The search for environmentally benign energy sources is becoming increasingly urgent. One such technology is fuel cells, e.g., the polymer electrolyte membrane (PEM) fuel cell which uses hydrogen as a fuel and emits only H2O. However, reforming hydrocarbon fuels to produce the needed hydrogen yields reformate streams containing CO2 as well as CO, which is toxic to the PEM fuel cell at concentrations above 100ppm. As the amount of CO permitted to reach the fuel cell increases, the performance of the PEM fuel cell decreases until it ultimately stops functioning. The water-gas-shift (WGS) reaction, CO + H2O <-> H2 + CO2, provides a method for extracting the energy from the toxic CO by converting it into usable H2 along with CO2 which can be tolerated by the fuel cell. Although a well established industrial process, alternate catalysts are sought for fuel cell application. Catalyst selection for the WGS reaction has, until recently, been based on trial-and-error screening of potential catalysts due to a lack of fundamental understanding of the catalyst's functioning. For this reason, we embarked on a deeper understanding of the molecular events involved in the WGS reaction such that a more systematic and theory-guided approach may be used to design and select catalysts more efficiently, i.e., rational catalyst design. The goal of this research was to develop a comprehensive predictive microkinetic model for the WGS reaction which is based solely on a detailed mechanism as well as theories of surface-molecule interactions (i.e., the transition-state theory) with energetic parameters determined a priori. This was followed by a comparison of the experimental results of sample catalysts to validate the model for various metal-based catalysts of interest including Cu, Fe, Ni, Pd, Pt, Rh, and Ru. A comprehensive mechanism of the plausible elementary reaction steps was compiled from existing mechanisms in the literature. These were supplemented with other likely candidates which are derivatives of those identified in the literature. Using established theories, we predicted the kinetics of each of the elementary reaction steps on metal catalysts of interest. The Unity Bond Index-Quadratic Exponential Potential Method (UBI-QEP) was used to predict the activation energies in both the forward and reverse direction of each step based solely on heats of chemisorption and bond dissociation energies of the species involved. The Transition State Theory (TST) was used to predict the pre-exponential factors for each step assuming an immobile transition state; however, the pre-exponential factors were adjusted slightly to ensure thermodynamic consistency with the overall WGS reaction. In addition, we have developed a new and powerful theoretical tool to gain further insight into the dominant pathways on a catalytic surface as reactants become products. Reaction Route (RR) Graph Theory incorporates fundamental elements of graph theory and electrical network theory to graphically depict and analyze reaction mechanisms. The stoichiometry of a mechanism determines the connectivity of the elementary reaction steps. Each elementary reaction step is viewed as a single branch with an assumed direction corresponding to the assumed forward direction of the elementary reaction step. The steps become interconnected via nodes which reflect the quasi-steady state conditions of the species represented by the node. A complete RR graph intertwines a series of routes by which the reactants may be converted to products. Once constructed, the RR graph may be converted into an electrical network by replacing, in the steady-state case, each elementary reaction step branch with a resistor and including the overall reaction as a power source where rate and affinity correspond to current and voltage, respectively. A simplification and reduction of the mechanism may be performed based on results from a rigorous De Donder affinity analysis as it correlates to Kirchhoff's Voltage Law (KVL), akin to thermodynamic consistency, coupled with quasi-steady state conditions, i.e., conservation of mass, analyzed using Kirchhoff's Current Law (KCL). Hence, given the elementary reaction step resistances, in conjunction with Kirchhoff's Laws, a systematic reduction of the network identifies the dominant routes, e.g., the routes with the lowest resistance, along with slow and quasi-equilibrium elementary reaction steps, yielding a simplified mechanism from which a predictive rate expression may possibly be derived. Here, we have applied RR Graph Theory to the WGS reaction. An 18-step mechanism was employed to understand and predict the kinetics of the WGS reaction. From the stoichiometric matrix for this mechanism, the topological features necessary to assemble the RR graph, namely the intermediate nodes, terminal nodes, empty reaction routes and full reaction routes, were enumerated and the graph constructed. The assembly of the RR graph provides a comprehensive overview of the mechanism. After reduction of the network, the simplified mechanism, comprising the dominant pathways, identified the quasi-equilibrium and rate-determining steps, which were used to determine the simplified rate expression which predicts the rate of the complete mechanism for different catalysts. Experimental investigations were conducted on the catalysts of interest to validate the microkinetic model derived. Comparison of the experimental results from the industrially employed catalysts (e.g., Cu, Ni, Fe, etc.) shows that the simplified microkinetic model sufficiently predicts the behavior of the WGS reaction for this series of catalysts with very good agreement. Other catalysis tested (Pt, Pd, Rh and Ru), however, had sufficient methanation activity that a direct comparison with WGS kinetics could not be made. In summary, we have developed a comprehensive approach to unravel the mechanism and kinetics of a catalytic reaction. The methodology described provides a more fundamental depiction of events on the surface of a catalyst paving the way for rational analysis and catalyst design. Illustrated here with the WGS reaction as an example, we show that the dominant RRs may be systematically determined through the application of rigorous fundamental constraints (e.g. thermodynamic consistency and mass conservation) yielding a corresponding explicit a priori rate expression which illustrates very good agreement not only with the complete microkinetic mechanism, but also the experimental data. Overall, RR graph theory is a powerful new tool that may become invaluable for unraveling the mechanism and kinetics of complex catalytic reactions via a common-sense approach based on fundamentals.

