Les supercondensateurs sont des systèmes de stockage et de conversion de l'énergie électrochimique dont les densités de puissance et d'énergie sont supérieures à celles des batteries et des condensateurs diélectriques. L’optimisation de leurs performances requiert l’utilisation de matériaux d’électrode à grande surface spécifique tels que les carbones poreux. En particulier, il est possible d’obtenir des systèmes microporeux de porosité prédéterminée par la synthèse de répliques carbonées de zéolithes. Simuler un supercondensateur à l’échelle atomique permettrait de guider le choix des matériaux le composant. Nous avons étudié un système modèle comprenant deux électrodes en réplique carbonée de zéolithe Faujasite ainsi que d’un électrolyte représenté par un système de sphères chargées. Des calculs en Liaisons Fortes de la structure électronique de la matrice carbonée fournissent la distribution de charge dans les électrodes. L’adsorption des ions dans la porosité est étudiée via des simulations Monte Carlo, dans lesquelles les interactions entre ions sont traitées par l’intermédiaire de la méthode de la sommation d’Ewald pour la partie électrostatique, et par un potentiel de Lennard-Jones pour la partie chimique. Les charges sont redistribuées de façon auto-cohérente au cours de la simulation, et la matrice poreuse est relaxée sous l’influence de l’électrolyte. Nous avons pu ainsi mettre en évidence la façon dont les différents éléments (ions, atomes de carbone), et donc la charge, se répartissent à l’interface entre électrode et électrolyte. / Electric double-layer capacitors, also known as supercapacitors, are electrochemical capacitors that have an unusually high energy density compared to that of usual high-capacity electrolytic ones. Being generally admitted that storage density is improved through the use of a nanoporous materials, a good way to optimize supercapacitors, which require carbon materials, is to synthesise carbon replica with predetermined porosity from microporous materials such as zeolites. Modeling such supercapacitors at the atomic scale should help with the choice of its components. Our model system has both electrodes in zeolite carbon replica C-FAU, and has hard charged spheres as its electrolyte. Tight-binding calculations of the electronic structure of the carbon template give the charge distribution in the electrodes, while the absorption of the ions into the pores is studied through Monte Carlo simulations, in which the interactions between the ions are treated using Ewald summations for coulombic interactions and a Lennard-Jones short-range potential for chemical interactions. Relaxation of the electrodes under the influence of the electrolyte has been tested as well. This shows how charge and matter locate themselves at the electrode/electrolyte interface.

This study elucidates the underlying relationships for the distribution of oak landcover on bedrock and soil orders in two counties in Texas and one in Oklahoma. ESRI's ArcGis and ArcMap was used to create surface maps for Denton and Coke Counties, Texas and Choctaw County, Oklahoma. Attribute tables generated in GIS were exported into a spreadsheet software program and frequency tables were created for every formation and soil order in the tri-county research area. The results were both a visual and numeric distribution of oaks in the transition area between the eastern hardwood forests and the Great Plains. Oak distributions are changing on this transition area of the South Central Plains. The sandy Woodbine and Antlers formations traditionally associated with the largest oak distribution are carrying oak coverage of approximately 31-32% in Choctaw and Denton Counties. The calcareous Blackland and Grand Prairies are traditionally associated with treeless grasslands, but are now carrying oak and other tree landcover up to 18.9%. Human intervention, including the establishment of artificial, political and social boundaries, urbanization, farming and fire control have altered the natural distribution of oaks and other landcover of this unique georegion.

