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.

Thesis (Ph.D.)--University of Melbourne, School of Chemistry, 2006. / Typescript. Includes bibliographical references.

This works begins by providing motivation for additional research and political interest in the use of passenger railway systems as a method of ‘green’ transportation. Additional motivation for the adoption of energy saving methods within new and existing railway systems is also provided. This motivation stems from the relatively small carbon dioxide emissions per passenger kilometer and large quantity of electrical energy used in association with passenger railway systems. In specific cases, both theoretical analyses and experimental implementations of energy storage in railway systems have shown a reduction in electrical energy use and/or vehicle performance gains. Current railway energy storage systems (ESS) commonly make use of battery or electric double layer capacitor (EDLC) cells. A review of select energy storage technologies and their application in railway systems is provided. For example, the developing Qatar Education City People Mover system makes use of energy dense batteries and power dense EDLCs to provide the range and power needed to operate without a conventional railway power source between stations, formally called catenary free operation. As an alternative to combining two distinct energy storage technologies, this work looks at experimentally characterizing the performance of commercially available lithium ion capacitors (LiCs); a relatively new energy storage cell that combines characteristics of batteries and EDLCs into one cell. The custom cell testing apparatus and lab safety systems used by this work, and others, is discussed. A series of five tests were performed on two EDLC cells and five LiC cells to evaluate their characteristics under various electrical load conditions at multiple temperatures. The general conclusion is that, in comparison to the EDLC cells tested, the LiC cells tested offer a superior energy density however, their power capabilities are relatively limited, especially in cold environments, due to larger equivalent series resistance values. The second topic explored in this work is the development of a MATLAB based DC powered passenger vehicle railway simulation tool. The simulation tool is connected to the experimental analysis of EDLC and LiC cells by comparing the volume and mass of an energy storage system needed for catenary free (no conventional DC power supply) operation between train stations using either energy storage technology. A backward facing modelling approach is used to quantify the drive cycle electrical power demands as a function of multiple vehicle parameters and driving parameters (eg. acceleration rate, travel distance and time). Additional modelling methods are provided as a resource to further develop the simulation tool to include multiple vehicles and their interactions with the DC power supply. Completion of the multi-vehicle simulation tool with energy storage systems remains a task for future work. / Thesis / Master of Applied Science (MASc)