Made available in DSpace on 2016-04-27T19:30:44Z (GMT). No. of bitstreams: 1 Edson Holanda Lima Barboza.pdf: 4849588 bytes, checksum: bb3c4e5e1c04717c71411b260f1a8c0d (MD5) Previous issue date: 2013-05-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / We will analyze interferences exerted by refugees from Ceará in the composition of migratory routes towards the provinces of the far North - Piauí, Maranhão, Pará and Amazonas. It interprets the impact of Diaspora of Ceará, between the years 1877 and 1880, due to drought, and how it was perceived by enslaved workers from Ceará and neighboring provinces as opportunities to reverse their identities and lifestyles, enabling captives or criminals to access denied projects of mobilization and social inclusion. The conflicting trajectories involved unruly captives and free paupers traversing provincial centers, public works and agricultural colonies. In this way, enslaved, national and foreign settlers formed contact zones in which it was possible to exchange experiences and solidarities. One main zone was the Núcleo Colonial de Nossa Senhora do Carmo de Benevides, next to Belém, a space planned by local elites to boost agricultural production in Pará, which, however, was a place of unexpected alliances joints that turned this core in place of riots and in focus of abolitionist struggles / Analisamos interferências exercidas por retirantes cearenses na composição de rotas migratórias em direção às províncias do extremo Norte Piauí, Maranhão, Pará e Amazonas. Interpretamos repercussões das Diásporas da população cearense, entre os anos de 1877 e 1880, em decorrência da seca, e como foram percebidas por parte de trabalhadores escravizados do Ceará e de províncias vizinhas, enquanto oportunidades para reverter suas identificações e modos de vida, possibilitando a cativos ou clandestinos acessos a projetos de mobilidade e inserção social até então negados. As trajetórias conflituosas, envolvendo cativos insubordinados e pobres livres, percorreram centros administrativos provinciais, frentes de trabalho e colônias agrícolas. Neste percurso, escravizados, colonos nacionais e estrangeiros formaram zonas de contato em que foi possível a troca de experiências e solidariedades. Um dos principais pontos de convergência foi o Núcleo Colonial de Nossa Senhora do Carmo de Benevides, nas proximidades de Belém, espaço planejado pelas elites locais para fomentar a produção agrícola no Pará, contudo, inesperadas articulações de alianças transformaram este núcleo em palco de motins e foco de lutas abolicionistas

Este trabalho tem a finalidade de analisar a compatibilidade do gabarito dos caminhões brasileiros com a geometria das interseções urbanas de uma cidade de médio porte. Foi utilizado um Sistema de Informações Geográficas para a elaboração de rotas de menor caminho, dentro da área de estudo. Foram realizados levantamentos de campo para a reconstituição da geometria das interseções. Em seguida, através de um programa de simulação cada conversão necessária foi analisada para saber se havia a possibilidade de realização da manobra, dentro das rotas de menor caminho. / This work has the objective of analyzing the template compatibility, of Brazilian trucks with the urban intersections geometry in a medium-sized city. It was used a Geographic Information System to elaborate the shortest path within the study area. Field data were carried out for reconstitution of the intersections geometry. Next, each necessary conversion was analyzed, through a simulation program in order to know if the trucks were able to negotiate the curves in the shortest path routes.

