Made available in DSpace on 2014-10-09T12:33:59Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:55Z (GMT). No. of bitstreams: 0 / O material (pó) de nanofase de Ce0,9W0,1O2 foi sintetizado por coprecipitação de oxalatos de cério (IV) e cátions de tungstênio (IV). A redução da platina (2%) foi feita pelo método da redução por álcool, utilizando uma solução de ácido hexacloroplatínico (H2PtCl6.6H2O) como fonte do metal, óxido de cério dopado com tungstênio (Ce0,9W0,1O2) utilizado como suporte e, uma solução de etilenoglicol/água (75/25, v/v) como solvente e agente redutor. Os materiais 2%Pt-Ce0,9W0,1O2 foram misturados em Pt/C E-TEK 20%, utilizando-se processo de mistura física para produzir os eletrocatalisadores de 20%Pt-(2%Pt-Ce0,9W0,1O2)/C. Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX) acoplado à microscopia eletrônica de varredura (MEV), análises de difração de raios X (DRX), e microscopia eletrônica de transmissão (MET). O conjunto eletrodos-membrana (MEAs) foram preparados para o ânodo com cargas iguais a 0,401, 0,364, 0,328 mg Pt cm-2 de eletrocatalisadores 20%Pt-(2%Pt-Ce0,9W0,1O2)/C produzidos. No cátodo foi usada uma carga de 0,4 mg Pt cm-2 de eletrocatalisador Pt/C ETEK. A polarização anódica foi realizada para oxidação de H2/CO (100 ppm de CO). A tolerância ao CO foi estudada utilizando o processo eletroquímico (stripping de CO e medidas de curvas de polarização). Os resultados obtidos mostraram que a oxidação de CO adsorvido a CO2 na superfície de platina ocorre em potenciais menos positivos mostrando tolerância ao CO adsorvido nestes eletrocatalisadores (20%Pt-(2%Pt-Ce0,9W0,1O2)/C (50:50, 60:40 e 70:30)) a uma temperatura de 85 ºC e com pressão absoluta de 2 bar para ânodo e cátodo, comparado com Pt/C E-TEK 20%. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:34:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:29Z (GMT). No. of bitstreams: 0 / As formulações de eletrocatalisadores Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C foram preparados pelo método da redução por álcool e caracterizados por difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). A tolerância ao CO foi estudada utilizando o stripping de CO e medidas de curvas de polarização em células unitárias alimentadas com misturas de H2/CO no ânodo e oxigênio no cátodo, na temperatura de 80ºC e pressão absoluta de 2 bar para ânodo e cátodo. Os testes em células a combustível tipo PEMFC mostraram que a oxidação do CO adsorvido a CO2 na superfície da platina ocorre em potenciais menos positivos quando comparado com o catalisador comercial, Pt/C Etek, mostrando tolerância ao CO adsorvido nos eletrocatalisadores de Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:36Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:29Z (GMT). No. of bitstreams: 0 / Os eletrocatalisadores Pt/C, PtBi/C, PtRu/C e PtRuBi/C foram preparados a partir do método de redução via borohidreto de sódio e testados na oxidação eletroquímica de etanol. No método de redução via borohidreto, adiciona-se uma solução contendo hidróxido de sódio e borohidreto de sódio a uma mistura contendo água/2-propanol, precursores metálicos e o suporte de carbono Vulcan XC72. Neste trabalho também foi estudada a forma de adição da solução de borohidreto (adição gota a gota ou adição rápida). Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX), análise termogravimétrica (TGA), difração de raios X (DRX), microscopia eletrônica de transmissão (MET) e voltametria cíclica. A eletro-oxidação do etanol foi estudada por voltametria cíclica e cronoamperometria utilizando a técnica do eletrodo de camada fina porosa. Os eletrocatalisadores obtidos foram avaliados em condições reais de operação em célula por meio de testes em células unitárias alimentadas diretamente por etanol. A dissolução de bismuto no eletrocatalisador PtRuBi/C foi avaliada pelas técnicas de voltametria cíclica, cronoamperometria e do eletrodo disco-anel. O eletrocatalisador PtRuBi/C aparentemente mostrou um bom desempenho para a eletro-oxidação do etanol, porém as evidencias experimentais indicam a dissolução do bismuto em meio ácido. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Este trabalho apresenta resultados de estudos e caracterizações de Conjuntos Eletrodo/Membrana (MEAs) de Células a Combustível a Membrana Polimérica (PEMFC). Algumas condições de operação de células e diferentes processos de produção de MEA foram investigados. A técnica de Espectroscopia de Impedância Eletroquímica (EIE) (em situ - 0 a 16 A) foi usada \"on-line\" como uma ferramenta de diagnóstico, relativa ao desempenho de célula. As medidas de EIE foram feitas através do Sistema de EIE para células a combustível FC350 (GAMRY), junto a um PC4 Potentiostato/Galvanostato e conectado à carga dinâmica (TDI) para experimentos de EIE \"on-line\" (100 mHz - 10 kHz, dU = 5 mV). MEAs com 25 cm2 de área ativa, usando eletrocatalisadores PtM/C 20 % (M = Ru, Sn ou Ni) fabricados usando o Método de Redução por Álcool (MRA). A tinta catalítica foi diretamente aplicada no Tecido de Carbono (GDL) e este prensado na membrana de Nafion® (105). MEAs usando eletrocatalisadores Pt/C e PtRu/C 20 % da E-TEK foram fabricados para comparação. Todos os cátodos foram confeccionados com Pt/C 20% da E-TEK. Foram fixadas as concentrações de metal nobre em 0,4 mg Pt.cm-2 no anodo e 0,6 mg Pt.cm-2 no catodo (E-TEK). Diagramas de Nyquist dos MEAs com Pt/C e PtRu/C da E-TEK ou PtM/C MRA apresentaram as mesmas resistências de ôhmicas para os MEAs. Este fato pode ser explicado por supressão de aglomerados durante o processo de preparação do MEA ou pela homogeneidade do eletrocatalisador ancorado ao carbono. Também pôde ser observado, a baixas densidades atuais que há uma diferença de desempenho significante entre o eletrocatalisadores da ETEK e os preparados pelo MRA. Os resultados das curvas de polarização confirmaram que PtM/C MRA apresentara um aumento de atividade para as células alimentadas com metanol e etanol. A técnica de EIE se mostrou eficiente para a avaliação do método de preparação dos MEAs e do desempenho da célula, os resultados de EIE mostraram uma coerência na escolha do modelo do circuito elétrico para os MEAs utilizando hidrogênio, metanol e etanol. Esta coerência indica que outras resistências não consideradas no modelo não são relevantes na resistência total dos MEAs. / This work reports results of studies and characterization on Membrane Electrode Assemblies (MEAs) for Proton Exchange Membrane Fuel Cell (PEMFC). Some cell operation conditions and different processes of MEA production were investigated. The Electrochemical Impedance Spectroscopy Technique (EIS) (in situ - 0 to 16 A) was used \"on-line\" as a tool for diagnosis, concerning the cell performance. The EIS measurements were carried out with a FC350 Fuel Cell EIS System (GAMRY), coupled to a PC4 Potentiostat/Galvanostat and connected to the electronic load (TDI) for \"on-line\" EIS experiments (100 mHz - 10 kHz, dU = 5 mV). MEAs with 25 cm2 surface area, using PtM/C 20% (M = Ru, Sn or Ni) electrocatalysts were manufactured using the Alcohol Reduction Process (ARP). The catalytic ink was applied directly into the Carbon Cloth (GDL) and pressed in the NafionR membrane (105). MEAs using Pt/C and PtRu/C 20% from E-TEK electrocatalysts were manufactured by comparison. All the cathodes were sprayed with Pt/C 20% from E-TEK. The noble metal concentrations used were set to 0.4 mg Pt.cm-2 at the anode and 0.6 mg Pt.cm-2 at the cathode (E-TEK). Nyquist diagrams of the MEAs with Pt/C and PtRu/C from E-TEK or PtM/C (M = Ru, Sn or Ni) ARP showed essentially the same ohmic resistances for the MEAs. This fact can be explained by suppression of agglomerates during the MEA preparation process or by the homogeneity of the anchored electrocatalysts at the carbon surface. It could also be observed, at low current densities, that there was a significant performance difference between the electrocatalysts from E-TEK and those prepared with the Alcohol Reduction Process. The polarization curves results confirmed that the PtM/C (M = Ru, Sn or Ni) ARP showed an activity increase for the methanol and ethanol fed cells. The technique of EIE was shown efficient for the evaluation of the method preparation of MEAs and the acting of the cell, the results of EIE showed coherence in the choice of the model the electric circuit for MEAs using hydrogen, methanol and ethanol. This coherence indicates that other resistances no considered in the model are not relevant in the total resistance of MEAs.

