Orientador: Carlos Alberto Rodrigues Anjos / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-24T02:04:55Z (GMT). No. of bitstreams: 1 Soares_BeatrizMariaCurtio_D.pdf: 4935391 bytes, checksum: 1fda7db59f6fdc54d9072cb0cff1fe61 (MD5) Previous issue date: 2013 / Resumo: Neste trabalho estudou-se a ação dos íons cloreto e de cobre no comportamento corrosivo de ligas de alumínio utilizadas na fabricação de latas de alumínio para bebidas. Foram avaliados seis tipos de refrigerantes (de cola, guaraná, de uva, de limão, de laranja e tônica) comumente comercializados em latas de alumínio, para determinação de pH, acidez, concentração de cloreto e de cobre e determinação do potencial de corrosão do alumínio frente a essas bebidas. Baseadas nessas informações, soluções simulantes de refrigerante foram definidas para emprego no estudo de corrosão. Através da obtenção de curvas de polarização, avaliou-se o efeito da concentração desses íons em solução acidificada com ácido cítrico (pH 3,0) no comportamento corrosivo das ligas de alumínio AA3104-H19 e AA5182-H19. Os resultados demonstraram que a presença concomitante de íons cloreto e de cobre em solução potencializa a corrosão da liga AA3104-H19, usada no corpo de latas de alumínio. Por fim, o estudo de estabilidade foi conduzido com solução ácida contendo apenas íons cloreto (250 mg.kg-1), apenas íons cobre (25 ?g.kg-1) e a mistura desses dois íons (250 mg.kg-1 + 25 ?g.kg-1). Duas alturas de enchimento também foram definidas para avaliar a influência do espaço-livre da lata no processo de corrosão. Durante a estocagem realizada a 35 °C por 180 dias confirmou-se o potencial de agressão da solução contendo a mistura dos íons cloreto e de cobre, com a ocorrência de perfuração da lata após 12 dias de estocagem e perda de 30% das embalagens após 180 dias estocagem. Também foi observada maior migração de alumínio para a bebida nas latas com maior espaço-livre. As latas que acondicionaram solução contendo apenas um dos elementos permaneceram íntegras até os 180 dias de estocagem, embora tenha sido observado início do processo corrosivo nessas embalagens / Abstract: In this work was studied the effect of chloride and copper ions on the corrosion behavior of aluminum alloys used in aluminum beverage cans. Firstly, six types of soft drink (cola, guarana, grape, lemon, orange and tonic), commercialized in aluminum cans, were evaluated for pH, acidity, chloride and copper concentration, and determination of the aluminum corrosion potential. Based on this information, model solutions simulating the soft drinks were defined for use in the corrosion study. Polarization curves were obtained to evaluate the effect of ions concentration in acidified solution using citric acid (pH 3.0) on corrosion potential of AA3104-H19 and AA5182-H19 aluminum alloys. The results obtained showed that the presence of chloride and copper ions in the same solution enhances the corrosion of AA3104-H19 aluminum alloy, which is used in the can body. Finally, the stability study was conducted with acid solutions containing only chloride ions (250 mg.kg-1) or copper ions (25 ?g.kg-1) or both ions (250 mg.kg-1 + 25 ?g.kg-1). Two filling levels have also been used to evaluate the influence of the can head-space in the corrosion process. During storage at 35 °C for 180 days, the aggression potential of the solution containing the mixture of chloride and copper ions was confirmed by the occurrence of can perforation after 12 days of storage and 30% of packaging loss after 180 days of storage. The aluminum migration was higher in beverages packaged in higher head-space cans. Cans containing only one element remained intact up to 180 days of storage, although the beginning of the corrosion process has been observed in the cans / Doutorado / Tecnologia de Alimentos / Doutora em Tecnologia de Alimentos

