Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Kirby S. Chapman / The increasingly strict air emission regulations may require implementing Non-Selective Catalytic Reduction (NSCR) systems as a promising emission control technology for stationary rich burn spark ignition engines. Many recent experimental investigations that used NSCR systems for stationary natural gas fueled engines showed that NSCR systems were unable to consistently control the exhaust emissions level below the compliance limits. Part of this thesis is devoted to show the results from the field testing of three engines working in natural gas gathering stations located in the “Four Corners” area. These three engines are retrofitted with NSCR systems. Emissions and engine operating data were monitored for more than one year. Data collected from October 2007 through December 2008 shows significant variation in emissions levels over hours, days, and longer periods of time, as well as seasonal variations. As a result of these variations, simultaneous control of NOx and CO below the compliance limit was achieved less than fifty percent of the monitored time. Modeling of NSCR components to better understand, and then exploit, the underlying physical processes that occur in the lambda sensor and the catalyst media is now considered an essential step toward improving NSCR system performance. The second portion of this thesis focuses on modeling the lambda sensor that provides feedback to the air-to-fuel ratio controller. Correct interpretation of the sensor output signal is necessary to achieve consistently low emissions level. The goal of this modeling study is to improve the understanding of the physical processes that occur within the sensor, investigate the cross-sensitivity of various exhaust gas species on the sensor performance, and finally this model serves as a tool to improve NSCR control strategies. This model simulates the output from a planar switch type lambda sensor. The model consists of three modules. The first module models the multi-component mass transport through the sensor protective layer. Diffusion fluxes are calculated using the Maxwell-Stefan equation. The second module includes all the surface catalytic reactions that take place on the sensor platinum electrodes. All kinetic reactions are modeled based on the Langmuir-Hinshelwood kinetic mechanism. The third module is responsible for simulating the reactions that occur on the electrolyte material and determine the sensor output voltage. The details of these three modules as well as a parametric study that investigates the sensitivity of the output voltage signal to various exhaust gas parameters is provided in the thesis.

Composições cerâmicas de CaxSr1-xTi1-yFeyO3-&delta;, x = 0, 0,5 e 1,0, y = 0 e 0,35, foram preparadas por meio de síntese reativa de CaCO3, SrCO3, TiO2 e Fe2O3 e pela técnica dos precursores poliméricos. Os pós-cerâmicos foram avaliados por meio de análise térmica (termogravimétrica e térmica diferencial), difração de raios X e microscopia eletrônica de varredura. Compactos cerâmicos sinterizados foram analisados por difração de raios X, microscopia eletrônica de varredura, microscopia de varredura por sonda e espectroscopia de impedância. A força eletromotriz gerada entre duas faces paralelas de amostras cilíndricas foi monitorada na faixa de temperatura 600 - 1100 oC para pressão parcial de oxigênio de ~50 ppm, utilizando-se uma bomba eletroquímica de oxigênio com transdutores de zircônia estabilizada com ítria. Foram refinadas, por meio de análise de Rietveld as estruturas cristalinas determinadas na análise por difração de raios X: perovskita cúbica (x = 0) e perovskita ortorrômbica (x 0). A condutividade elétrica foi analisada por medidas de espectroscopia de impedância na faixa de freqüências 5 Hz-13 MHz da temperatura ambiente até ~200 C. A deconvolução dos diagramas de impedância [-Z\"() x Z\'()] na faixa de temperaturas 300 < T(K) < 500 mostra dois semicírculos atribuídos às contribuições intragranular (grãos) e intergranular (contornos de grão) à resistividade elétrica. Os compactos sinterizado utilizando pós preparados pela síntese de estado sólido apresentam valores de resistividade intergranular e intragranular maiores que os compactos preparados com pós obtidos pela síntese química. O sinal elétrico (força eletromotriz) gerado sob exposição a oxigênio mostra que esses compostos podem ser utilizados em dispositivos sensores de oxigênio entre 600 e 1100C. Análises topográficas em microscópio de varredura por sonda em superfícies polidas e atacadas termicamente mostram detalhes morfológicos dos grãos, permitindo concluir que compactos sinterizados preparados com pós obtidos pela rota química são menos porosos que os preparados com pós obtidos pela rota convencional de síntese de estado sólido. Estes resultados estão de acordo com os resultados de medidas de espectroscopia de impedância. / CaxSr1-xTi1-yFeyO3-&delta;, x = 0, 0.5 and 1.0, y = 0 and 0.35, ceramic compounds were synthesized by reactive solid state synthesis of CaCO3, SrCO3, TiO2 and Fe2O3, and by the polymeric precursor technique. The ceramic powders were evaluated by thermogravimetry and differential thermal analysis, X-ray diffraction and scanning electron microscopy. Sintered ceramic pellets were analyzed by X-ray diffraction, scanning electron microscopy, scanning probe microscopy and impedance spectroscopy. The electromotive force resulting from the exposing the pellets to partial pressure de oxygen in the ~50 ppm in the 600-1100 oC range was monitored using an experimental setup consisting of an oxygen electrochemical pump with yttria-stabilized zirconia transducer and sensor. Rietveld analysis of the X-ray data allowed for determining the crystalline structures: cubic perovskite (y = 0) and orthorhombic perovskite (y 0). The electrical conductivity was determined by the two probe impedance spectroscopy measurements in the 5 Hz-13 MHz frequency range from room temperature to approximately 200 C. The deconvolution of the [-Z\"() x Z\'()] impedance diagrams in the 300 < T(K) < 500 range shows two semicircles due to intragranular (bulk) and intergranular (grain boundary) contributions to the electrical resistivity. Sintered pellets using powders prepared by the ceramic route present higher inter- and intragranular resistivity values than pellets prepared with chemically synthesized powders. The emf signal under exposure oxygen shows that these compounds may be used in oxygen sensing devices in the 600 - 1100 C range. Scanning probe microscopy topographic analysis of the polished and thermally etched surfaces of the pellets gave details of grain morphology, showing that pellets prepared with powders synthesized by the chemical route are less porous than the ones obtained by the ceramic route. These results are in agreement with the impedance spectroscopy results.