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.

As foodstuffs are being produced, transported and stored in greater quantities than ever before in human history and with an alarming amount of food products being lost to spoilage every year, new, environmentally friendly ways of preserving food products are being actively researched and developed in today’s world. Oxygen is a key pathway towards food decay and destruction, due to its dual roles as a source of respiration for the multitude of microorganisms that can cause food spoilage and through direct destruction through oxidation reactions within food products that cause oxidative deterioration. Fuel cells have the theoretical potential to be an energy efficient and environmentally friendly way of preserving food, such as fish, fruit and vegetables.  Because of their nature to consume oxygen through the electrochemical reactions that produces their electrical power, they have the potential to be used to reduce localised oxygen content for the storage and transportation of foods, minimising their spoilage, as well as potentially providing electrical energy for other components in potential control systems for the fuel cell. The purpose of this project is to design and build a PEM fuel cell and examine its potential for lowering of oxygen concentrations at the gas output at the cathode.  The outcome of these experiments are designed to validate the  theoretical capacity of fuel cells to reduce output oxygen concentrations to levels that are able to aid in the preservation of foodstuffs.  It is hoped that this study, in conjunction with the researched literature, can be used as a guide for future food shipping and storage methods. The experimental stage of this diploma work was unsatisfactory. The fuel cell was unable to produce a voltage and the reactant gases were unable to flow through the fuel cell due to a design flaw. Therefore the effectiveness of a fuel cell for depletion of oxygen to levels able to preserve food is based on the theoretical basis of the internal PEM fuel cell reactions, as well as studying past literature and patents. If the theoretical ability of the fuel cell is proven, it can be asserted that PEM fuel cells have the potential to be a real contender in the field of food preservation in shipping and storage, as well as offering greater levels of control for supplies for how and when they can ship their product. However this will require more independent research development work on the effects of low oxygen concentrations on a fuel cell operation as well as the preservation effects on a greater variety of foodstuffs. Furthermore, more research is required for more efficient and cheaper fuel cell catalysts or innovative designs are required to avoid concentration losses that arise from oxygen reduction at low oxygen levels.

[ES] Las pilas de combustibles son dispositivos de un coste elevado y frágiles ante ambientes contaminados o condiciones inadecuadas de operación como: temperaturas extremas o mala gestión del agua producida como residuo de la pila. Para mejorar la fiabilidad de una pila de combustible es necesario diagnosticar de una manera oportuna los fallos y así evitar daños que reduzcan el desempeño del módulo o que lo inhabiliten. Este trabajo busca contribuir al mejoramiento de la fiabilidad de las pilas de combustible de baja temperatura y de esta forma favorecer el uso de hidrógeno en la transición a una energía descarbonizada. Para lograrlo, se realizaron tres actividades principales: modelado de una pila de hidrógeno, ajuste paramétrico del modelo desarrollado y, por último, aplicación de técnicas de diagnóstico de fallos basados en modelos. En el laboratorio de Recursos Energéticos Renovables Distribuidos LabDER de la Universitat Politècnica de València, se estudia el desempeño de sistemas híbridos renovables, incluyendo una línea de hidrógeno, desde la producción, almacenamiento y reconversión en electricidad en una pila de combustible, por tanto, se ha podido validar el modelo. En un primer momento se identificó la necesidad de un modelo que emplee la temperatura como señal de salida y que retroalimente el sistema, y que tuviese en cuenta señales propias del módulo comercial; sin embargo, el uso de la temperatura como señal y la no linealidad de las ecuaciones físicas, químicas, eléctricas y empleadas, generan un modelo altamente complejo. El ajuste paramétrico del modelo se realizó empleando algoritmos de optimización. Tomando como base al algoritmo de Enjambre de Partículas, se desarrolló una nueva propuesta llamada Scout GA, este algoritmo fue utilizado en otras aplicaciones y pruebas de convergencia para verificar su desempeño frente al fenómeno de