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Brewster Angle Microscopy Study of Model Lung Surfactant Systems at the Air-Water and Air-Physiological Buffer InterfacesCastada, Hardy Zingalaoa 22 October 2010 (has links)
No description available.
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Surface Forces in Thin Liquid FilmsHuang, Kaiwu 10 January 2020 (has links)
Thin liquid films (TLFs) of water are ubiquitous in daily lives as well as in many industrial processes. They can be formed between two identical phases, as in colloid films between two macroscopic surfaces and foam films between two air bubbles; and between two dissimilar phases, as in wetting films. Stability of the colloids, foams, and wetting films is determined by the surface forces in the TLFs. Depending on the nature of the surfaces involved, the stabilities can be predicted using combinations of three different forces, i.e., the van der Waals, electrical double layer (EDL), and hydrophobic forces. The objective of the present work is to study the roles of these forces in determining the stabilities of the TLFs of water confined between i) an air bubble and a hydrophobic surface and ii) an oil drop and a hydrophobic surface, with particular interest in studying the role of the hydrophobic force.
The first part of the study involves the measurement of the surface forces in the TLFs confined between bitumen drops and mineral surfaces. Deformation of bitumen drops has been monitored by interferometry while it approaches a flat surface. By analyzing the spatiotemporal film profiles, both the capillary and hydrodynamic forces have been calculated using the Young-Laplace equation and the Reynolds lubrication approximation, respectively, with the surface forces being determined by subtracting the latter from the former. The results are useful for better understanding the effects of electrolyte and pH on bitumen liberation and recovery by flotation and for developing a filtration model from first principles.
The second part of the study involves the surface force measurement in wetting (flotation) films. Surface forces in the TLFs of water on silica surfaces have been measured using the force apparatus for deformable surfaces (FADS) using an air bubble as a force sensor. The measurements have been conducted in the presence of various cationic surfactants such as dodecylamine hydrochloride (DAH), and alkyltrimethylammonium chloride (CnTACl), electrolytes, and polymers. The results show that film stability and hence the kinetics of film thinning can be greatly improved by the control of bubble ζ-potentials, whose role in flotation has long been neglected in flotation studies.
Force measurements have also been conducted in the TLFs of water confined between oil drops and hydrophobic surfaces. Stability of this type of film plays an important role in a process of using oil drops rather than air bubbles to collect hydrophobic particles from aqueous phase. The force measurements conducted in the present work show that hydrophobic forces are much stronger in water films formed between oil drops and hydrophobic surfaces than in water films formed between air bubbles and hydrophobic surfaces, which can be attributed to the differences in the Hamaker constants involved. / Doctor of Philosophy / When two macroscopic surfaces in water are brought to a close proximity, a thin liquid film (TLF) is formed in between, with its stability being determined by the surface forces present in the film. TLFs are ubiquitous in daily lives and play a decisive role in many industrial processes such as mineral flotation, food processing, oil extraction, heat transfer, etc. In the present work, the surface forces present in wetting films have been measured by approaching an air bubble (or an oil drop) slowly toward a flat surface while monitoring the curvature changes during film thinning by interferometry and calculating the capillary forces using the Young-Laplace equations. By analyzing the results in view of the Frumkin-Derjaguin isotherm and the extended DLVO theory, it was possible to determine the changes in the van der Waals, electrical double-layer (EDL), and hydrophobic forces during film thinning. The results show that both the EDL and the long-range component of the hydrophobic force control the kinetics of film thinning and rupture while the contact angle formation is controlled by the van der Waals force and the short-range hydrophobic force. It has been found also that n-alkane drops form substantially larger contact angles than air bubbles on a hydrophobic surface due to the fact that the van der Waals force is attractive in the drop-surface interactions while the same is repulsive in the bubble-surface interactions. These observations have a profound implication in flotation, that is, oil drops can recover hydrophobic particles from an aqueous phase better than air bubbles.
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Investigation of Static and Dynamic Reaction Mechanisms at Interfaces and Surfaces Using Density Functional Theory and Kinetic Monte Carlo SimulationsDanielson, Thomas Lee 27 May 2016 (has links)
The following dissertation is divided into two parts. Part I deals with the modeling of helium trapping at oxide-iron interfaces in nanostructured ferritic alloys (NFAs) using density functional theory (DFT). The modelling that has been performed serves to increase the knowledge and understanding of the theory underlying the prevention of helium embrittlement in materials. Although the focus is for nuclear reactor materials, the theory can be applied to any material that may be in an environment where helium embrittlement is of concern. In addition to an improved theoretical understanding of helium embrittlement, the following DFT models will provide valuable thermodynamic and kinetic information. This information can be utilized in the development of large-scale models (such as kinetic Monte Carlo simulations) of the microstructural evolution of reactor components. Accurate modelling is an essential tool for the development of new reactor materials, as experiments for components can span decades for the lifetime of the reactor.