Composições cerâmicas de CaxSr1-xTi1-yFeyO3-&delta;, x = 0, 0,5 e 1,0, y = 0 e 0,35, foram preparadas por meio de síntese reativa de CaCO3, SrCO3, TiO2 e Fe2O3 e pela técnica dos precursores poliméricos. Os pós-cerâmicos foram avaliados por meio de análise térmica (termogravimétrica e térmica diferencial), difração de raios X e microscopia eletrônica de varredura. Compactos cerâmicos sinterizados foram analisados por difração de raios X, microscopia eletrônica de varredura, microscopia de varredura por sonda e espectroscopia de impedância. A força eletromotriz gerada entre duas faces paralelas de amostras cilíndricas foi monitorada na faixa de temperatura 600 - 1100 oC para pressão parcial de oxigênio de ~50 ppm, utilizando-se uma bomba eletroquímica de oxigênio com transdutores de zircônia estabilizada com ítria. Foram refinadas, por meio de análise de Rietveld as estruturas cristalinas determinadas na análise por difração de raios X: perovskita cúbica (x = 0) e perovskita ortorrômbica (x 0). A condutividade elétrica foi analisada por medidas de espectroscopia de impedância na faixa de freqüências 5 Hz-13 MHz da temperatura ambiente até ~200 C. A deconvolução dos diagramas de impedância [-Z\"() x Z\'()] na faixa de temperaturas 300 < T(K) < 500 mostra dois semicírculos atribuídos às contribuições intragranular (grãos) e intergranular (contornos de grão) à resistividade elétrica. Os compactos sinterizado utilizando pós preparados pela síntese de estado sólido apresentam valores de resistividade intergranular e intragranular maiores que os compactos preparados com pós obtidos pela síntese química. O sinal elétrico (força eletromotriz) gerado sob exposição a oxigênio mostra que esses compostos podem ser utilizados em dispositivos sensores de oxigênio entre 600 e 1100C. Análises topográficas em microscópio de varredura por sonda em superfícies polidas e atacadas termicamente mostram detalhes morfológicos dos grãos, permitindo concluir que compactos sinterizados preparados com pós obtidos pela rota química são menos porosos que os preparados com pós obtidos pela rota convencional de síntese de estado sólido. Estes resultados estão de acordo com os resultados de medidas de espectroscopia de impedância. / CaxSr1-xTi1-yFeyO3-&delta;, x = 0, 0.5 and 1.0, y = 0 and 0.35, ceramic compounds were synthesized by reactive solid state synthesis of CaCO3, SrCO3, TiO2 and Fe2O3, and by the polymeric precursor technique. The ceramic powders were evaluated by thermogravimetry and differential thermal analysis, X-ray diffraction and scanning electron microscopy. Sintered ceramic pellets were analyzed by X-ray diffraction, scanning electron microscopy, scanning probe microscopy and impedance spectroscopy. The electromotive force resulting from the exposing the pellets to partial pressure de oxygen in the ~50 ppm in the 600-1100 oC range was monitored using an experimental setup consisting of an oxygen electrochemical pump with yttria-stabilized zirconia transducer and sensor. Rietveld analysis of the X-ray data allowed for determining the crystalline structures: cubic perovskite (y = 0) and orthorhombic perovskite (y 0). The electrical conductivity was determined by the two probe impedance spectroscopy measurements in the 5 Hz-13 MHz frequency range from room temperature to approximately 200 C. The deconvolution of the [-Z\"() x Z\'()] impedance diagrams in the 300 < T(K) < 500 range shows two semicircles due to intragranular (bulk) and intergranular (grain boundary) contributions to the electrical resistivity. Sintered pellets using powders prepared by the ceramic route present higher inter- and intragranular resistivity values than pellets prepared with chemically synthesized powders. The emf signal under exposure oxygen shows that these compounds may be used in oxygen sensing devices in the 600 - 1100 C range. Scanning probe microscopy topographic analysis of the polished and thermally etched surfaces of the pellets gave details of grain morphology, showing that pellets prepared with powders synthesized by the chemical route are less porous than the ones obtained by the ceramic route. These results are in agreement with the impedance spectroscopy results.