estancamiento prematuro y logrando mejorar la precisión y velocidad de convergencia de otras propuestas. Como resultado de la validación de este modelo, en una primera simulación usando datos reales de funcionamiento correspondientes a 1500 segundos, el error de simulación fue del 2,21% en la señal de tensión y del 1,97% en la señal de temperatura, obteniendo un error medio del 2,09%. En un segundo conjunto de datos de algo más de 2.500 segundos de funcionamiento, el error de simulación fue del 2,40% y del 1,96% para las señales de tensión y temperatura, respectivamente. Se estima que el error medio de simulación para ambas señales y condiciones de funcionamiento similares es inferior al 2,5%. Buscando mejorar la fiabilidad de la pila, se realizó el trabajo de diagnóstico de fallos, este partió de la simulación de fallos, mediante la modificación de algunas señales de entrada del modelo, los fallos se caracterizaron mediante el tratamiento estadístico de 12 residuos, obteniendo firmas de fallos, que, en su conjunto, formaron una matriz de fallos. Luego, un algoritmo de diagnóstico propuesto permitió identificar y aislar 14 fallos. permitiendo concluir que, el modelo predice eficazmente los fallos de las pilas PEMFC y podría extrapolarse a otras pilas de combustible. / [CA] Les piles de combustibles són dispositius d'un cost elevat i fràgils davant ambients contaminats o condicions inadequades d'operació com: temperatures extremes o dolenta gestió de l'aigua produïda com a residu de la pila. Per a millorar la fiabilitat d'una pila de combustible és necessari diagnosticar d'una manera oportuna les fallades i així evitar danys que reduïsquen l'acompliment del mòdul o que l'inhabiliten. Este treball busca contribuir al millorament de la fiabilitat de les piles de combustible de baixa temperatura i d'esta manera afavorir l'ús d'hidrogen en la transició a una energia *descarbonizada. Per a aconseguir-ho, es van realitzar tres activitats principals: modelatge d'una pila d'hidrogen, ajust paramètric del model desenvolupat i, finalment, aplicació de tècniques de diagnòstic de fallades basades en models. En el laboratori de Recursos Energètics Renovables Distribuïts *LabDER de la Universitat Politècnica de València, s'estudia l'acompliment de sistemes híbrids renovables, incloent-hi una línia d'hidrogen, des de la producció, emmagatzematge i reconversió en electricitat en una pila de combustible, per tant, s'ha pogut validar el model. En un primer moment es va identificar la necessitat d'un model que empre la temperatura com a senyal d'eixida i que retroalimente el sistema, i que tinguera en compte senyals propis del mòdul comercial, no obstant això, l'ús de la temperatura i la no linealitat de les equacions físiques, químiques, elèctriques i tèrmiques empleades, deriven en un model altament complex. L'ajust paramètric del model de pila de combustible es va realitzar emprant algorismes d'optimització. Prenent com a base a l'algorisme d'Eixam de Partícules, es va desenvolupar una nova proposta anomenada Scout GA, aquest algorisme va ser utilitzat en altres aplicacions i proves de convergència per a verificar el seu acompliment enfront del fenomen d'estancament prematur i aconseguint millorar la precisió i velocitat de convergència d'altres propostes. La simulació i identificació del model té un cost computacional entre 7 i 20 ms per iteració, on es van aconseguir errors de simulació menors al 2.5% Com a resultat de la validació d'aquest model, en una primera simulació usant dades reals de funcionament corresponents a 1500 segons, l'error de simulació va ser del 2,21% en el senyal de tensió, del 1,97% en el senyal de temperatura i un error mitjà del 2,09%. En un segon conjunt de dades d'una mica més de 2.500 segons de funcionament, l'error de simulació va ser del 2,40% i del 1,96% per als senyals de tensió i temperatura, respectivament. S'estima que l'error mitjà de simulació per a tots dos senyals i condicions de funcionament similars és inferior al 2,5%. Buscant millorar la fiabilitat de la pila, es va fer el treball de diagnòstic de fallades, aquest va partir de la simulació de fallades, mitjançant la modificació d'alguns senyals d'entrada del model, les fallades es van caracteritzar mitjançant el tractament estadístic de 12 residus, obtenint signatures de fallades, que en el seu conjunt, van formar una matriu de fallades. després un algorisme de diagnòstic proposat, va permetre identificar i aïllar 14 fallades. Permetent concloure que, el model prediu eficaçment les fallades de les piles PEMFC i podria extrapolar-se a altres piles de combustible. / [EN] Fuel cells are high-cost devices that are fragile in contaminated environments or in inadequate operating