Part II of this dissertation deals with the development, and use of, kinetic Monte Carlo (KMC) simulations for improved efficiency in investigating catalytic chemical reactions on surfaces. An essential technique for the predictive development and discovery of catalysts relies on modelling of large-scale chemical reactions. This requires multi-scale modelling where a common sequence of techniques would require parameterization obtained from DFT, simulation of the chemical reactions for millions of conditions using KMC (requiring millions of separate simulations), and finally simulation of the large scale reactor environment using computational fluid dynamics. The tools that have been developed will aid in the predictive discovery, development and modelling of catalysts through the use of KMC simulations. The algorithms that have been developed are versatile and thus, they can be applied to nearly any KMC simulation that would seek to overcome similar challenges as those posed by investigating catalysis (such as the need for millions of simulations, long simulation time and large discrepancies in transition probabilities). / Ph. D.
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L'influence des cultivars sur les proprietés fonctionnelles de la caroube Libanaise / The influence of cultivar on functional properties of the lebanese carobHaddarah, Amira 12 December 2013 (has links)
Le caroubier est considéré comme l'un des arbres fruitiers et forestiers qui présente le plus grand potentiel de valorisation puisque toutes les parties de cette plante sont utilisables dans plusieurs applications industriels. Le caroubier est cultivé dans plusieurs régions du Liban mais peu d'études sont disponibles sur les voies de valorisation et sur les propriétés fonctionnelles et structurales des graines et des gousses. Ainsi, dans le cadre d'une démarche qui vise à promouvoir et contribuer à une meilleure valorisation et gestion de cette ressource renouvelable, nous avons entrepris dans cette thèse des travaux consacrés à la caractérisation et à l'évaluation de la valeur nutritive et fonctionnelle des gousses de caroube issues de plusieurs régions libanaise. Ces travaux ont porté notamment sur la caractérisation morphologique et physico-chimique des gousses et sur la purification des gommes extraits des graines. Ces gommes ont fait l'objet d'une étude approfondie portant sur leur comportement rhéologique et la relation entre ce comportement, la variété et le lieu géographique. Nous avons aussi déterminé les isothermes de sorption de ces gommes pour prédire les conditions idéales de leur conservation. Les résultats obtenus à l'issue de cette étude ont démontré clairement la présence des corrélations morphologie, composition chimique et coordonnées géographiques de différents cultivars étudiés. De même, les études structurales et rhéologiques ont montré des différences significatives entre les gommes purifiées. Cette différence semble être liée à une variation du rapport galactose/mannose et de la masse molaire observée selon les variétés. Par ailleurs, les études des isothermes de sorption ont permis de fournir des informations complémentaires sur leurs hygroscopicités et par conséquence sur les conditions idéales de leur conservation / The carob plant is considered as one of the fruit and forester tree that has the greatest potential of valorization since all the parts of this plant can be used in several food and cosmetic applications. The carob is cultivated in several areas of lebanon but few studies are available on the ways of valorization and the functional and structural properties of the different fractions of this tree (seeds and pods). Thus, in view to develop a strategy aims to promote and contribute to a better valorization and management of this renewable resource, we undertook in this thesis of work devoted to the characterization and the evaluation of nutritive and functional properties of the carob pods resulting from several lebanese areas. This work focused particularly on the morphological and physicochemical characterization of the pods and the purified fraction of gum. These gums were the subject of a thorough study relating to their rheological behavior and the relation between this behavior, the variety and the geographical localization of the studied varieties. We also determined the isotherms of sorption of these gums to predict the ideal conditions of their conservation. The obtained results clearly showed the presence of the correlations between morphology, chemical composition and geographical localization of the different studied cultivars. In the same way, the structural and rheological studies showed significant differences between purified gums. This difference seems to be related to a variation of the galactose /mannose ratio and molar mass according to the varieties. These interesting rheological properties open the carob gums a new niches of valorization with added values. In addition, the studies of the isotherms of sorption provided additional information on their hygroscopicities and by consequence on the ideal conditions of their conservation