Ionomeric polymer transducers consist of an ion-exchange membrane plated with conductive metal layers on its outer surfaces. Such materials are known to exhibit electromechanical coupling under the application of electric fields and imposed deformation (Oguro et al., 1992; Shahinpoor et al., 1998). Compared to other types of electromechanical transducers, such as piezoelectric materials, ionomeric transducers have the advantage of high-strain output (> 9% is possible), low-voltage operation (typically less than 5 V), and high sensitivity in the charge-sensing mode. A series of experiments on actuators with various ionic polymers such as Nafion and novel poly(Arylene ether disulphonate) systems (BPS and PATS) and electrode composition demonstrated the existence of a linear correlation between the strain response and the capacitance of the material. This correlation was shown to be independent of the polymer composition and the plating parameters. Due to the fact that the low-frequency capacitance of an ionomer is strongly related to charge accumulation at the electrodes, this correlation suggests a strong relationship between the surface charge accumulation and the mechanical deformation in ionomeric actuators. The strain response of water-hydrated transducers varies from 50 μstrain/V to 750 μstrain/V at 1Hz while the strain-to-charge response is between 9 ^μstrain_{^c_m²} and 15 ^μstrain_{^c_m²}. This contribution suggests a strong correlation between cationic motion and the strain in the polymer at the ionomer-conductor interface. A novel fabrication technique for ionic polymer transducers was developed for this dissertation for the purpose of quantifying the relationship between electrode composition and transducer performance. It consists of mixing an ionic polymer dispersion (or solution) with a fine conducting powder and attaching it to the membrane as an electrode. The Direct Assembly Process (DAP) allows the use of any type of ionomer, diluent, conducting powder, and counter ion in the transducer, and permits the exploration of any novel polymeric design. Several conducting powders have been incorporated in the electrode including single-walled carbon nanotubes (SWNT), polyaniline (PANI) powders, high surface area RuO2, and carbon black electrodes. The DAP provided the tool which enabled us to study the effect of electrode architecture on performance of ionic polymer transducers. The DAP allows the variation in the electrode architecture which enabled us to fabricate dry transducers with 50x better performance compared to transducers made using the state of the art impregnation-reduction technique. DAP fabricated transducers achieved a strain of 9.4% at a strain rate of 1%/s. Each electrode material had an optimal concentration in the electrode. For RuO2, the optimal loading was approximately 45% by volume. This study also demonstrated that carbon nanotubes electrodes have an optimal performance at loadings around 30 vol%, while PANI electrodes are optimized at 95 vol%. Extensional actuation in ionic polymer transducers was first reported and characterized in this dissertation. An electromechanical coupling model presented by Leo et al. (2005) defined the strain in the active areas as a function of the charge. This model assumed a linear and a quadratic term that produces a nonlinear response for a sine wave actuation input. The quadratic term in the strain generates a zero net bending moment for ionic polymer transducers with symmetric electrodes, while the linear term is canceled in extensional actuation for symmetric electrodes. Experimental results demonstrated strains on the order of 110 μstrain in the thickness direction compared to 1700 μstrain peak to peak on the external fibers for the same transducer, could be achieved when it is allowed to bend under +/-2V potential at 0.5 Hz. Extensional and bending actuation in ionic polymer transducers were explained using a bimorph active area model. Several experiments were performed to compare the bending actuation with the extensional actuation capability. The active area in the model was assumed to be the high surface area electrode. Electric double layer theory states that ions accumulate in a thin boundary layer close to the metal-polymer interface. Since the metal powders are evenly dispersed in the electrode area of the transducer, this area is expected to actuate evenly upon voltage application. This active area model emphasizes the importance the boundary layer on the conductor-ionomer interfacial area. Computing model parameters based on experimental results demonstrated that the active areas model collapses the bending data from a maximum variation of 200% for the strain per charge, to less than 68% for the model linear term. Furthermore, the model successfully predicted bending response from parameters computed using thickness experimental results. The prediction was particularly precise in estimating the trends of non-linearity as a function of the amount of asymmetry between the two electrodes. / Ph. D.

The electrical potential differences which arise across the length of capillary tubes containing 1 N perchloric acid and mercury drops are studied experimentally and theoretically for constant acceleration and different lengths of the drops of mercury. A relatively simple theory explains many features of the voltage on the experimental parameters. The results suggest that surface modes exist on the mercury drops which, in association with the Gibbs-Thompson effect, is the coupling between the mechanical and electrochemical phenomena. / Ph. D.