conditions, such as extreme temperatures or poor water management, produced as battery waste. To improve the reliability of a fuel cell, it is necessary to diagnose failures promptly and thus avoid damage that reduces the module's performance or disables it. This work seeks to contribute to improving the reliability of low-temperature fuel cells and thus promote the use of hydrogen in the transition to decarbonized energy. To achieve this, three main activities were carried out: modeling a hydrogen fuel cell, parametric adjustment of the developed model, and application of model-based fault diagnosis techniques. In the LabDER Distributed Renewable Energy Resources laboratory of the Polytechnic University of Valencia, the performance of renewable hybrid systems is studied, including a hydrogen line, from production, storage, and reconversion into electricity in a fuel cell, therefore, has been able to validate the model. Initially, a fuel cell model that uses temperature as an in/output signal is required. Also, the model must be able to use the reals signals supplied for the commercial module. However, using temperature and an equation set that includes the non-linearity of the physical, chemical, electrical, and thermal equations resulted in a highly complex model. The parametric adjustment of the fuel cell model was performed using optimization algorithms. Based on the Particle Swarm algorithm, a new proposal called Scout GA was developed. This algorithm was used in other applications and convergence tests to verify its performance against the premature stagnation phenomenon and improved the accuracy and speed of convergence of other proposals. The simulation and identification of the model have a computational cost between 7 and 20 ms per iteration, where simulation errors of less than 2.5% were achieved. As a result of the validation of this model, in a first simulation using real operating data corresponding to 1,500 seconds, the simulation error was 2.21% for the voltage signal, 1.97% for the temperature signal, and an average error of 2.09%. In a second data set for slightly more than 2500 seconds of operation, the simulation error was 2.40% and 1.96% for the voltage and temperature signals, respectively. The average simulation error for both signals and similar operating conditions is estimated to be less than 2.5%. To improve the reliability of the stack, the fault diagnosis work was carried out, starting from the simulation of faults by modifying some input signals of the model; the faults were characterized by the statistical treatment of 12 residuals, obtaining fault signatures, which formed a fault matrix. Then, a proposed diagnostic algorithm allowed to identify and isolate 14 faults. Allowing to conclude that the model effectively predicts the PEMFC stack faults and could be extrapolated to other fuel cells. / Ariza Chacón, HE. (2024). Contribuciones al modelado y diagnóstico de fallos en PEMFC para mejorar la fiabilidad en sistemas híbridos renovables [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203614

Les membranes fluorées sont utilisées en particulier dans les dénommées piles à combustible à membrane électrolyte polymère. Grâce à sa grande mobilité en protons, le célèbre ionomer Nafion® (Dupont) est un matériau de référence pour les applications liées aux piles à combustible. En présence d’eau ou d’autres solvants hydrophiles la membrane se sépare en une matrice polymérique hydrophobe et une sous-phase aqueuse contenant des clusters d’eau et ions, dont les tailles et la connectivité augmente quand la quantité d’eau augmente [1]. Quelle est la morphologie du Nafion et la structure du solvant, dans de tels systèmes?Il a été récemment montré [2] sur des simulations de large systèmes que plusieurs modèles morphologiques reproduisent les données expérimentales de diffusion, évoquant l’incapacité des mesures de diffusion seules à élucider la véritable structure du Nafion.Néanmoins, un modèle ’aléatoire’ décrit dans [2], c’est à dire l’unique modèle étudié sans présumer d’une structure initiale particulière, n’a pas pu reproduire les données expérimentales.Générer en simulations moléculaires des configurations du système qui soient vraiment décorrélées de la configuration initiale reste un vrai défi statistique. Les échelles de temps réalisables ne permettent simplement pas d’obtenir des mouvements significatifs du polymère (comme des transitions de conformations, repliements de chaînes, etc.). Nous proposons ainsi dans cette étude un nouveau modèle de Nafion à morphologie aléatoire. Un algorithme récemment développé est utilisée pour générer des chaînes de Nafion avec des chemins et des points de départ aléatoires. Une différence