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Estudo comparativo de sílicas mesoporosas organofuncionalizadas magnéticas como adsorventes de Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) / Comparative study of magnetic organofunctionalized mesoporous silica for adsorption of BTEX from aqueous solutionOsorio, Daniel Santos Garcia 08 October 2018 (has links)
A contaminação de aguas pela mistura Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) vem gerando a necessidade do desenvolvimento de metodologias altamente eficientes na remoção de poluentes e de metodologias analíticas para monitoramento ambiental suficientemente sensíveis, seletivos, reprodutíveis e rápidos. Nesse contexto, adsorventes com propriedades magnéticas aparecem como alternativas eficientes, de baixo custo e de fácil automação, inclusive possibilitando o desenvolvimento de metodologia analítica baseada na extração em fase sólida magnética (m-SPE), que vem ganhando interesse crescente por permitir extração rápida e análise efetiva dos poluentes com alta sensibilidade. A busca por adsorventes adequados exige o estudo de materiais com grande área superficial, funcionalizáveis e estáveis como as sílicas, mais especificamente uma comparação entre os tipos de sílica e do tipo de agente funcionalizante nas propriedades de adsorção/dessorção. Sílicas mesoporosas oraganofuncionalizas magnéticas com diferentes morfologias foram preparadas: sílica mesoporosa ordenada MCM-48 e MCM-41, bem como nanoparticulas esféricas de sílica mesoporosa (NPSiO2). A formação da silica mesoporosa ordenada começa com a preparação de um template de CTAB sobre o qual são depositados/formados os materiais MCM-41 e MCM-48. A concentração de CTAB deve ser controlada com cuidado pois estruturas com diferentes morfologias podem ser geradas variando-se esse parâmetro. As análises de espectroscopia FTIR, DRX e sorção de N2 revelaram que os materiais preparados são sílicas mesoporosas ordenadas com arranjo tipo giroide 3D (MCM-48) ou do tipo hexagonal (MCM-41) com área superficial respectivamente de 1212 m2.g-1 e 1159 m2.g-1. Além disso, as imagens de MET do material MCM-48 mostraram tamanho médio de partícula igual a 116 nm ± 15 nm. Para facilitar a remoção do adsorvente, nanopartículas de magnetita (SPION) foram incorporadas na superfície dos materiais adsorventes. O tempo de remoção típico foi determinado como sendo de 1 minuto. A organofuncionalização da sílica com octadecilssilano (C18), octilssilano (C8) e difenilssilano (Ph2) foi confirmada por espectroscopia FTIR e análise termogravimétrica demostrando a presença e a percentagem em massa dos grupos orgânicos em cada tipo de sílica mesoporosa. Usando como referência sílica gel 60 comercial (Sílica), foram comparadas as propriedades de adsorção frente a BTEX em agua, quando o agente funcionalizante é C8, C18 ou Ph2. Os resultados indicaram que as capacidades de adsorção, segundo o modelo de Langmuir, seguem a seguinte ordem C8≥C18>>Ph2. A partir disso, as propriedades de adsorção das demais sílicas funcionalizadas com C8 foram comparadas determinando-se que as capacidades de adsorção, segundo o modelo de Langmuir, estão na seguinte ordem: MCM-48>Sílica>NPSiO2>MCM-41. O nanocompósito organofuncionalizado MCM48-C8/SPION, que mostrou as melhores propriedades de adsorção, foi usado para a extração em fase sólida magnética (m-SPE) de BTEX em agua de posto de gasolina. Verificou-se que apenas 30 mg de adsorvente, 5 min de contato com a solução de BTEX, 1 min para remoção do adsorvente e 1 min para a extração foram suficientes para concentração/recuperação de BTEX de agua pela técnica de m-SPE, viabilizando a análise quantitativa, no caso por CG-MS. / The contamination of water bodies by Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) has prompted the development of more efficient methodologies for their removal and the development of sufficiently sensitive, selective, reproducible and fast analytical methods for environmental monitoring. In this context, adsorbent materials with magnetic properties appear as efficient, low cost and easy automation alternatives, including the development of analytical methods based on magnetic solid phase extraction (m-SPE), which has gaining increasing interest since allows rapid extraction and effective analysis of pollutants with high sensitivity. The search for suitable