No description available.

This thesis was concerned with the proof of concept for mid-grade, 250-500oC, industrial waste heat recovery using a thermally regenerative electrochemical system. Proposed thermally regenerative electrochemical systems are limited to high operating temperatures (> 900oC) and suffer from poor conversion efficiencies (< 20%). As such, a single chamber design that is free of moving parts was presented in this work. The concept for this novel regenerative system relies on gravity and a liquid medium to convey dissolved sodium hydride in a hydride-borohydride solution from cold to hot regions in a continuous circuit. Such a liquid transport medium could allow for operation below 500oC while stabilizing the hydride from thermal decomposition. Investigations on this system were carried out using a custom pressure differential thermal analyzer that was able to operate above temperatures of 700oC and pressures of 2.2MPa. The results of the experiments provided valuable information concerning the phase diagrams of various hydride-borohydride mixtures. The eutectic composition of the NaH-KBH4 system was found to be 43 mole% NaH. The corresponding eutectic temperature (503oC) was determined using the differential cooling curves. Appreciable NaH decomposition was noticed in mixtures above 59.0 mole% NaH. Mixtures up to 42.5 mole% KH in KBH4 were also investigated. The eutectic composition of the KH-KBH4 binary system was determined by extrapolating the liquidus curve to intersect the solidus curve. The KH-KBH4 eutectic temperature was found to be 390oC at 66 mole% KH. The experimental work successfully demonstrates that thermally unstable hydrides can be obtained in the liquid phase below their melting points, under moderate pressures, when mixed with alkali borohydrides. This significantly lowers the achievable operating temperature of the thermally regenerative electrochemical systems currently proposed. The use of the single chamber design with a hydride-borohydride liquid medium offers numerous advantages including: reduced maintenance, reduced operating temperature, reduced system weight, reduced parasitic losses, increased voltage, and increased reliability. The viability for mid-grade industrial waste heat recovery requires construction of a prototype which optimizes power outputs and explores the hydrodynamic transport of material. / Thesis (Master, Mining Engineering) -- Queen's University, 2009-09-24 14:33:22.627

In screen-printed silicon-crystalline solar cells, the contact resistance of a thin interfacial glass layer between the silicon and the silver electrode plays a limiting role for electron transport. The motivation of this project is to gain increased understanding of the transport mechanisms of the electrons across this layer, which can be exploited to provide higher performance crystalline silicon solar cells. Our methodology throughout is to formulate and analyse mathematical models for the electron transport, based on the drift diffusion equations. In the first chapter we outline the problem and provide a summary of relevant theory. In Chapter 2 we formulate a one-dimensional model for electron transport across the glass layer, that we solve both numerically and by employing asymptotic techniques. Chapter 3 extends the model presented in Chapter 2 to two dimensions. To solve the two-dimensional model numerically we devise and validate a new spectral method. The short circuiting of current through thinner regions of the glass layer enables us to find limiting asymptotic expressions for the average current density for two different canonical glass layer profiles. In Chapter 4 we include quantum mechanical effects into the one-dimensional model outlined in Chapter 2 and find that they have a negligible effect on the contact resistance of the glass layer. We model the boundary effects present at the silicon emitter-glass interface in Chapter 5. Finally, in Chapter 6 we summarise our key results, suggest possible future work, and outline the implications of our work to crystalline silicon solar cell manufacturers.