majeure avec le modèle aléatoire dans [2] est que nous ne construisons pas nos systèmes à une densité proche de la densité finale. Pour ne pas démarrer avec des chaînes trop enchevêtrées, les systèmes sont initialement préparés à une densité en dessous de la référence expérimentale. La densité après équilibration est de nouveau proche de l’expérience. Bien qu’il soit facilement envisageable d’améliorer les nouveaux algorithmes, nous démontrons ici qu’avec la présente version plusieurs séries de configurations compatibles avec les données expérimentales de diffusion disponibles peuvent être générées et équilibrées. Douze large systèmes de Nafion à morphologie aléatoire sont construits avec des positions initiales des atomes ainsi que des quantités d’eau et des longueurs de chaînes (Nafion/Hyflon) différentes. Ils sont équilibrés puis simulés sur plusieurs dizaines de nanosecondes. Après équilibration, les structures sont, comme indiqué ci-dessus,compatibles avec les données expérimentales de diffusion. En plus nous étudions un modèle ressemblant à celui de Schmidt-Rohr and Chen [3], c’est à-dire le plus récent modèle morphologique. Avec ce modèle, les données expérimentales sont également reproduites de manière satisfaisante, d’où la prolongation du débat sur la structure du Nafion. La cohésion entre les valeurs calculées et celles mesurées expérimentalement incite à des analyses plus en détails de ces configurations obtenues. Nous caractérisons et analysons les structures locales, intermédiaires et à grande échelle avec divers paramètres structuraux et distributions des tailles de domaines. Nous calculons donc, par exemple, des fonctions de distribution radiale (rdf), des facteurs de structure (S(q)) totaux et partiels tout comme des nombres et des tailles de clusters hydrophiles (selon la définition d’un cluster). La dynamique de diverses espèces dans le système est également examinée,par exemple au travers des déplacements carrés moyens (msd) et des coefficients de diffusion. Ces simulations sont probablement à la limite de ce qui est réalisable aujourd’hui avec des simulations ’full-atom’ du type MD. Nous espérons que ce travail fera avancer le débat sur la structure et la dynamique de ces matériaux importants. / Perfluorinated membranes are used in particular in polymer electrolyte fuel cells(PEFC). The well-known ionomer Nafion® (Dupont) is, due to its high proton mobility,a reference material for fuel cell applications. In water or other hydrophilic solvents themembrane segregates into a hydrophobic backbone matrix and a hydrophilic sub-phasecontaining clusters of both water and ions, where the cluster sizes and connectivity increasewith increasing water content [1].What is the Nafion morphology and the structure of the solvent in such systems? It hasbeen shown recently [2] on large simulated systems that several morphological modelsfit the experimental scattering data, suggesting the inability of scattering experimentsalone to elucidate the true structure of Nafion. However, a ’random’ model describedin [2], i.e. the only explored model that did not assume a particular initial structure,could not reproduce the experimental data.It remains a real computational challenge to generate in molecular simulations systemconfigurations which are really decorrelated from the initial one. The time scales thatcan be achieved simply do not allow to obtain significant motions of the polymer (e.g.conformational changes, folding, etc.). We thus propose in this work a new randommodel of Nafion. A newly developped algorithm is used to generate Nafion chains withrandom growth paths and random starting points. A significant difference with therandom model in [2] is that we do not build our systems at a density close to the finalone. In order not to start with too much entangled chains, the systems are initiallybuilt at a density below the experimental one. The density after equilibration is againclose to the experimental one.Even though further improvements of the new algorithms can easily be envisaged,we demonstrate here that with the present version several sets of configurations thatare compatible with the available scattering data can be generated and equilibrated.Twelve large random Nafion systems are built with different initial positions of theatoms as well as different water contents and side chain lengths (Nafion/Hyflon). Theyare equilibrated and then simulated for several ten nanoseconds. After equilibration,the structures are, as mentioned, compatible with the experimental scattering data. Inaddition we study a model similar to the one by Schmidt-Rohr and Chen [3], i.e. thenewest morphological model of Nafion. The experimental scattering data are also