adsorbents requires the study of materials with large surface area, functionalizable and stable as the silica\'s family, more specifically a comparison between the types of silica and the type of functionalizing agent on their adsorption/desorption properties. Magnetic organofunctionalized mesoporous silicas with different morphologies were prepared: ordered mesoporous silica MCM-48 and MCM-41, as well as spherical nanoparticles of mesoporous silica (NPSiO2). The formation of ordered mesoporous silica begins with the preparation of a CTAB template on which silica is deposited/formed to produce MCM-41 and MCM-48 materials. The CTAB concentration must be carefully controlled since colloidal structures with different morphologies can be generated by varying this parameter. The FTIR, XRD and N2 sorption spectroscopy analyzes confirmed the preparation of ordered mesoporous silica materials with a gyroid 3D (MCM-48), or hexagonal type (MCM-41) arrangement respectively with a surface area of 1212 m2.g-1 and 1159 m2.g-1. In addition, the MET images of the MCM-48 material showed mean particle size equal to 116 nm ± 15 nm. To facilitate removal from water, magnetite nanoparticles (SPIONs) were incorporated into the surface of adsorbent materials. The typical removal time was determined to be 1 minute. The organofunctionalization of the silica with octadecylsilane (C18), octylsilane (C8) and diphenylsilane (Ph2) was confirmed by FTIR spectroscopy and thermogravimetric analysis demonstrating the presence and allowing the determination of the mass percentage of the organic fraction in each type of mesoporous silica. Using commercial silica gel (Silica) as reference, the adsorption properties toward BTEX in water were compared when the functionalizing agent is C8, C18 or Ph2. The results indicated that the adsorption capacities, according to the Langmuir model, decrease in the following order C8 ≥ C18 >> Ph2. From this, the adsorption properties of the C8 functionalized silicas were compared showing that the adsorption capacities according to the Langmuir model decrease in the following order: MCM-48 > Silica > NPSiO2 > MCM-41. The organofunctionalized nanocomposite MCM48-C8/SPION, exhibiting the best adsorption properties, was used in magnetic solid phase extraction (m-SPE) of BTEX from gas station water. Only 30 mg of adsorbent, 5 min of contact with the BTEX solution, 1 min to remove the adsorbent and 1 min for extraction were enough for concentration/recovery of BTEX in water by m-SPE technique suitable for quantitative analysis, in this case by CG-MS.
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Estudo comparativo de sílicas mesoporosas organofuncionalizadas magnéticas como adsorventes de Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) / Comparative study of magnetic organofunctionalized mesoporous silica for adsorption of BTEX from aqueous solutionDaniel Santos Garcia Osorio 08 October 2018 (has links)
A contaminação de aguas pela mistura Benzeno, Tolueno, Etilbenzeno e Xilenos (BTEX) vem gerando a necessidade do desenvolvimento de metodologias altamente eficientes na remoção de poluentes e de metodologias analíticas para monitoramento ambiental suficientemente sensíveis, seletivos, reprodutíveis e rápidos. Nesse contexto, adsorventes com propriedades magnéticas aparecem como alternativas eficientes, de baixo custo e de fácil automação, inclusive possibilitando o desenvolvimento de metodologia analítica baseada na extração em fase sólida magnética (m-SPE), que vem ganhando interesse crescente por permitir extração rápida e análise efetiva dos poluentes com alta sensibilidade. A busca por adsorventes adequados exige o estudo de materiais com grande área superficial, funcionalizáveis e estáveis como as sílicas, mais especificamente uma comparação entre os tipos de sílica e do tipo de agente funcionalizante nas propriedades de adsorção/dessorção. Sílicas mesoporosas oraganofuncionalizas magnéticas com diferentes morfologias foram preparadas: sílica mesoporosa ordenada MCM-48 e MCM-41, bem como nanoparticulas esféricas de sílica mesoporosa (NPSiO2). A formação da silica mesoporosa ordenada começa com a preparação de um template de CTAB sobre o qual são depositados/formados os materiais MCM-41 e MCM-48. A concentração de CTAB deve ser controlada com cuidado pois estruturas com diferentes morfologias podem ser geradas variando-se esse parâmetro. As análises de espectroscopia FTIR, DRX e sorção de N2 revelaram que os materiais preparados são sílicas mesoporosas ordenadas com arranjo tipo giroide 3D (MCM-48) ou do tipo hexagonal (MCM-41) com área superficial respectivamente de 1212 m2.g-1 e 1159 m2.g-1. Além disso, as imagens de MET do material MCM-48 mostraram tamanho médio de partícula igual