The evaluation of concentration of ions and molecules with the help of biosensors have been regarded as an emerging technology. Bio and chemical sensors have a variety of applications in the field of medicine, military, environmental and food industries alike. With an estimated investment growth of over 4.31% in the development of pH sensors in the next five year, the objective of a developing a robust measurement system is all the more required. The scope of this research is to evaluate the ability of conducting polymer-based gel electrolytes for pH sensitivity, as a function of the transistor characteristics using an Extended Gate Field Effect Transistor or a conducting film in an electrochemical cell. Polymer gels were prepared by dissolving a suitable conducting polymer in an acidic media. The interaction of the gel with a buffer solution of known pH was collected as electric signals using a glassy carbon as an electrode. The electrochemical cell was further connected to the gate of a Metal-Oxide-Semiconductor Field Effect transistor (MOS-FET). The drain current was measured under two conditions; a) voltage across the gate (VGS) was kept constant, with varying voltage across the drain (VDS) and b) voltage across drain was fixed, while gate voltage changed. The drain current versus voltage of the transistor was plotted as a function of the ion interaction between the gel and the buffer. Different plots were recorded for different values of pH solutions. Final results were plotted to calculate the change in threshold voltage, for every change in pH of the observed solution. pH sensitivity of the gels was further tested through the Electrochemical Impedance Spectroscopy method, using a potentiostat and a three-electrode electrochemical cell. With a small excitation, the AC current flowing through the circuit at different frequencies were recorded and the plots discussed, to evaluate sensitivity to pH.

No description available.

Removal of nitrogen elements in culture water is one of the major concerns in recirculating aquaculture system (RAS). Maintaining a low concentration of nitrogen compounds is essential for a good quality of aquaculture production. Due to fish is very sensitive to the toxic ammonium/ammonia, nitrification biofiltration tank is often an integrate part of filtration in RAS to remove ammonium via nitrification. However, nitrate accumulation via nitrification in RAS is often observed during the operation, which is usually solved by replacing with the fresh water into the system. With the concern of water consumption, bio-electrochemical system (BES) is introduced in this study to realize simultaneous nitrate removal for the system while generating the electricity through electron transferring. A microbial fuel cell (MFC) with an anion exchange membrane (AEM) was constructed. The removal of nitrate from aquaculture water generated from RAS was achieved by nitrate migration across the AEM and heterotrophic denitrification in the anode chamber. To further investigate the potential application of BES in RAS, the cathode chamber was incubated with biofilm to do the nitrification while the denitrification processing in the anode chamber. The study gave a total inorganic nitrogen removal efficiency of 38.72% ± 4.99, and a COD removal of 86.09% ± 9.83. The average daily electricity generation was 67.98 A m-3 ± 13.91, and nitrate-nitrogen concentration remained at 21.02 ± 2.62 mg L-1 throughout the experiment. These results of treating aquaculture water indicate that BES has a potential to install within RAS for enhanced nitrogen removal. / MS

Electrodeposition is one of the main techniques for fabricating conductive parts with one or two dimensions in the micron size range. This technique is utilized to coat surfaces with protective films of several micrometers thickness or fabricate standalone microstructures. In this process, an electrochemical reaction occurs on the electrode surface by applying an electric voltage, called overpotential. Different electrochemical practices were presented in the literature to obtain kinetic parameters of an electrochemical reaction but most of these practices are hard to implement for the reactions occur on a microelectrode. Toward addressing this issue, the first part of the dissertation work presents a combined experimental and analytical method which can more appropriately provides for the kinetic measurement on a microelectrode. Another issue which occurs for electrodeposition on microscale recessed areas is the deviation of the profile of the deposition front from the substrate shape. Non-uniform deposition front usually obtains for a deposit evolved from a flat substrate with microscale size. Consequently, a subsequent precision grinding process is required to level the surface of the electrodeposited microparts. In order to remove the need for this subsequent process, in the second and third parts of the dissertation work, multiphysics modeling was used to study the effects of the fabrication parameters on the uniformity of the deposit surface and suggest a design strategy. Surface texture of the deposit is another parameter which depends on the fabrication parameters. Several important characteristics of the electrodeposited coating including its wettability depend on the surface texture. The next part of the dissertation work presents an experimental investigation and a theoretical explanation for the effects of the overpotential and bath concentration on the surface texture of the copper deposit. As a result of this investigation, a novel two-step electrodeposition technique is developed to fabricate a superhydrophobic copper coating. In the last part of the dissertation work, similar investigation to the previous sections was presented for the effects of the fabrication parameters on the crystalline structure of the deposit. This investigation shows that nanocrystalline and superplastic materials can be fabricated by electrodeposition if appropriate fabrication parameters are applied. / Ph. D.