satisfactorilyreproduced with this model, hence, the prolonged debate over the structureof Nafion.This agreement gives confidence that a more detailed analysis of the so-obtained configurationsis scientifically warranted. We characterize and analyze the local, intermediateand large-scale structures by various structural parameters and domain size distributions.We therefore compute, for example, radial distribution functions (rdf), total andpartial structure factors (S(q)) as well as numbers and sizes of hydrophilic clusters (dependingon the definition of a cluster). The dynamics of various species in the systemis also investigated, e.g. via the computation of the mean square displacements (msd)and the self-diffusion coefficients. These simulations are probably at the limit of whatcan today be achieved with all-atom molecular simulations of the MD type. We hopethat this work will advance the ongoing debate on the structure and dynamics of theseimportant materials. / Perfluorierte Membranen werden insbesondere in Polymerelectrolyt-Brennstoffzellen(PEFC) eingesetzt. Das wohlbekannte Ionomer Nafion® (Dupont) ist wegen seinerhohen Protonenbeweglichkeit ein Referenzmaterial für solche Anwendungen in Brennstoffzellen.Die Membran separiert in Wasser oder anderen hydrophilen Lösungsmittelin eine hydrophobe Polymermatrix und eine hydrophile Subphase, die Cluster mitWasser und Ionen enthält. Dabei vergroeßern sich die Ausdehnung der Cluster und ihreKonnektivität mit zunehmendem Wassergehalt [1].Welche ist die Morphologie des Nafions und die Struktur des Lösungsmittels in diesenSystemen? Es ist jüngst anhand großer simulierter Systeme gezeigt worden [2], dassmehrere morphologische Modelle die experimentellen Streudaten wiedergeben können,was nahelegt, dass solche Streudaten alleine nicht geeignet sind, die wahre Strukturdes Nafion aufzudecken. Ein in [2] beschriebenes ’Zufallsmodell’, d.h. das einzigeder untersuchten Modelle, das keine besondere Anfangsstruktur annahm, konnte dieexperimentellen Daten allerdings nicht wiedergeben.In molekularen Computersimulationen Konfigurationen zu erzeugen, die wirklich nichtmehr mit der angenommenen Anfangskonfiguration korreliert sind, bleibt eine echteHerausforderung. Die erreichbaren Zeitskalen sind zu kurz, um eine signifikante Bewegungdes Polymers (z.B Konformationsänderungen, Faltungen, usw.) zuzulassen. Indieser Arbeit wird daher ein neues Zufallsmodell für Nafion vorgestellt. Ein neuentwickelterAlgorithmus erzeugt Nafionketten mit zufälligem Wachstumspfad ausgehendvon zufälligen Anfangspunkten. Ein signifikanter Unterschied zu dem Zufallsmodellvon [2] ist, dass hier nicht versucht wird, die Systeme bei einer Dichte vergleichbarder experimentellen Dichte aufzubauen. Anstattdessen werden die Systeme, um alzustarkes Verknäuelung zu vermeiden, anfangs bei einer deutlich kleineren Dichte erzeugt.Nach äquilibrierung ist die Systemdichte wieder in etwa gleich der experimentellen.Wiewohl weitere Verbesserungen des neu Algorithmuses leicht ins Auge gefaßt werdenkönnen, so kann hier doch gezeigt werden, dass mit der gegenwärtigen VersionKonfigurationen erzeugt und äquilibriert werden können, die mit den verfügbarenStreudaten kompatibel sind. Zwölf große Nafion Zufallssysteme, mit verschiedenenAnfangspositionen der Atome, verschiedenem Wassergehalt und Längen der Seitenketten(Nafion/Hyflon) werden aufgebaut. Diese werden äquilibriert und mehrerezehn Nanosekunden lang simuliert. Nach der äquilibrierung sind die Strukturen, wieerwähnt, kompatibel mit den experimentellen Streudaten. Weiterhin wird ein Modellähnlich dem von Schmidt-Rohr und Chen [3], d.h. dem neuesten morphologischen Modellfür Nafion, studiert. Auch hier werden die experimentellen Streudaten zufriedenstellendwiedergegeben, daher die weiterhin bestehende Debatte über die Struktur desNafion.Die gefundenen übereinstimmungen lassen darauf vertrauen, dass eine detaillierte Analyseder simulierten Konfigurationen wissenschaftlich sinnvoll ist. So wird die Strukturder Systeme auf verschiedenen Längenskalen charakterisiert, zum Beispiel durch radialePaarverteilungsfunktionen (rdf), totale und partielle Strukturfaktoren (S(q)) sowieAnzahl- und Größenverteilungen hydrophiler Cluster (abhängig von der Definition einesClusters). Die Dynamik einzelner Spezies im System wird ebenfalls untersucht, zumBeispiel durch die Berechnung der mittleren quadratischen Verschiebungen (msd) undder Selbstdiffusionskoeffizienten. Diese Simulationen sind wahrscheinlich an der Grenzedessen, was heute mit ’all-atom’ molekularen MD-Simulationen möglich ist. Ich vertrauedarauf, dass diese Arbeit dennoch einen Fortschritt in der aktuellen Debatte überdie Struktur und Dynamik dieser wichtigen Materiale darstellt.