O objetivo do presente trabalho é avaliar o uso de borracha triturada de pneu como carburante substituto do coque após a fusão e durante o refino primário oxidante em um forno elétrico a arco na produção de aço 1020. Para o teste foram produzidas 40 toneladas de borracha de pneu triturado em condições granulométricas semelhantes ao coque e abastecido nos silos que alimentam injetoras que adicionaram este material durante o refino primário oxidante. No sistema existem 3 silos e 3 injetoras que são capazes de operar com vazões independentes. O silo n° 1 e o silo n° 3 foram abastecidos com borracha triturada, enquanto que o silo n° 2 foi abastecido com o coque. Testou-se durante 152 corridas situações com injeção de borracha em 4 níveis como substituto do coque: 0% de borracha (somente coque), 33% de borracha, 66% de borracha e 100% de borracha. As vazões e quantidades totais injetadas de carburante foram mantidas em relação ao processo usual. Para evitar interferências manteve-se a receita de carga fria metálica para abastecer o forno bem como os programas elétricos e químicos. Em todas as corridas testadas foram coletadas amostras do aço e da escória no momento antes do vazamento. As amostras foram analisadas através de um espectrômetro de RX. Os resultados obtidos mostraram que é possível a substituição total do coque pela borracha de pneu triturada sem incorrer prejuízos ao processo. Não se observou incorporação de Enxofre no aço, preocupação esta que existia pelo fato da borracha triturada conter teores mais elevados deste elemento em comparação com o coque. / The purpose of this research is to evaluate the use of grinded wasted rubber tires as a carbon source to substitute the coke during the refine in an Electric Arc Furnace to produce steel - grade 1020. For the tests, it was produced 40 tons of grinded rubber in similar size grains of the coke and the material was filled up inside the tanks that feeds the carbon injectors and added the carbon source during the primary oxidant refine. The system is composed by 3 tanks and 3 injectors that can be operate independent. The tank number 1 and number 3 were filled up with grinded rubber, and the tank number 2 was filled up with coke. It was tested during 152 heats 4 different levels of rubber injection to substitute coke: 0% of rubber, 33% of rubber, 66% of rubber and 100% rubber. The flow and injected quantities were kept in the same levels of the normal process. The metallic raw material and electrical and chemical profile were kept the same to avoid interferences. Samples of the steel and the slag were taken before the tap. The samples were analyzed in the RX Spectrometer. The results showed that is it possible to substitute completely the coke with rubber without causing any issues to process. The sulfur content in the rubber did not contaminated the steel, although the rubber contains higher sulfur compared to the coke.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.

Catalisadores ativos e estáveis, preparados a partir dos hidróxidos duplos lamelares (HDLs) contendo os cátions Ni2+, Zn2+, Al3+ e Zr4+(NiZn-Al, NiZn-AlZr e NiZn-Zr), foram avaliados na reação de reforma seca do metano. Os precursores foram caracterizados por difração de raios X, confirmando a formação das fases para as amostras de NiZn-Al e NiZn-AlZr. As espectroscopias no infravermelho/Raman elucidaram a ocorrência dos ânions (CO32-) e das moléculas de água na intercamada. A Fisissorção de nitrogênio ( método de BET) determinou a presença de poros e a área superficial específica. As formas das isotermas foram do tipo IV, de acordo com a IUPAC, e representa uma estrutura mesoporosa. A análise termogravimétrica foi utilizada para determinar a temperatura de calcinação dos precursores para obtenção dos catalisadores e as temperaturas utilizadas foram 550 °C, 650 °C e 750 °C. Os resultados de difração de raios X dos catalisadores apresentaram uma mistura de óxidos binários (NiO, ZnO, ZrO2 e Al2O3) e óxidos ternários (NiAl2O4 e ZnAl2O4). As fases de espinélios foram observadas nos catalisadores obtidos a 650°C (Ni/ZnAl-6 e Ni/ZnAlZr-6) e 750°C (Ni/ZnAl-7 e Ni/ZnAlZr-7). A redução a temperatura programada de hidrogênio (TPR-H2) forneceu informações sobre a redução do catalisador. Os resultados exibiram interações entre a fase ativa com as outras fases presentes no intervalo entre 350 - 800 °C, enquanto que a dessorção àtemperatura programada de CO2 (DTP-CO2) mostrou que os catalisadores possuem sítios básicos fracos. Ademais, os catalisadores foram caracterizados por fisissorção de nitrogênio, microscopia eletrônica de varredura (MEV), espectroscopia Raman e basicidade usando um indicador de Hammett. O desempenho dos catalisadores foi avaliado na reação de reforma seca do metano utilizando uma razão molar de alimentação de CH4: CO2 = 1,5:1,0; a fim de simular a composição do biogás. Os resultados mostraram uma maior conversão para o CO2 em todos os catalisadores investigados, o que pode ser atribuído ao maior teor de CH4 alimentado. Além disso, é importante ressaltar a contribuição dos sítios básicos presentes nas amostras, o que pode também contribuir para a conversão do CO2. A maior conversão de CH4 foi observada para os catalisadores tratados a 750 °C. Após as reações, foi observada a formação de carbono grafite sobre todos os catalisadores, com menor percentual para a amostra Ni/ZnAl, calcinadas a 550 °C e 650 °C, e Ni/ZnZr-7, calcinada a 750 °C. Finalmente, os catalisadores calcinados a 650 °C e 750 °C também foram ativados na temperatura de 750°C e os resultados reacionais mostraram que essa temperatura favoreceu o processo de aglomeração e, portanto, promoveu baixas conversões para o CH4 e CO2. / Active and stable catalysts, prepared from the lamellar double hydroxides (HDLs) containing the cations Ni2 +, Zn2 +, Al3 + and Zr4 + (NiZn-Al, NiZn-AlZr and NiZn-Zr) were evaluated in the dry reforming reaction of methane. The precursors were characterized by X-ray diffraction method, confirming the formation of phases for NiZn-Al and NiZn-AlZr samples. Infrared / Raman spectroscopies elucidated the occurrence of anions (CO32-) and water molecules in the interlayer. Nitrogen physisorption (BET method) determined the presence of pores and the specific surface area. The shape of the isotherms were type IV, according to the IUPAC, representing a mesoporous structure. The thermogravimetric analysis was used to determine the calcination temperature of the precursors to obtain the catalysts and the temperatures used were 550 ° C, 650 ° C and 750 ° C. The X-ray diffraction results of the catalysts showed a mixture of binary oxides (NiO, ZnO, ZrO2 and Al2O3) and ternary oxides (NiAl2O4 and ZnAl2O4). The spinel phases were observed in the catalysts obtained at 650 °C (Ni/ZnAl-6 and Ni/ZnAlZr-6) and 750°C (Ni/ZnAl-7 and Ni/ZnAlZr-7) Temperature- programmed reduction with hydrogen (H2-TPR) provided information on catalyst reduction. The results showed interactions between the active phase and the other phases present in the range of 350 - 800 ° C, while temperature- programmed desorption of CO2 (CO2-TPD) showed that the catalysts have weak basic sites. In addition, the catalysts were characterized by Nitrogen physisorption, scanning electron microscopy (SEM), Raman spectroscopy and basicity using a Hammett indicator. The performance of the catalysts was evaluated in the dry reforming reaction of the methane using a CH4: CO2 molar feed ratio = 1.5: 1.0; In order to simulate the biogas composition. The results showed a higher conversion to CO2 in all the catalysts investigated, which can be attributed to the higher content of CH4 fed. In addition, it is important to restate the contribution of the basic sites present in the samples, which may also contribute to the conversion of CO2.The higher conversion of CH4 was observed for the catalysts treated at 750 ° C. After the reactions, the formation of graphite carbon was observed on all the catalysts, with a lower percentage for Ni / ZnAl samples, calcined at 550 ° C and 650 ° C, and Ni / ZnZr-7, calcined at 750 ° C. Finally, the catalysts calcined at 650 ° C and 750 ° C were also activated at the temperature of 750 ° C. and the reaction results showed that this temperature favored the agglomeration process and, therefore, promoted low conversions for CH4 and CO2.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.

