the precious on-board energy that comes in a form that cannot be directly utilized by the motor. At present, most of the research in the area of power electronics for automotive is focused in volume and cost reduction techniques. The increase in power density is pursued by developing components that can be operated at higher temperature, thus relieving the requirements on cooling. In this thesis, the focus is on the development of alternative topologies for the power electronics converters that make use of some peculiarities of the energy storage components and of the electrical drive train in general, rather than being a mere component-level optimization of well established topologies. A novel converter topology is proposed for hybridization of the energy source with a supercapacitor-based power buffer being used to assist the main traction battery. From the functional point of view, the topology implements a bidirectional DC/DC converter. Making use of the fact that the battery terminal voltage is close to constant, an arrangement for the supercapacitors is devised allowing for bidirectional power flow by using power electronics devices of lower ratings than the ones needed in conventional DC/DC converters. At the same time, much smaller magnetic components are needed. Theoretical analysis of the operation of the proposed converter is given, allowing for optimized design. A full-scale experimental prototype rated at 30 kW, intended for use in a pure EV, has been built and tested. Results validate the theory and show that no particular impediment exist to the deployment of the concept in practical applications. Another concept introduced in the thesis is an architecture where the traction inverter is embedded in the energy storage device. The latter is constituted by several modules, as in the case of modern Li-ion battery systems, and each module is equipped with a local power electronics interface, making it functionally equivalent to a controllable voltage source. The result is a modular, distributed system that can be engineered to have very high reliability and also to exhibit self-healing properties. A prototype with a minimum number of modules has been built and tested. Results confirm the effectiveness of the system, and make it a good candidate for deployment in applications where reliability is the most important requirement.

This doctoral thesis gives background to the field of electrochemical energy storage in supercapacitors. It attempts to place the supercapacitor device in context of available and future technologies for alternative energy systems for transportation. Limitations of cells and electrodes and key challenges in the supercapacitor development are introduced. One objective of the thesis is to investigate and describe ionic transport in active carbon and possible restrictions in nanostructured porous systems with focus on small (micro and meso) pores. Another is to develop a model suitable for investigations of concentration and potential profiles from a single particle perspective. The results from the studies are presented in this thesis together with the scientific papers this thesis is based on. Studying electrochemical gradients (concentration and potential) of large electrodes and single particles may give important information of the limitations of the material. In larger three-electrode experimental set-ups, these gradients can be studied for electrodes but single particles are not available for experimental studies to the same extent since the matrix of an electrode consist of many particles, all adding to the total gradient of the electrode. The experimental part of this thesis is based on different experimental techniques: Three-electrode experiments for larger electrodes, microelectrode experiments for single particles, numerical simulations using Multiphysics (software) of large electrodes consisting of single particles. Four Papers are appended to the thesis. They present results and discussions regarding ionic transport, surface functionalities and modeling of a particle based supercapacitor electrode. Estimated effective diffusivities for an active carbon containing micro, meso and macropores are presented. Surface functionalities in the form of oxygen-containing groups were present in a carbon studied using two experimental set-ups. Faradaic peaks, previously not reported in activated carbon were seen. The occurrence of Faradaic phenomena in one experimental set-up but not the other is further analyzed and the origin of these peaks discussed. The particle based mathematical model, where galvanostatic and cyclic voltammetry is simulated, is presented. Concentration profiles both in the particles and electrodes are discussed and some of the numerical results are compared with experimental data. / QC 20100809

Finite element analysis of electric double layer capacitors using a transient nonlinear Nernst-Planck-Poisson (NPP) model and Nernst-Planck-Poisson-modified Stern layer (NPPMS) model are presented in 1D and 2D. The NPP model provided unrealistic ion concentrations for high electrode surface potential. The NPPMS model uses a modified Stern layer to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The finite element solution algorithm uses the Newton-Raphson method to solve the nonlinear problem and the alpha family approximation for time integration to solve the NPP and NPPMS models for transient cases. Cubic Hermite elements are used for interfacing the modified Stern and diffuse layers in 1D while serendipity elements are used for the same in 2D. Effects of the surface potential and bulk molarity on the electric potential and ion concentrations are studied. The ability of the models to predict energy storage capacity is investigated and the predicted solutions from the 1D NPP and NPPMS models are compared for various cases. It is observed that NPPMS model provided realistic and correct results for low and high values of surface potential. Furthermore, the 1D NPPMS model is extended into 2D. The pore structure on the electrode surface, the electrode surface area and its geometry are important factors in determining the performance of the electric double layer capacitor. Thus 2D models containing a porous electrode are modeled and analyzed for understanding of the behavior of the electric double layer capacitor. The effect of pore radius and pore depth on the predicted electric potential, ion concentrations, surface charge density, surface energy density, and charging time are discussed using the 2D Nernst-Planck-Poissonmodified Stern layer (NPPMS) model.