The use of mineral additions and substitutions in concrete production is highly beneficial to society. When used as substitutes for cement, they provide an alternative destination to polluting waste while contributing to reducing the power consumption and air pollution associated with cement production. This study investigated the influence of different concentrations of additions and curing periods of concrete mixes with water treatment plant sludge ash (CLETA), rice husk ash (CCA) and blast furnace slag (EAF) on total shrinkage and chloride penetration in concrete prepared with high early strength Portland cement. Ten mixes with water/binder ratios of 0.35, 0.50 and 0.65, with wet cure periods of 3 and 7 days were tested. CLETA substitutions for Portland cement ranged from 0% to 30%. Three-component mixes with 20% CLETA and 5% EAF, 20% CLETA and 10% EAF and a four-component mix with 15% CLETA, 5% EAF and 5% CCA were also tested. Shrinkage was measured using a length comparator at 0, 7, 14, 21, 28, 35, 56, 91, 182 and 365 days after removing the sample from the controlled humidity chamber. After 91 days of drying, samples were tested for chloride penetration to check chloride penetration depths in shrinking test samples. Results indicate that even though shrinkage values at 3 days are slightly higher, no significant variation was found for different curing periods. The lowest shrinkage value was found in the reference sample for all tested periods and in the two curing periods. Next, in an increasing shrinkage values, came the following samples: 5%CLETA (5 L), 10% CLETA (10 L), 15% CLETA (15 L), which displayed, for most mixes, a similar behavior to that of 10% CLETA (10 L), followed by mixes 20% CLETA (20 L), 25 %CLETA (20 L) and 30% CLETA (30 L). Chloride penetration resistance increased when the curing time was increased from 3 to 7 days. Three- and four-component mixes showed improved performance when compared to binary samples with CLETA and Portland cement. / O uso de adições minerais e de substituições destas no processo de produção do concreto traz grande benefício à sociedade, por dar um destino a resíduos poluentes e, principalmente, por reduzir o consumo de energia e a poluição do ar gerados pela produção do cimento, ao substituir grande parte desse produto na indústria da construção civil. Neste estudo, investigou-se a influência do teor e do período de cura na utilização de misturas contendo diferentes teores de cinza de lodo de ETA (CLETA), cinza de casca de arroz (CCA) e escória de alto forno (EAF), frente à retração total e à penetração de cloretos de concretos com cimento Portland de alta resistência inicial. Para isso, foram testadas dez misturas aglomerantes, nas relações água/aglomerante 0,35, 0,50 e 0,65, com períodos de cura úmida de 3 e 7 dias. As substituições do cimento Portland por CLETA variaram de 0% a 30%, havendo ainda misturas ternárias, 20% CLETA e 5% EAF, 20% CLETA e 10% EAF, e quaternária, 15% CLETA, 5% EAF e 5% CCA. As leituras de retração foram realizadas com o uso do comparador de expansibilidade nas idades de ensaio, 0, 7, 14, 21, 28, 35, 56, 91, 182 e 365 dias após a retirada da câmara úmida. Após o período de 91 dias de secagem, foi realizado o ensaio de penetração de cloretos por imersão, a fim de analisar a profundidade de penetração de cloretos em corpos de prova em estado de retração. Dos resultados obtidos, constatou-se que, de maneira geral, embora tenham sido observados valores de retração pouco maiores para a cura de 3 dias, não foi constatada variação pronunciada entre os prazos de cura. De todas as misturas investigadas, a que apresentou menor valor de retração foi a de referência, em todas as idades de ensaio e nos dois períodos de cura. Seguido desta, em ordem crescente de retração, vem 5%CLETA (5 L), 10% CLETA (10 L), 15% CLETA (15 L), que tiveram na maioria das misturas um comportamento similar ao de 10% CLETA (10 L), seguido das misturas 20% CLETA (20 L), 25 %CLETA (20 L) e 30% CLETA (30 L). No que diz respeito à penetração de íons cloreto, houve um aumento na resistência quando o tempo de cura passou de 3 para 7 dias. Constatou-se que as misturas ternárias e quaternárias apresentam melhores desempenhos quando comparadas às misturas binárias, compostas por CLETA e cimento Portland.