This work involved the development of new perovskite oxides based on SmFeO3 and testing their performances as sensors for reducing gases (H2, CO & CH4) and as anode materials for dry methane oxidation in solid oxide fuel cells. The new perovskite oxide materials with formula Sm0.95Ce0.05Fe1-xMxO3-δ (M= Co, Ni & Cr) were synthesized by a sol gel method using citric acid as a complexing agent. The resulting materials were characterized by using a battery of techniques including XRD, XRF, XPS, SEM and electrochemical methods. Sensing experiments revealed that both cobalt doped and Cr doped materials can detect H2, CO and CH4 in air at different temperatures including room temperature. The Ni doped materials did not prove good candidates as sensors. However, their reduction treatment studies showed the formation of metallic nanoparticles on the surface which deeply influence their electrical conductivity as well as sensing ability. Consequently, this modification in surface structure and chemical composition enabled them to sense hydrogen gas at 300oC very effectively. The response of sensors based on these reduced materials was measurable and reversible. Some materials were also selected on the basis of their reduction stability and electrical properties, and their electrochemical performances were evaluated as SOFC anodes under dry methane and dry hydrogen fuels separately. The performance tests as SOFC anode revealed that the best anode material for the oxidation of dry hydrogen fuel is Sm0.95Ce0.05FeO3-δ. Furthermore, Sm0.95Ce0.05FeO3-δ proved to be coke resistant anode under dry methane fuel and exhibited reasonably low charge transfer resistance values at temperatures between 600-700oC. The doping of Co and Ni at the B-site of Sm0.95Ce0.05FeO3-δ found to be very effective in further improving its performance as SOFC anode towards oxidation of dry methane fuel at the lower temperatures.