Submitted by Leonardo Lima (leonardoperlim@gmail.com) on 2017-04-03T14:24:18Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) SILVEIRA,Marília Brandão Amaro da.pdf: 1463584 bytes, checksum: 060984355c65b2ee1490fcef1f9d644b (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-05-09T14:46:23Z (GMT) No. of bitstreams: 2 SILVEIRA,Marília Brandão Amaro da.pdf: 1463584 bytes, checksum: 060984355c65b2ee1490fcef1f9d644b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-05-09T14:48:28Z (GMT) No. of bitstreams: 2 SILVEIRA,Marília Brandão Amaro da.pdf: 1463584 bytes, checksum: 060984355c65b2ee1490fcef1f9d644b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-05-09T14:48:36Z (GMT). No. of bitstreams: 2 SILVEIRA,Marília Brandão Amaro da.pdf: 1463584 bytes, checksum: 060984355c65b2ee1490fcef1f9d644b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-04-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / No presente trabalho intenta-se trazer novos elementos sobre a pesquisa em ditadura civil militar focando um tema cuja produção é ainda muito escassa. Propõe-se explorar a forma como o período expressou-se, no que remete ao Rio Grande do Sul, em cidades do interior onde percebemos uma grande particularidade: a organização das rotas de exílio. Delimitaremos o presente trabalho às atividades de oposição à ditadura civil militar nas cidades de interior e de fronteira, considerando as principais atividades de oposição e, também, a repressão, os apoios ao golpe, dentre diversas particularidades. Focar-se-á, mais especificamente, na organização das rotas de exílio, atividade peculiar que envolveu diversos grupos em solidariedade para garantir a vida de militantes procurados e, também, para a organização da militância no exílio. A principal fonte será a memória, tanto dos organizadores das atividades, quanto dos transladados para fora do país. Deter-se-á o período compreendido entre o ano do golpe até o início dos anos de 1970, em que os grupos de resistência foram duramente combatidos e se encontravam bastante desarticulados. / The present paper attempts to bring new elements to civil-military dictatorship research focusing at a topic which production is yet scarse. It is proposed to explore the way, concerning the Rio Grande do Sul state, which the period was expressed in the countryside cities and we can point it out a certain particularity: the organization of the exile's routes. Therefore, we'll limit the present paper to the opposing activities against the civil-military dictatorship at the contryside and boundary cities accounting opposing activities, repression, the coup support, among many other particularities. However, it will focus on the establishment of the exile's routes, singular activity which envolved many groups in symphaty to ensure the life of the wanted militants and, also, to the militancy arrengement at the exile. The main source will be the memory from both - activities organizers and exileds. It will concentrate on the period counting from the year of the takeover until the early 1970s in which resistance groups were starkly fought and could be found very disarticulated.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Esta pesquisa caminha em primeira pessoa, a partir de reflexÃes com o desenhar disparadas por memÃrias de vida e o desenhar de forma compartilhada, exercÃcio que desenvolvo mais recentemente. O convite para o desenho a dois possibilita o encontro com jovens skatistas em Fortaleza e a criaÃÃo de uma sÃrie de mapas-retratos, inspirados em seus percursos errantes pela cidade. Esses mapas-retratos consistem em desenhos que acontecem em duas camadas que se sobrepÃem: uma à o mapa de percursos do jovem sobre o skate, outra à o retrato desse jovem. FaÃo uma camada e a outra à feita por aquele que convido a desenhar comigo. No processo de produÃÃo dos desenhos e de escrita, reinvento a relaÃÃo com a cidade à procura desses jovens e na companhia deles. Sou levada a pensar na intimidade com o desenho e nas porÃÃes do desenho que escapam; comeÃo a refletir sobre o fazer cartogrÃfico e o conversar (MATURANA, 1988) como possibilidades de operar na pesquisa em que desejo me envolver com o outro - aquele que nÃo conheÃo e de quem quero me aproximar -, assim como sinalizo um interesse acerca dos usos do mapa que subvertem a geografia tradicional. Suspeitando que a errÃncia (JACQUES, 2012) desses corpos juvenis em aÃÃo pela cidade configure outros modos de sentir e praticar o espaÃo urbano, reflito acerca do poder dos encontros que reverbera em alteraÃÃes na linha, no gesto, na composiÃÃo, no movimento e tambÃm no jogo de olhares, narrativas e silÃncios que se instaura no contexto de nossas relaÃÃes.