a 116 nm ± 15 nm. Para facilitar a remoção do adsorvente, nanopartículas de magnetita (SPION) foram incorporadas na superfície dos materiais adsorventes. O tempo de remoção típico foi determinado como sendo de 1 minuto. A organofuncionalização da sílica com octadecilssilano (C18), octilssilano (C8) e difenilssilano (Ph2) foi confirmada por espectroscopia FTIR e análise termogravimétrica demostrando a presença e a percentagem em massa dos grupos orgânicos em cada tipo de sílica mesoporosa. Usando como referência sílica gel 60 comercial (Sílica), foram comparadas as propriedades de adsorção frente a BTEX em agua, quando o agente funcionalizante é C8, C18 ou Ph2. Os resultados indicaram que as capacidades de adsorção, segundo o modelo de Langmuir, seguem a seguinte ordem C8≥C18>>Ph2. A partir disso, as propriedades de adsorção das demais sílicas funcionalizadas com C8 foram comparadas determinando-se que as capacidades de adsorção, segundo o modelo de Langmuir, estão na seguinte ordem: MCM-48>Sílica>NPSiO2>MCM-41. O nanocompósito organofuncionalizado MCM48-C8/SPION, que mostrou as melhores propriedades de adsorção, foi usado para a extração em fase sólida magnética (m-SPE) de BTEX em agua de posto de gasolina. Verificou-se que apenas 30 mg de adsorvente, 5 min de contato com a solução de BTEX, 1 min para remoção do adsorvente e 1 min para a extração foram suficientes para concentração/recuperação de BTEX de agua pela técnica de m-SPE, viabilizando a análise quantitativa, no caso por CG-MS. / The contamination of water bodies by Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) has prompted the development of more efficient methodologies for their removal and the development of sufficiently sensitive, selective, reproducible and fast analytical methods for environmental monitoring. In this context, adsorbent materials with magnetic properties appear as efficient, low cost and easy automation alternatives, including the development of analytical methods based on magnetic solid phase extraction (m-SPE), which has gaining increasing interest since allows rapid extraction and effective analysis of pollutants with high sensitivity. The search for suitable adsorbents requires the study of materials with large surface area, functionalizable and stable as the silica\'s family, more specifically a comparison between the types of silica and the type of functionalizing agent on their adsorption/desorption properties. Magnetic organofunctionalized mesoporous silicas with different morphologies were prepared: ordered mesoporous silica MCM-48 and MCM-41, as well as spherical nanoparticles of mesoporous silica (NPSiO2). The formation of ordered mesoporous silica begins with the preparation of a CTAB template on which silica is deposited/formed to produce MCM-41 and MCM-48 materials. The CTAB concentration must be carefully controlled since colloidal structures with different morphologies can be generated by varying this parameter. The FTIR, XRD and N2 sorption spectroscopy analyzes confirmed the preparation of ordered mesoporous silica materials with a gyroid 3D (MCM-48), or hexagonal type (MCM-41) arrangement respectively with a surface area of 1212 m2.g-1 and 1159 m2.g-1. In addition, the MET images of the MCM-48 material showed mean particle size equal to 116 nm ± 15 nm. To facilitate removal from water, magnetite nanoparticles (SPIONs) were incorporated into the surface of adsorbent materials. The typical removal time was determined to be 1 minute. The organofunctionalization of the silica with octadecylsilane (C18), octylsilane (C8) and diphenylsilane (Ph2) was confirmed by FTIR spectroscopy and thermogravimetric analysis demonstrating the presence and allowing the determination of the mass percentage of the organic fraction in each type of mesoporous silica. Using commercial silica gel (Silica) as reference, the adsorption properties toward BTEX in water were compared when the functionalizing agent is C8, C18 or Ph2. The results indicated that the adsorption capacities, according to the Langmuir model, decrease in the following order C8 ≥ C18 >> Ph2. From this, the adsorption properties of the C8 functionalized silicas were compared showing that the adsorption capacities according to the Langmuir model decrease in the following order: MCM-48 > Silica > NPSiO2 > MCM-41. The organofunctionalized nanocomposite MCM48-C8/SPION, exhibiting the best adsorption properties, was used in magnetic solid phase extraction (m-SPE) of BTEX from gas station water. Only 30 mg of adsorbent, 5 min of contact with the BTEX solution, 1 min to remove the adsorbent and 1 min for extraction were enough for concentration/recovery of BTEX in water by m-SPE technique suitable for quantitative analysis, in this case by CG-MS.