En la presente tesis se desarrolla un sistema de control de la mezcla de aire y gasolina en un motor alternativo de cuatro tiempos, basado en redes neuronales. Para que el catalizador logre un grado de depuración aceptable con todos los gases contaminantes simultáneamente, debe mantenerse la proporción de aire y combustible, dentro de una banda muy estrecha. En estado estacionario, este objetivo se cumple sin demasiados problemas, pero el funcionamiento habitual de un vehículo es en régimen muy transitorio, donde los sistemas convencionales no logran evitar desviaciones importantes del punto de consigna. Estos se basan además en una gran cantidad de tablas estáticas, que deben calibrarse de forma experimental, lo cual es bastante costoso tanto en tiempo como en dinero.Para evitar estos problemas se ha diseñado un modelo matemático de un motor, que comprende todo el proceso de formación de la mezcla, sensores, la generación del par motor y la dinámica del vehículo. La realización final se ha realizado en el lenguaje de simulación MatLab/Simulink®. Los datos requeridos son fácilmente obtenibles bien por metrología, bien de forma experimental. Se ha validado con un motor SEAT de 1,6 l y 74 kW.Como primer paso se ha aplicado una estrategia de control convencional bastante simple, consistente en un controlador feedforward estático, más un controlador feedback de tipo PI ó PID. Esto ha permitido el estudio de las principales características del motor desde el punto de vista de control. Con los resultados obtenidos se ha diseñado un observador basado en una red neuronal, que elimine los retardos puros del sistema y que pueda ser utilizado para cerrar el lazo de control. Primero se ha usado una red feedforward, pero vistos los malos resultados, se ha desarrollado una red neuronal recurrente a partir de la red de Elman, que se ha modificado convenientemente para adaptarla a las dificultades propias del problema. El algoritmo de entrenamiento utilizado se basa en el de retropropagación clásico, y modifica no sólo los pesos entre capas, sino también los correspondientes a las neuronas de contexto, las cuales permiten memorizar estados internos. La principal mejora consiste en separar las neuronas de contexto en tantos grupos como entradas tiene la red, y entrenarlos por separado, de modo que cada grupo se adapte a la dinámica particular de la entrada a la que va asociado. Se muestra mediante simulación el comportamiento del conjunto motor más observador en lazo cerrado, y se compara con el esquema convencional. Se prueba asimismo la robustez del sistema frente a distintas consignas, ruido en la planta y defectos de sintonía. / In the present thesis a control system for the air-fuel mixture in a reciprocating four-stroke engine is developed, based on neural networks. The air-fuel ratio has to be kept within a very narrow window so that the catalyst achieves an acceptable degree of purification simultaneously with all the polluting gases. In steady state, this goal can be fulfilled without difficulties, but the usual operation of a vehicle is in a very transient state, where the conventional systems are not able to avoid important excursions from the set point. They also rely on a great number of look-up tables, which have to be tuned experimentally, thus with an enormous investment of money and time.To avoid those problems a mathematical model of an engine has been designed, in such a way that it comprises of the whole mixture formation process, sensors, the torque generation and the vehicle dynamics. Finally it has been implemented in the simulation language MatLab/Simulink®. The required data is easily available both from metrology, and experimental work. It has been validated with a 1,6 litre 74 kW SEAT engine.As a first step, a quite simple conventional control strategy has been applied, consisting of a static feedforward controller, and a PI or PID feedback controller. This has permitted studying the main features of the engine from the control point of view.With the obtained results an observer based on a neural network has been designed, which eliminates the delays of the system and that can be used to close the control loop. First a feedforward network has been used, but due to the bad results, a recurrent neural network has been developed starting from the Elman network, which has been properly modified in order to adapt it to the characteristic difficulties of the problem. The training algorithm used is based on that of classical backpropagation, and it modifies not only the weights interconnecting different layers, but also those corresponding to the context neurons, which allow the memorising of internal states. The main improvement consists in separating the context neurons in as many groups as the network has inputs, and to train them separately, so that each group adapts to the particular dynamics of the input with which it is associated. The behaviour of the engine plus the observer in closed loop is shown by means of simulation, and is compared with the conventional scheme. It is proven the robustness of system response to different set points, noise in the plant and tuning defects.