Au cours de cette thèse, nous nous sommes intéressés à la synthèse de photo-interrupteurs organiques [DAE, di(hétéro)arylethenes] via activation de liaisons sp² C-H d'hétéroaromatiques catalysées par le palladium. Le système catalytique pour l'arylation directe précédemment établi, Pd(OAc)₂/KOAc/DMAc, s'est montré adapté aux nouvelles transformations souhaitées. Cette méthode permet l'accès direct à une grande variété de molécules photo-commutable en peu d'étapes. En outre, concernant le développement de nouvelles procédures de fonctionnalisation de liaisons C-H d'hétéroaromatiques, nous avons constaté que le système catalytique Pd(CH₃CN)₂Cl2/Li₂CO₃/dioxane, pour le couplage de thiophènes avec des chlorures d'arylsulfonyle conduit à des thiophènes β-arylés. Ce nouveau système catalytique peut également être utilisé dans une réaction d'addition conjuguée, en utilisant des énones et des chlorures d'arylsulfonyle en tant que partenaires de couplage. Enfin, nous avons décrit la formation de 4-aryl-1,2,3,4-tetrahydroquinolines via Heck/sp² C-H activation co-catalysée par PdCl₂/CuBr. / During this thesis, we were interested in the synthesis of organic photo-switches [DAE, di(hetero)arylethenes] via palladium catalyzed sp2 C-H bond activation of heteroaromatics. The previously established catalysts system for direct arylation, Pd(OAc)₂/KOAc/DMA, was found to be suitable for the new desired transformations. This method allows the straightforward access to a wide variety of useful photo-switchable molecules in a few steps. Moreover, during the course of further developments of C-H bond functionalization of heteroaromatics, we found that a phosphine free catalytic system, Pd(CH₃CN)₂Cl2/Li ₂CO₃/dioxane, promotes the coupling of thiophenes and arylsulfonyl chlorides to afford unexpected β-arylated products. This new catalytic system can also be utilized in conjugate addition reaction by using enones and arylsulfonyl chlorides as coupling partners. Finally, we describe PdCl2/CuBr co-catalyzed formation of 4-aryl-1,2,3,4-tetrahydroquinolines via cascade desulfitative Heck/sp² C-H activation sequence.

No description available.

This study was made to compare rates of reactions between thionyl chloride, sulfuryl chloride, and chlorosulphonic acid, separately, with various types of hydrocarbons.