De nombreux systèmes électrochimiques sont composés d'un grand nombre d'éléments électroactifs en interaction. Si la réaction électrochimique possède une cinétique non linéaire, des comportements coopératifs complexes peuvent émerger suivant la nature et l’intensité des interactions entre les éléments du système. L'objectif de cette thèse est de comprendre l'influence de la taille finie de l’électrode et des interactions entre les microélectrodes sur le comportement coopératif d'un groupe de microélectrodes de platine soumis à un couplage global. Les réactions choisies pour cette étude sont l’électrooxydation du monoxyde de carbone (CO), une réaction avec une cinétique bistable et l’électrooxydation du formaldéhyde (HCHO), qui présente des oscillations de potentiel sous contrôle galvanostatique. Au cours de l’électrooxydation galvanodynamiques du CO sur une seule microélectrode de Pt, la branche S-NDR a pu être mise en évidence contrairement au comportement observé sur une macroélectrode de Pt. En outre, les nouveaux comportements coopératifs comme l'activation séquentielle des microélectrodes, des oscillations de courant et de potentiel spontanées et un régime de commutation dynamique entre les électrodes ont été découverts pour cette réaction lorsque quatre électrodes ont été couplées globalement. Pendant l’électrooxydation de HCHO, l'introduction du couplage global à deux électrodes conduit à des oscillations de courant en opposition de phase. / Many electrochemical systems are composed of a large number of interacting electroactive elements. If the reaction taking place on them has nonlinear kinetics and their interactions allow them to exchange information, complex cooperative behaviors can emerge. The objective of this thesis is to understand the influence of finite-size effects and cooperative phenomena on the global behavior of a group of coupled Pt microelectrodes. The reactions chosen for this study were CO electrooxidation, a reaction with current bistability, and HCHO electrooxidation, which exhibits oscillations under galvanostatic control. During the galvanodynamic electrooxidation of CO on a single microelectrode the S-NDR branch could be evidenced, on macroelectrodes this is not possible due to the formations of stationary domains. Additionally, novel cooperative behaviors (i.e., sequential activation, oscillations and complex switching) were discovered for this reaction when four electrodes were globally coupled. During HCHO electrooxidation the introduction of global coupling to two electrodes led to anti-phase current oscillations.

Electrochemical systems, which rely on coupled phenomena of the chemical change and electricity, have been utilized for development an interface between biological systems and conventional electronics.  The development and detailed understanding of the operation mechanism of such interfaces have a great importance to many fields within life science and conventional electronics. Conducting polymer materials are extensively used as a building block in various applications due to their ability to transduce chemical signal to electrical one and vice versa. The mechanism of the coupling between the mass and charge transfer in electrochemical systems, and particularly in conductive polymer based system, is highly complex and depends on various physical and chemical properties of the materials composing the system of interest. The aims of this thesis have been to study electrochemical systems including conductive polymer based systems and provide knowledge for future development of the devices, which can operate with both chemical and electrical signals. Within the thesis, we studied the operation mechanism of ion bipolar junction transistor (IBJT), which have been previously utilized to modulate delivery of charged molecules. We analysed the different operation modes of IBJT and transition between them on the basis of detailed concentration and potential profiles provided by the model. We also performed investigation of capacitive charging in conductive PEDOT:PSS polymer electrode. We demonstrated that capacitive charging of PEDOT:PSS electrode at the cyclic voltammetry, can be understood within a modified Nernst-Planck-Poisson formalism for two phase system in terms of the coupled ion-electron diffusion and migration without invoking the assumption of any redox reactions. Further, we studied electronic structure and optical properties of a self-doped p-type conducting polymer, which can polymerize itself along the stem of the plants. We performed ab initio calculations for this system in undoped, polaron and bipolaron electronic states. Comparison with experimental data confirmed the formation of undoped or bipolaron states in polymer film depending on applied biases. Finally, we performed simulation of the reduction-oxidation reaction at microband array electrodes. We showed that faradaic current density at microband array electrodes increases due to non-linear mass transport on the microscale compared to the corresponding macroscale systems.  The studied microband array electrode was used for developing a laccase-based microband biosensor. The biosensor revealed improved analytical performance, and was utilized for in situ phenol detection.