Eine der Faustregeln der Kolloid- und Oberflächenphysik ist, dass die meisten Oberflächen geladen sind, wenn sie mit einem Lösungsmittel, normalerweise Wasser, in Kontakt treten. Dies ist zum Beispiel bei ladungsstabilisierten Kolloidalen Suspensionen der Fall, bei denen die Oberfläche der Kolloidteilchen geladen ist (gewöhnlich mit einer Ladung von mehreren Hunderttausend Elementarladungen), oder bei Monoschichten ionischer Tenside, die auf einer Luft-Wasser Grenzfläche sitzen (wobei die wasserliebenden Kopfgruppen durch die Freisetzung von Gegenionen geladen werden), sowie bei Doppelschichten, die geladene phospholipide enthalten (wie Zellmembranen). In dieser Arbeit betrachten wir einige Modellsysteme, die zwar eine vereinfachte Fassung der Realität darstellen, von denen wir aber dennoch erwarten koennen, dass wir mit ihrer Hilfe einige physikalische Eigenschaften realer geladener Systeme (Kolloide und Elektrolyte) einfangen können. / One of the rules-of-thumb of colloid and surface physics is that most surfaces are charged when in contact with a solvent, usually water. This is the case, for instance, in charge-stabilized colloidal suspensions, where the surface of the colloidal particles are charged (usually with a charge of hundreds to thousands of e, the elementary charge), monolayers of ionic surfactants sitting at an air-water interface (where the water-loving head groups become charged by releasing counterions), or bilayers containing charged phospholipids (as cell membranes). In this work, we look at some model-systems that, although being a simplified version of reality, are expected to capture some of the physical properties of real charged systems (colloids and electrolytes).<br /> <br /> We initially study the simple double layer, composed by a charged wall in the presence of its counterions. The charges at the wall are smeared out and the dielectric constant is the same everywhere. The Poisson-Boltzmann (PB) approach gives asymptotically exact counterion density profiles around charged objects in the weak-coupling limit of systems with low-valent counterions, surfaces with low charge density and high temperature (or small Bjerrum length). Using Monte Carlo simulations, we obtain the profiles around the charged wall and compare it with both Poisson-Boltzmann (in the low coupling limit) and the novel strong coupling (SC) theory in the opposite limit of high couplings. In the latter limit, the simulations show that the SC leads in fact to asymptotically correct density profiles. We also compare the Monte Carlo data with previously calculated corrections to the Poisson-Boltzmann theory. We also discuss in detail the methods used to perform the computer simulations.<br /> <br /> After studying the simple double layer in detail, we introduce a dielectric jump at the charged wall and investigate its effect on the counterion density distribution. As we will show, the Poisson-Boltzmann description of the double layer remains a good approximation at low coupling values, while the strong coupling theory is shown to lead to the correct density profiles close to the wall (and at all couplings). For very large couplings, only systems where the difference between the dielectric constants of the wall and of the solvent is small are shown to be well described by SC.<br /> <br /> Another experimentally relevant modification to the simple double layer is to make the charges at the plane discrete.<br /> The counterions are still assumed to be point-like, but we constraint the distance of approach between ions in the plane and counterions to a minimum distance D. The ratio between D and the distance between neighboring ions in the plane is, as we will see, one of the important quantities in determining the influence of the discrete nature of the charges at the wall over the density profiles. Another parameter that plays an important role, as in the previous case, is the coupling as we will demonstrate, systems with higher coupling are more subject to discretization effects than systems with low coupling parameter.<br /> <br /> After studying the isolated double layer, we look at the interaction between two double layers. The system is composed by two equally charged walls at distance d, with the counterions confined between them. The charge at the walls is smeared out and the dielectric constant is the same everywhere. Using Monte-Carlo simulations we obtain the inter-plate pressure in the global parameter space, and the pressure is shown to be negative (attraction) at certain conditions. The simulations also show that the equilibrium plate separation (where the pressure changes from attractive to repulsive) exhibits a novel unbinding transition. We compare the Monte Carlo results with the strong-coupling theory, which is shown to describe well the bound states of systems with moderate and high couplings. The regime where the two walls are very close to each other is also shown to be well described by the SC theory.<br /> <br /> Finally, Using a field-theoretic approach, we derive the exact low-density ("virial") expansion of a binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). The free energy obtained is valid for systems where the diameters d_+ and d_- and the charge valences q_+ and q_- of positive and negative ions are unconstrained, i.e., the same expression can be used to treat dilute salt solutions (where typically d_+ ~ d_- and q_+ ~ q_-) as well as colloidal suspensions (where the difference in size and valence between macroions and counterions can be very large). We also discuss some applications of our results.