Abstract : One of the aims of the thesis is to study corrosion development in cracked concrete, in relation to the effect of concrete cover depth, exposure direction, load-induced transverse cracks, defects in the steel-concrete interface under horizontal bars caused by top-casting and self-healing of the transverse cracks. The other aim is to study the mechanical performance of reinforced concrete beams damaged by corrosion accelerated by a climate accelerated method (wetting/drying cycles in salt fog). Two main parts are included in this thesis. The first part discusses corrosion development, including corrosion initiation and propagation, in cracked concrete. The second part discusses the mechanical performance of slender and deep beams damaged by climate accelerated corrosion, in terms of failure mode, yield capacity, ultimate capacity and ultimate deflection. According to the experimental study, it was found that, corrosion always initiated under the load-induced cracks. It should be noted that corrosion initiation is related to appearance of cracks but not crack width. The surface exposure condition is also an important parameter influencing corrosion development. Top-tensioned surface is the worst exposure condition, because corrosion development was accelerated by both ponding and gravity effect of chloride solution. Furthermore, top-casting-induced defects formed in steel-concrete interface under horizontal top-cast bars due to bleeding, segregation and settlement of fresh concrete, and they were favorable for both corrosion initiation and propagation. Self-healing occurred when the cracked samples were cured in a humidity room with 100% R.H due to the formation of ettringite in the inner zone and calcite in the outer zone of crack planes. Self-healing reduced air flow through the cracks and reduced the risk of corrosion considerably. The flexural performances of slender beams were tested. Corrosion of the reinforcements modified the failure mode of reinforced concrete beams. Both yield and ultimate capacity were correlated to the maximum cross-sectional loss of tensile bars. The experimental results indicated that 1% reduction in cross-section corresponds to 1% reduction in yielding capacity and ultimate capacity. For mechanical performance of deep beams, the results show that, serious pitting corrosion on the tensile bars changed the failure mode from shear to flexure. The failure mode of corroded deep beams depends not only on span to effective depth ratio and corrosion degree of tensile bars, but also on the corrosion degree of stirrups. / Résumé : Un des objectifs de la thèse est d'étudier le développement de la corrosion dans le béton armé fissuré, en fonction de l’enrobage des armatures, des conditions d’exposition, de l’endommagement de l’interface acier-béton induit par le chargement et des défauts de l'interface acier-béton sous les barres horizontales liés à la mise en œuvre du béton frais en prenant en compte l'auto-cicatrisation des fissures transversales. L'autre objectif est d'étudier la performance mécanique des poutres en béton armé endommagées par la corrosion naturelle en ambiance agressive (des cycles humifification/séchage en brouillard salin). Deux parties principales constituent cette thèse. La première partie traite du développement de la corrosion, à la fois initiation et propagation, dans le béton armé en présence de fissures. La deuxième partie traite de la performance mécanique des poutres longues et courtes endommagés par la corrosion des armatures, en termes de mode de défaillance, seuil de plastification, capacité ultime résiduelle et flèche ultime à rupture. Les résultats de l'étude expérimentale confirment que la corrosion est toujours initiée dans les fissures induites par le chargement. Il convient de noter que la corrosion est liée à la présence des fissures mais pas à leur largeur. Les conditions d'exposition sont également un paramètre important influençant le développement de la corrosion. Ainsi, une surface tendue correspondant à la surface supérieure est la pire condition d'exposition, parce que le développement de la corrosion est accéléré par les effets de l’accumulation des chlorures ainsi que l’effet gravitaire favorisant leur pénétration. En outre, les dommages induits par le “top-cast effect” qui sont formés à l'interface acier-béton sous les barres horizontales par le ressuage et le tassement du béton frais, sont favorables à la fois à la l’initiation et à la propagation de la corrosion. Le phénomène d’auto-cicatrisation des fissures survient lorsque les échantillons fissurés sont conservés à 100% d'humidité relative en raison de la formation d'ettringite dans la zone intérieure et de la calcite dans la zone extérieure du plan de fissuration. L’auto-cicatrisation réduit le débit d'air à travers les fissures et réduit considérablement le risque de corrosion. Les performances en flexion de poutres longues ont été testées. La corrosion des armatures modifie le mode de défaillance des poutres en béton armé. La diminution de la charge de plastification et de la capacité ultime a été corrélée à la perte de section transversale des barres tendues. Les résultats expérimentaux indiquent qu’une réduction de 1% de la section transversale correspond à une réduction de 1% de la charge de plastification et de la capacité ultime. En ce qui concerne les performances mécaniques des poutres courtes, les résultats montrent qu’une corrosion sévère par piqûres sur les armatures tendues change le mode de défaillance par cisaillement à celui en flexion. Le mode de rupture des poutres courtes corrodées dépend non seulement du ratio entre la portée et la hauteur utile, mais également du degré de corrosion des cadres d’effort tranchant.

The aim of this study was to investigate the diffusion of chloride ions into concrete samples that were exposed in scenarios that simulate the splash, tidal, atmospheric, and immersed portions of a marine structure. To study the atmospheric deposition, the project also investigated the relationship between chloride ion deposition on the wet candle and its accumulation into concrete samples. Results from the wet candle experiment indicated that between 2% and 45% of the chlorides deposited per square meter of exposed area could be found within the concrete samples. After 6 months, slag G1a blocks showed the most resistance to chloride penetration in the tidal and splash simulations. After 10 months of exposure, fly ash samples had the slowest rates of diffusion in the tidal simulation while the fly ash + silica fume samples and the slag samples measured similar rates of diffusion within the tidal zone. After 90 days of curing, cylinders composed of 20% fly ash & 8% silica fume measured the highest average resistivity values and were found to be less vulnerable to chloride ion penetration than the 20% fly ash and the 50% slag concrete through rapid migration tests. / by Victor Anthony Echevarria. / Thesis (M.S.C.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