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L’impact du séchage au jeune âge sur la carbonatation des matériaux cimentaires avec additions minérales / The impact of drying at the early age of the carbonation cementitious materials with mineral admixturesBertin, Matthieu 27 November 2017 (has links)
De nos jours, l’utilisation de liants à faible teneur en clinker est de plus en plus courante. Or la cinétique de réaction des additions minérales utilisées est plus lente que celle du clinker. Si les conditions de cure ne sont pas adaptées, le matériau aura une structure poreuse plus importante, ce qui le rendra plus sensible à la pénétration des agents agressifs extérieurs comme le CO2 ou les Cl-. La carbonatation du béton est l’un des principaux phénomènes pouvant diminuer la durée de vie d’une structure en béton armé. En effet, elle entraine une diminution du pH de la solution interstitielle qui a pour conséquence une dépassivation des armatures, puis la corrosion de ces dernières si les conditions s’y prêtent.L’objectif de cette thèse est d’étudier l’impact de la carbonatation au jeune âge sur des liants à faible teneur en clinker. Pour cela l’étude se compose de deux aspects : le premier est l’étude de l’impact de l’hydratation et de la carbonatation sur les propriétés de transport et les isothermes de sorption hydrique, et le second est l’étude de l’impact du couplage hydratation-séchage-carbonatation sur la microstructure et la structure poreuse. Pour le premier aspect, les propriétés de transport étudiées sont la diffusion de l’O2, la diffusion de la vapeur d’eau, la perméabilité à l’eau liquide qui sont des données d’entrée dans les modèles de carbonatation ainsi que la perméabilité aux gaz qui est un indicateur de durabilité. Pour le second aspect, l’impact du couplage est mesuré par ATG et DRX pour déterminer l’assemblage de phases, de plus de la porosimétrie par intrusion de Mercure et des pesées hydrostatiques sont effectuées pour détecter le changement de la structure poreuse. Les matériaux étudiés sont des pâtes de ciment et des bétons avec un rapport eau/ liant de 0,57 avec l’un des trois liants suivants : CEM I, CEM I +30% de cendres volantes et CEM I +60% de laitiers.Pour le premier aspect, les résultats montrent que pour les pâtes de CEM I le temps de cure a un faible impact sur les isothermes de sorption de vapeur d’eau s’il est compris entre 3 jours et 6 mois. Alors que, pour les pâtes de CEM I + 60% de laitier, l’augmentation du temps de cure accroit significativement la teneur en eau (pour HR=65%, tcure=3 jours et pour tcure=6 mois ) dû à une augmentation de la teneur en C-S-H. D’autre part, la carbonatation entraine une diminution de la teneur en eau de l’échantillon, ainsi que l’amplitude de l’hystérésis. De plus, le gel a une porosité plus grossière. Par ailleurs, la carbonatation entraine une augmentation de la perméabilité aux gaz des matériaux. Pour le second aspect, les résultats montrent que l’utilisation d’additions minérales diminue la résistance à la carbonatation du matériau et que cette résistance augmente avec le temps de cure si l’échantillon contient des additions. La carbonatation de la portlandite, des C-S-H et des aluminates est concomitante. De plus, pour les matériaux aux laitiers, les résultats montrent qu’ils sont plus sensibles à la carbonatation des C-S-H et des aluminates que les CEM I. En effet quand le rapport variation molaire de CaCO3 sur variation molaire de Portlandite est calculé, il vaut 1.8 pour le CEM I et environ 3.5 pour les matériaux aux laitiers. Enfin, la carbonatation entraine une diminution du degré de saturation de l’échantillon. En effet, le degré de saturation à la surface de l’échantillon passe de 50% à 35% après carbonatation pour les échantillons de CEM I et de 50% à 5% pour les échantillons de CEM I + 60% de laitiers. Cette diminution peut s’expliquer par la diminution de la surface spécifique qui est divisée par 2 après carbonatation due à la décalcification des C-S-H. Même si la carbonatation entraine une diminution de porosité cette dernière est trop faible dans ce cas pour contrer cet effet / Nowaday, low clinker content binders are used more and more often. But the kinetics reactions of the supplementary cementitious materials (SCM) are slower than this one of clinker. If the curing conditions are not adapted, material will have a bigger pore structure and becomes more sensitive to the ingress of aggressive species from the environment like the CO2 or Cl-. Carbonation is one of main phenomena which can lead to decrease the life time of reinforced concrete structure. Indeed, it leads to a decrease of pore solution pH which leads to the depassivation of rebar. Then these rebars can be corroded if the conditions are appropriate.The aim of this thesis is to study the impact of carbonation at early age for binder with a low clinker content. This study was composed of two aspects: the first one is focus on the impact of hydration and carbonation on the transport properties and the water vapour sorption isotherms (WVSI), and the second one is focus on the impact of coupling hydration – drying-carbonation on the microstructure and the pore structure. For the first aspect, the studied transport properties was O2 