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology))--Vaal University of Technology. / Industrial countries, such as South Africa, rely heavily on energy sources to function profitably in today’s economy. Based on the 2008 fossil fuel CO2 emissions South Africa was rated the 13th largest emitting country and also the largest emitting country on the continent of Africa, and is still increasing. It was found that fuel cells can be used to generate electricity and that hydrogen is a promising fuel source. A fuel cell is an energy generation device that uses pure hydrogen (99.999%) and oxygen as a fuel to produce electric power. A regenerative fuel cell is a fuel cell that runs in reverse mode, which consumes electricity and water to produce hydrogen. This research was aimed at designing and constructing an optimised control system to control the hydrogen pressure in a proton exchange membrane regenerative fuel cell. The hydrogen generated by the fuel cell must be stored in order to be used at a later stage to produce electricity. A control system has been designed and constructed to optimise the hydrogen pressure control in a regenerative proton exchange membrane fuel cell. An experiment that was done to optimise the hydrogen system included the effects that the cathode chamber pressure has on the production of hydrogen and the most effective method of supplying hydrogen to a storage tank. The experiment also included the effects of a hydrogen buffer tank on the output hydrogen pressure and if the system can accommodate different output pressures. It was found that the cathode chamber pressure doesn’t need to be controlled because it has no effect on the rate of hydrogen produced. The results also showed that the flow of hydrogen need not to be controlled to be stored in a hydrogen storage tank, the best method is to let the produced hydrogen flow freely into the tank. The hydrogen produced was also confirmed to be 99.999% pure. The system was also tested at different output pressures; the control system successfully regulated these different output pressures.

A tecnologia de células a combustível associada à crescente exigência de baixo impacto ambiental tornou-se bastante promissora no cenário mundial de energia. As células a combustível são, em princípio, dispositivos que convertem energia química diretamente em energia elétrica e térmica, possuindo, entretanto, uma operação contínua, graças à alimentação constante de um combustível. Particularmente, o negro de fumo Vulcan XC72 é usualmente empregado como suporte dos eletrocatalisadores, e alguns fatores como uma superfície acessível e área superficial suficientemente grande para uma máxima dispersão dos cristalitos dos eletrocatalisadores, além de tamanho dos poros, distribuição dos poros adequada e a presença de grupos funcionais na superfície do negro de fumo são considerados fundamentais para o desenvolvimento de materiais inovadores. Entretanto, o material denominado Vulcan XC72 ainda revela condições insuficientes para este fim. Este estudo consiste na preparação e caracterização físico-química de carbono funcionalizado por peróxido de hidrogênio e com cadeias poliméricas do tipo poliestireno sulfonado condutoras de prótons, visando sua posterior utilização como suporte de eletrocatalisadores para células a combustível tipo PEMFC e DMFC. Após a funcionalização do carbono, obteve-se uma melhora da dispersibilidade do negro de fumo em solução aquosa, efeito este benéfico para a preparação dos eletrocatalisadores. Observou-se também que os grupos funcionais e as cadeias poliméricas funcionaram como estabilizadores do crescimento dos cristalitos produzindo catalisadores mais homogêneos e com menor diâmetro médio dos cristalitos; e especialmente, no caso da funcionalização com cadeias poliméricas, obteve-se uma diminuição da queda ôhmica do sistema, referente à melhoria da transferência protônica. / The fuel cell technology associated with the growing exigency of low environmental impact energy became prosperous in the world energy scenery. The fuel cell is basically a device that converts directly the chemical energy of a fuel into electrical and thermal energy with a continuous operation by the constant feed of a fuel. Especially, the carbon black Vulcan XC72 is usually employed as an electrocatalyst support, and some factors as an accessible and high surface area in order to get maximum particles dispersion, pore size, adequate pore distribution and the presence of functional groups in the carbon black surface are considered fundamental characteristics for an innovative materials development. However, the Vulcan XC72 still reveals insufficient conditions for these purposes. This study consists in the preparation and in the physical chemical characterization of functionalized carbon black by hydrogen peroxide and by polymeric chains with proton conduction properties, and its posterior utilization as electrocatalyst support for PEMFC and DMFC application. After the carbon functionalization, an improvement in the carbon black dispersibility in water media was observed, a beneficial effect for electrocatalyst preparation. It was also observed, that the functional groups and the polymeric chains worked as stabilizers in the particle growing, producing much more homogeneous electrocatalysts, exhibiting smaller average particle size. Especially, in the case of polymeric chains functionalization, a decrease in the ohmic drop was observed for this system, attributed to an improvement in the proton transference.