La durabilité des ouvrages en béton armé est étroitement liée à la composition des matériaux dont ils sont formés, et plus particulièrement aux propriétés de ces derniers. Cette durabilité est caractérisée par des indicateurs parmi lesquels se trouve le coefficient de diffusion des chlorures. Ceux-ci pénètrent le béton et interagissent avec les ions composant la solution interstitielle (contenue dans les pores) ainsi que les composants de la matrice cimentaire. Il existe peu de travaux dans la littérature qui décrivent toutes ces interactions ioniques de façon simultanée et encore moins leur prise en compte dans l’étude et la modélisation des transferts. Ce travail de thèse présente une étude des interactions multi-espèces se produisant lors du transfert des ions chlorure. Pour ce faire, l’évolution de la composition de la solution interstitielle, de plusieurs pâtes de ciment contenant diverses additions minérales, est étudiée. La solution interstitielle des pâtes de ciment est extraite suite à un essai de migration par pressage et analysée par chromatographie ionique. Par ailleurs, l’évolution de la microstructure de ces matériaux suite au transfert des chlorures est caractérisée par porosimétrie à intrusion de mercure (PIM) et microscopie électronique à balayage (MEB). Ceci a permis de mettre en évidence les modifications provoquées par la diffusion des ions chlorures. Dans un second temps, et afin de simuler le transfert des chlorures dans la matrice cimentaire, un modèle de transfert multi-espèces est développé. Dans ce sens, plusieurs modèles de transfert mono et multi-espèces, sous l’effet d’un champ électrique ou non, en régime stationnaire et transitoire ont été développés auparavant. L’objectif de cette partie numérique est d’étendre ces modèles à la prise en compte de l’ensemble des ions composant la solution interstitielle ainsi que leurs interactions multi-espèces conduisant à la précipitation de composés à base de chlore et à la dissolution des hydrates. La formulation mathématique des phénomènes étudiés est établie à partir de la loi de conservation de masse et les équations de la thermodynamique. Les conditions initiales et aux limites sont adaptées pour tenir compte à la fois de la composition chimique réelle de l’eau de mer et de celle de la solution interstitielle. Les résultats obtenus permettent de mettre en exergue l’effet de ces phénomènes sur la composition chimique de la solution interstitielle ainsi que sur le transfert des chlorures. / The durability of the reinforced concrete structures is closely related to the composition of their materials and, particularly to their properties. This durability is characterized by indicators among which we quote the diffusion coefficient of chlorides. These ionic species penetrate through the concrete and interact with the other species present in the interstitial solution (contained in concrete pores) as well as the cementitious matrix components. In the literature, there is a lake of data describing simultaneously these ionic interactions, especially their consideration in the study or modeling the ionic transport phenomena. This work focuses on the study of multispecies interactions that occur during the chloride transfer. To this purpose, the evolution of pore solutions chemistry of hardened cement pastes manufactured with different mineral additions is investigated. This solution is extracted, before and after migration test, using a specific press and analyzed by ionic chromatography. Furthermore, the microstructure evolution of these cement pastes is characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). This allows highlighting the modification caused by chloride penetration. Secondly, for the modeling of chloride transport in cement based materials, a multispecies transport model is developed. In this context, several mono and multispecies transport models, under an electrical field or not, in transitory or steady state were developed previously. The aim of this numerical study is to extend these models in order to consider the ions present in the interstitial solution and their multispecies interactions leading to the precipitation of new chloride compound and the dissolution of some hydrates. The mathematical formulation of the phenomena studied was established from the principle of mass conservation and the thermodynamic equations. Initial and boundary conditions were adopted to take into account both the chemical composition of sea water and that of pore solution. Results highlight the effect of these phenomena on the pore solution chemistry and the chloride transport.

D. Tech. Chemical, Metallurgical and Materials Engineering / This study provides experimental data and new perspectives on selective precipitation of platinum group metals (PGMs) in the presence of base metals while at the same time reviewing the mass transfer characteristics and models associated with metal sulphides precipitation in liquid-liquid and gas-liquid systems. In this study, the objective was to investigate and validate the concept of selective precipitation of platinum from chloride media using sulphur-bearing liquids or gases.

Thesis (Ph.D. in Neuroscience) -- University of Colorado at Denver and Health Sciences Center, 2006. / Typescript. Includes bibliographical references (leaves 86-96). Free to UCDHSC affiliates. Online version available via ProQuest Digital Dissertations;