diffusivity, water vapour diffusivity, water liquid permeability which are inputs for carbonation modelling and the intrinsic gas permeability which is a durability factor. For the second aspect, the coupling impact was measured by TGA and DRX to determine the phase assemblage; moreover Mercury intrusion porosimetry (MIP) and hydrostatic weigh were carried out to measure the change in the pore structure. The studied materials were cement pastes and concretes with water to binder ratio of 0.57 with one of the following binders: CEM I, CEM I +30% PFA and CEM I + 60% GGBS.For the first part, results show that a curing time between 3 days and 6 months has a low impact on the WVSI for the CEM I paste. Whereas, in the CEM I +60% GGBS paste, when the curing time increases, the water content increases (for a RH=65%, tcuring=3 days and for tcuring=6 months ), this is due to the increase of the C-S-H content. Moreover, carbonation leads to decrease the water content and the hysteresis becomes flat. Additionally, carbonation leads to increase the intrinsic gas permeability. For the second part, the results show that the use of SCM decreases the carbonation resistance and this resistance increases with the curing time. Carbonation of Portlandite, C-S-H and aluminates occurs in the same time. Moreover, the CEM I +60% GGBS paste are more sensitive to the carbonation of C-S-H and aluminates than the CEM I paste. Indeed, the molar variation of CaCO3 to the molar variation of Portlandite ratio has a value around 3.5 for the CEM I +60% GGBS and 1.8 for the CEM I. Finally, carbonation leads to decrease the water saturation degree at the surface of sample. Indeed, the degree of saturation at the surface of the sample increases from 50% to 35% after carbonation for the CEM I paste and from 50% to 5% for the CEm I +60% GGBS paste. This decrease can be explained by the decrease of the BET specific surface which is divided by 2 after carbonation. It is due to the decalcification of C-S-H. Although carbonation leads to a decrease of porosity, this one is too small in this case to counter this effect
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Estudo da corros?o no a?o carbono 1020 protegido com ?leo de coco saponificado: an?lise f?sico-qu?mica do comportamento qu?mico do tensoativoAraujo, Danyelle Medeiro de 29 July 2010 (has links)
Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1
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Previous issue date: 2010-07-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Corrosion inhibitors in solution are utilized to minimize processes from
corrosion in steel. Of the present dissertation was evaluated the efficiency by
inhibition from the surfactant saponified coconut oil (OCS) in the carbon steel 1020
through in linear polarization electrochemistry technique, well as, studied the process
from adsorption through from the isotherms from Langmuir, Frumkin and Temkin.
The corrosion current was determined through in Tafel extrapolation from the curves
in the polarization, and then, was calculated the efficiency in the inhibitor to each
concentration and temperature. Were studied four concentrations (12,5 ppm, 25
ppm, 50 ppm, and 75 ppm) in the inhibitor OCS and one in the NaCl salt (10.000
ppm) in six temperatures (301 K, 308 K, 313 K, 318 K, 323 K, and 328 K) in triplicate.
By the results obtained observed that the technique applied can evaluated with
rapidity and efficiency corrosion inhibitors. In relation to the isotherms, the than best
appropriated was the in Langmuir and in the concentrations studied, the that
obtained the best efficiency was the concentration of 75 ppm / Inibidores de corros?o em solu??o s?o utilizados para minimizar processos de
corros?o em a?o. Na presente disserta??o foi avaliada a efici?ncia de inibi??o do
tensoativo ?leo de coco saponificado (OCS) no a?o carbono 1020, atrav?s da
t?cnica eletroqu?mica polariza??o linear, bem como, estudado o processo de
adsor??o atrav?s das isotermas de Langmuir, Frumkin e Temkin. A corrente de
corros?o foi determinada atrav?s da extrapola??o de Tafel nas curvas de
polariza??o e, ent?o, foi calculada a efici?ncia do inibidor para cada concentra??o e
temperatura. Foram estudadas quatro concentra??es (12,5, 25,0, 50,0 e 75,0 ppm)
do inibidor OCS e uma do sal NaCl (10.000 ppm) em seis temperaturas (301, 308,
313, 318, 323 e 328 K) em triplicata. Pelos resultados obtidos, observou-se que a
t?cnica utilizada pode avaliar com rapidez e efici?ncia inibidores de corros?o. Em
rela??o ?s isotermas, a que melhor se adequou foi a de Langmuir e dentre as
concentra??es estudadas a que obteve a melhor efici?ncia foi ? concentra??o de 75
ppm
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Retenção de metais pesados em solos agricultáveis do Estado de Goiás / Retention of heavy metals in agricultural soils of the State of GoiásCASTRO, Mara Lucia Lemke de 31 July 2009 (has links)
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Previous issue date: 2009-07-31 / The intensification of the use of land for farming has caused great concern, mainly due to the impacts that these activities are causing the environment, particularly with regard