<p>Ferroelectric thin films (FETFs) offer a promising new platform for advancing liquid-phase interfacial sensing devices. FETFs are capable of expressing surface charge densities that are an order of magnitude higher than those of traditional charged surfaces in liquid environments (e.g., common oxides, self-assembled monolayers, or electrets). Furthermore, the switchable polarization state of FETFs enables patterning of charge-heterogeneous surfaces whose charge patterns persist over a range of environmental conditions. Integration of FETFs into liquid-phase interfacial sensing devices, however, requires the fabrication of films with nanometer-scale surface roughness, high remnant polarization values, and interfacial stability during prolonged exposure. The objectives of my research were to i) fabricate ferroelectric ultra-smooth lead zirconium titanate (US-PZT) thin films with nanometer-scale surface roughness, ii) establish the interfacial stability of these films after prolonged exposure to aqueous environments, iii) measure the interfacial forces as a function of film polarization and ionic strength, iv) calculate the surface potential of the US-PZT surface using electric double layer (EDL) theory, and v) demonstrate the guided deposition of charged colloidal particles onto locally polarized US-PZT thin films from solution. </p><p>I demonstrate the use of ferroelectric US-PZT thin films to manipulate EDL interaction forces in aqueous environments. My work conclusively shows that the polarization state of US-PZT controls EDL formation and can be used to induce the guided deposition of charged colloidal particles in solution. </p><p>I present a robust fabrication scheme for making ferroelectric US-PZT thin films from a sol-gel precursor. By optimizing critical thermal processing steps I am able to minimize the in-plane stress of the film and reliably produce US-PZT thin films on the wafer-scale with mean surface roughness values of only 2.4 nm over a 25 &#956;m2 area. I then establish US-PZT film stability in water by measuring changes in film topography, crystallinity, surface chemistry, and electrical properties as a function of exposure duration. My results show that fabrication of crack-free US-PZT thin film is critical for long-term film fidelity in aqueous environments. Furthermore, I found no change in film topography or bulk composition with increasing exposure duration. Prolonged exposure to aqueous environments, however, gradually oxidizes the surface of the US-PZT wich results in a decrease in film resistivity and polarization saturation. Next, I used colloidal probe force microscopy (CPFM) to measure the EDL interaction force as a function of separation distance between polarized US-PZT thin films and a clean borosilicate probe. CPFM measurements were performed on oppositely polarized US-PZT thin films, which expressed either a positive or negative surface charge, and over a range of ionic strengths. The inner-Helmholtz plane (IHP) potential of the US-PZT was determined by fitting the CPFM force-separation data to number of EDL models, including; an analytical EDL model using a constant potential boundary condition with a Stern layer, a charge regulation EDL model, and a numerical EDL model using the non-linear Poisson-Boltzmann equation. Each model provides good agreement with the experimentally measured and predict high IHP surface potential for the polarized US-PZT thin films in solution. Finally, I demonstrate the use of polarized US-PZT to induce the guided deposition of positively or negatively charged colloidal particles from aqueous environments. I explore the effects of ionic strength, particle size, surface roughness, and pH on particle deposition. </p><p>Overall, this work demonstrates, for the first time, that FETFs can be used as a platform to manipulate colloidal particles in aqueous environments. The experimental results demonstrate that the surface charge of the FETF is reduced by charge shielding and perform similarly to traditional, charged surfaces in aqueous environments.</p> / Dissertation

No description available.

Surgical correction of scoliosis is a complicated mechanical process. Understanding the loads applied to the spine and providing immediate feedback to surgeons during scoliosis surgery will prevent overloading, improve surgical outcome and patient safety. Long-term development of residual forces in the spinal instrument after surgery with the continual curvature changes over time has been unknown. The goal of this research work was to develop a wireless implantable sensor platform to investigate the loads during and after surgery. This thesis describes research leading to the design of a sensor platform that uses both 403 MHz and 2.45 GHz for wireless communication, and reports the resolution and accuracy of the built-in temperature sensor, the A/D accuracy of the sensing platform, the power consumption at different operation modes, the range of the wireless communication and the discharge characteristics of a potential capacitive power module. / Biomedical Engineering

Bibliography : leaves 154-163 / ix, 163 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics, and Mathematical Physics, 1993