Gaslight, an Industrial Revolution technology, developed in the period 1780–1820. The foundations for the technology are partly found in the pneumatic chemistry of the eighteenth century, both in terms of the knowledge of gases and their properties, and the instruments used to manipulate them, such as the gasometer, making gaslight one of the earliest instances of a technology heavily based on science. Although many people experimented with lighting with gases in the late eighteenth century, the move to a commercial technology began with Philippe Lebon and William Murdock who had a clear commercial purpose in mind. The technology in its early phases was found everywhere in Europe, but it was at Boulton & Watt in Birmingham that it was first successfully applied. As Boulton & Watt developed the technology they identified many and solved some of the problems associated with scaling up the technology. They were not, however, very interested in gaslight and only sporadically gave attention to it, before effectively abandoning it around 1812. They nevertheless had an important role to play in its development not only because if their technical work, but also because they demonstrated the technology’s viability to the broad public, and by giving people experience in gas engineering. The technology's final form as a network utility was partly as a result of a battle fought between Boulton & Watt and Frederick Winsor's Gas Light and Coke Company in London during 1807–1810. Boutlon & Watt did not want a large limited-liability corporation as a competitor, and the contest in Parliament between the two groups resulted in a negotiated compromise where the Gas Light and Coke Company gave up all rights to manufacture apparatus, and focused exclusively on gas provision, effectively making it a utility. The years from 1812–1820 saw the technology mature into a large network which included not only technical development, such as the pressure balancing with valves and regulators, but also political and social elements, such as the control of user expectations through education and usage enforcement through inspectors. By 1820, the technology was sufficiently developed to be transferred to the Continent.

Gaslight, an Industrial Revolution technology, developed in the period 1780–1820. The foundations for the technology are partly found in the pneumatic chemistry of the eighteenth century, both in terms of the knowledge of gases and their properties, and the instruments used to manipulate them, such as the gasometer, making gaslight one of the earliest instances of a technology heavily based on science. Although many people experimented with lighting with gases in the late eighteenth century, the move to a commercial technology began with Philippe Lebon and William Murdock who had a clear commercial purpose in mind. The technology in its early phases was found everywhere in Europe, but it was at Boulton & Watt in Birmingham that it was first successfully applied. As Boulton & Watt developed the technology they identified many and solved some of the problems associated with scaling up the technology. They were not, however, very interested in gaslight and only sporadically gave attention to it, before effectively abandoning it around 1812. They nevertheless had an important role to play in its development not only because if their technical work, but also because they demonstrated the technology’s viability to the broad public, and by giving people experience in gas engineering. The technology's final form as a network utility was partly as a result of a battle fought between Boulton & Watt and Frederick Winsor's Gas Light and Coke Company in London during 1807–1810. Boutlon & Watt did not want a large limited-liability corporation as a competitor, and the contest in Parliament between the two groups resulted in a negotiated compromise where the Gas Light and Coke Company gave up all rights to manufacture apparatus, and focused exclusively on gas provision, effectively making it a utility. The years from 1812–1820 saw the technology mature into a large network which included not only technical development, such as the pressure balancing with valves and regulators, but also political and social elements, such as the control of user expectations through education and usage enforcement through inspectors. By 1820, the technology was sufficiently developed to be transferred to the Continent.

This work involved the development of new perovskite oxides based on SmFeO3 and testing their performances as sensors for reducing gases (H2, CO & CH4) and as anode materials for dry methane oxidation in solid oxide fuel cells. The new perovskite oxide materials with formula Sm0.95Ce0.05Fe1-xMxO3-δ (M= Co, Ni & Cr) were synthesized by a sol gel method using citric acid as a complexing agent. The resulting materials were characterized by using a battery of techniques including XRD, XRF, XPS, SEM and electrochemical methods. Sensing experiments revealed that both cobalt doped and Cr doped materials can detect H2, CO and CH4 in air at different temperatures including room temperature. The Ni doped materials did not prove good candidates as sensors. However, their reduction treatment studies showed the formation of metallic nanoparticles on the surface which deeply influence their electrical conductivity as well as sensing ability. Consequently, this modification in surface structure and chemical composition enabled them to sense hydrogen gas at 300oC very effectively. The response of sensors based on these reduced materials was measurable and reversible. Some materials were also selected on the basis of their reduction stability and electrical properties, and their electrochemical performances were evaluated as SOFC anodes under dry methane and dry hydrogen fuels separately. The performance tests as SOFC anode revealed that the best anode material for the oxidation of dry hydrogen fuel is Sm0.95Ce0.05FeO3-δ. Furthermore, Sm0.95Ce0.05FeO3-δ proved to be coke resistant anode under dry methane fuel and exhibited reasonably low charge transfer resistance values at temperatures between 600-700oC. The doping of Co and Ni at the B-site of Sm0.95Ce0.05FeO3-δ found to be very effective in further improving its performance as SOFC anode towards oxidation of dry methane fuel at the lower temperatures.