Apresenta-se inicialmente o problema do Circuito Impresso na Automação de Projetos de Sistemas Digitais. É descrito um processo de fabricação, já em uso mencionando-se as principais fases da implementação de circuitos impressos. Dá-se ênfase aos algoritmos desenvolvidos para a definição do mapa de rotas, bem como à forma de descrição dos dados para processamento de problemas. São descritos sumariamente os arquivos e programas usados para a realização do \"Lay-out\", e complementarmente, discute-se um caso exemplo desde o seu preparo até as saídas gráficas. Alguns exemplos reais são expostos a na forma como foram processados. Dá-se destaque ainda ao conjunto de mensagens de erro emitidas pelos programas, que auxiliam o usuário no projeto do mapa de rotas de interconexão. / The problem of printed circuit boards in digital systems Project automation is initially presented. A manufacturing process for printed circuit boards is considered and the important phases of its implementation are described. This manufacturing process has been already successfully implemented. The central point of this dissertation is the set of algorithms developed for route mapping. The format description for processing is also a problem of importance and concern. The files and program for lay-out construction are briefly described, and an example illustrates all the relevant steps in the process, starting from data preparation and ending with the graphic outputs. Several real case examples are also presented in the form they were processed. A set of error messages printed by the program is presented. These messages are of great help to the user in projecting interconnection routing map.

Neste trabalho, realiza-se o estudo das letras ramistas [j] e [v] e de suas variantes [i], [y] e [u] em dois roteiros de viagem lavrados no século XVIII. Para tanto, faz-se uma recolha exaustiva e minuciosa em ambos os manuscritos e há também um mapa que ilustra o tema dos documentos. Gramáticas e ortografias dos séculos XVI, XVII e XVIII foram consultadas e demonstra em que medida o emprego das letras [i], [y], [j], [u] e [v] segue ou não a norma apresentada. A vida e obra de Pierre de la Ramée são abordadas de modo sintético, para que se conheça o contexto de diferenciação das ramistas, [j] e [v] de [i] e [u]. No capítulo dedicado à toponímia, pretende-se analisar como se comportam as ramistas e suas variantes em geral; além de um grafema especial, um tipo de [y] com a cauda cortada: [y], cuja referência fonética e semântica traduz-se, em tupi, no vocábulo água. A análise de dois textos com proximidade temática e cronológica e punhos diferentes deixa entrever hábitos freqüentes de uma determinada época da história da escrita e revela tendências no uso das ramistas e suas variantes. É possível constatar que a preferência no uso desta ou daquela letra dá-se muito mais por idiossincrasias dos autores do que por respeito à normatização imposta pelas gramáticas a eles contemporâneas. / The object of this investigation is the research of the ramist letters [j] and [v] and its differences [i], [y] and [u] made in two travel routes in the century XVIII. Therefore, it is made a very detailed and exhausted selection of both handwritings and there is a map which illustrates the title of the documents. It is also studied grammar books used in centuries XVI, XVII and XVIII and they show whenever the use of [i], [y], [j], [u] and [v] took place in standard grammar. The bibliography of Pierre de la Rameé is used shortly, only to recognize the context of differences in the ramist letters [j] and [v] of [i] and [u]. In the chapter dedicated to toponym, the intention is to analyze the behavior of ramist and its variability in general. It is seen a special writing, a kind of [y] with a dash in the tail like [y], whose phonetic reference and semantic is translated, in tupi, in the word water. The analysis of both texts are close in chronologic and thematic aspects but different treats permit different and frequent manners of a certain time in writing history and reveal some tendencies in the use of ramist writing and its possible for this or that letter is taken by much more for author\'s idiosyncrasies than the normatization imposed by grammar books at that age.

Este trabalho tem a finalidade de analisar a compatibilidade do gabarito dos caminhões brasileiros com a geometria das interseções urbanas de uma cidade de médio porte. Foi utilizado um Sistema de Informações Geográficas para a elaboração de rotas de menor caminho, dentro da área de estudo. Foram realizados levantamentos de campo para a reconstituição da geometria das interseções. Em seguida, através de um programa de simulação cada conversão necessária foi analisada para saber se havia a possibilidade de realização da manobra, dentro das rotas de menor caminho. / This work has the objective of analyzing the template compatibility, of Brazilian trucks with the urban intersections geometry in a medium-sized city. It was used a Geographic Information System to elaborate the shortest path within the study area. Field data were carried out for reconstitution of the intersections geometry. Next, each necessary conversion was analyzed, through a simulation program in order to know if the trucks were able to negotiate the curves in the shortest path routes.

Bridges, railways stations, warehouses, bandstands, fountains, shop fronts, lamps, gates and other cast-iron elements can still be found throughout Argentina. Some of these elements are impressive, others humble; some are abandoned, others are still in use. Many are part of important monuments; others are so incorporated into the urban landscape that they almost go unnoticed. When one's attention is drawn to these features, however, a company nameplate and place of origin - 'London', 'Liverpool', 'Glasgow' - is usually visible. These elements are so far from Argentina that their appearance begs several questions: why are most of the visible nameplates British? Are they the same as those found in London, Liverpool and Glasgow, or in former British colonies like India, South Africa or Australia? If so, why? Can we think of these elements as British imperial architecture in Argentina? In what context can their arrival in Argentina be understood? Who commissioned and designed them? Are there more Scottish nameplates than English, or any other? Does it matter? Did these elements act as models that were later copied or imitated by local manufacturers? Did they affect architecture and urban development in Argentina? If architecture reflects the view of a society, what do these elements reflect? Considering the wider context of British cast iron manufacturing, this dissertation asks what role Scotland's burgeoning cast iron industry played in the export of British iron products to Argentina during the late nineteenth and early twentieth centuries. If in recent years historians have reconsidered the specific contributions of Scotland and its people to the growth and expansion of Great Britain as an imperial power, this dissertation takes this analysis into the realm of cast iron as an export industry. If British cast iron was ubiquitous throughout the developed world during this period, how do we begin to understand the Scottish cast iron industry as a major contributor to this trade? Here Argentina is used as a micro-study in an attempt to measure and understand that contribution. In addressing some of the above questions, the dissertation attempts to form a coherent analysis of the architectural, historic, cultural and economic dimensions of the phenomenon of Scottish architectural ironwork in Argentina. In so doing, the study hopes to shed light on larger questions concerning British 'informal' imperialism, considering exports of cast iron as a significant component in Britain's attempts at economic leverage and coercion in Argentina during that country's most dramatic period of development and urbanisation. The dissertation arrives at the conclusion that British cast-iron elements found in Argentina are the same or similar to elements found in Great Britain and its colonial empire because they arrived in Argentina through a process of commercial expansion that involved imperial trade routes, global networks, cooperation between British architects and engineers, as well as migration and the assistance of the pro-British elite in Argentina. It is argued that British iron in general, and Scottish in particular, contributed to the expansion of British power and influence in the region through helping shape the architectural and urban environments of Argentina. To reach this conclusion, the thesis is structured in three sections dealing with the three most significant aspects of the thesis: informal empire in Argentina, the iron trade, and Scottish cast-iron architecture in Argentina.

Custom T-shirt Designs is a web-based application. The purpose of this project is to provide a website that would allow customers to be able to customize T-shirt and place an order of custom T-shirt. Customers can sign up, sign in, select T-shirt color, add text, choose Font, choose Font color, upload an image, apply filters to images, transform text or images, choose T-shirt size and save designs for future references. Customers would be able to add the design to a cart, manage cart and checkout with their credit card to purchase for the order and view their previous orders. The project focuses on object-oriented programming paradigm using PHP framework Laravel along with JavaScript, CSS, and HTML, Bootstrap and jQuery. Custom T-shirt Designs application uses Model-view-controller architecture. Stripe API is used to handle the credit card payments tokens providing a secure way for customers to purchase a T-shirt. Google SMTP is used to send confirmation of purchase order to administrator and customer. The project implements AJAX technology to send and receive parts of data from the server asynchronously making Custom T-shirt Designs a fast and efficient real-time web application.