to it s contamination by chemicals. The application of chemicals and waste ground and in several, or in plants in order to take agronomically solid waste, improve productivity and increase agricultural production has been growing in the practices of cultivation. The form of improper disposal of waste in the soil, without any control of dose and form of application, and without knowledge of their ability to assimilate the different soil types, possibly predisposing the
occurrence of contamination and pollution along the profile these soils and may reach the water table and contaminate groundwater. This work aimed the analysis of the retention of
some heavy metals in Ultisol, Oxisol Typic Acrustox, Quartzipsamment and Kandic Oxisol found in savannah soil of the Goiás. Heavy metals in tests were Cadmium (Cd+2), lead
(Pb+2), copper (Cu+2), chromium (Cr+3 and Cr+6), nickel (Ni+2) and zinc (Zn+2). The sorption of the heavy metals in soil was evaluated by batch method and described by potential and linear models of the Freundlich isotherm. For the establishment of sorption isotherm were added in 5,0 cm3 of soil and 50,0 cm3 of solution containing the heavy metal being assessed with different concentrations within the limits acceptable soil. The potential and linear sorption isotherm submitted a good adjusted to describe the behavior of adsorption of heavy metals in different classes of soil studied. The detention of heavy metals in descending order was
the Ultisol: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Oxisol Typic Acrustox: Cr+3 > Cr+6 > Ni+2 > Cu+2 > Cd+2 > Zn+2 > Pb+2; Quartzipsamment: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Kandic Oxisol: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. The Quartzipsamment presented a less retention metal comparison other classes of soil, and therefore more vulnerable to contamination of groundwater. / A intensificação do uso das terras para fins agropecuários tem causado grande preocupação, devido, principalmente, aos impactos que essas atividades vêm causando ao meio
ambiente, sobretudo no que diz respeito à sua contaminação por substâncias químicas. A aplicação de produtos químicos e de resíduos diversos no solo e, ou, nas plantas, com o propósito de aproveitar agronomicamente resíduos sólidos, melhorar a produtividade e aumentar a produção agrícola, tem sido crescente nas práticas de cultivo. A forma inadequada de disposição de resíduos no solo, sem qualquer controle das doses e da forma de aplicação, e sem o conhecimento da
capacidade de sua assimilação pelos diferentes tipos de solos, possivelmente, predispõem a ocorrência de contaminação e de poluição ao longo do perfil desses solos, podendo alcançar o lençol freático e contaminar as águas subterrâneas. Objetivou-se com este trabalho a análise da retenção de alguns metais pesados nas classes de solo Argissolo Vermelho Eutrófico, Latossolo Vermelho Acriférrico, Neossolo Quartzarênico e Nitossolo Vermelho Eutroférrico encontrados em áreas de cultivo do Estado de Goiás. Os metais tóxicos avaliados nos ensaios de sorção foram cádmio (Cd+2), chumbo (Pb+2), cobre (Cu+2), cromo (Cr+3 e Cr +6),
níquel (Ni+2) e zinco (Zn+2). A sorção dos metais foi avaliada pelos modelos potencias e lineares da isoterma de Freundlich. Para o estabelecimento de isotermas de sorção foram adicionados em 5,0 cm3 de solo e 50,0 cm3 de solução contendo o metal tóxico a ser avaliado com diferentes concentrações, respeitando os limites aceitáveis. As isotermas de sorção potencial e linear apresentaram um bom ajuste para descrever o comportamento de adsorção dos metais tóxicos nas diferentes classes de solos estudadas. A sequência da retenção dos metais tóxicos em ordem decrescente foi, para o Argissolo Vermelho Eutrófico: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Latossolo Vermelho Acriférrico: Cr+3 > Cr+6 > Ni+2 >
Cu+2 > Cd+2 > Zn+2 > Pb+2; Neossolo Quartzarênico: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Nitossolo Vermelho Eutroférrico: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. O Neossolo Quartzarênico apresentou uma menor retenção de metais em comparação às demais classes de solo, sendo, portanto, mais vulnerável à contaminação das águas subterrâneas.
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Remoção de corantes sintéticos de efluentes aquosos usando adsorventes carbonadosProla, Liziê Daniela Tentler January 2016 (has links)
A casca de pinhão manso é um resíduo abundante da indústria de biocombustível e foi usada em sua forma natural (PN) e tratada por plasma não térmico (PP) como biossorvente para a remoção do corante Vermelho reativo 120 (VR-120) de soluções aquosas. Os nanotubos de carbono de parede múltipla (NTCPM) e carvão ativo (CA) foram investigados como adsorventes na remoção do corante Azul direto 53 (AD-53) a partir de águas residuais. Os materiais adsorventes foram caracterizados por espectroscopia Raman, espectroscopia de infravermelho, isotermas de adsorção/dessorção de N2, microscopia eletrônica de varredura e transmissão. As melhores condições para adsorção dos corantes foram alcançadas em pH 2,0. O tempo de contato para obter o equilíbrio de isotermas, em 298-323 K, foi fixado em 10 horas para os biossorventes PN e PP. Para estes, o modelo cinético de ordem geral forneu o melhor ajuste aos dados experimentais em comparação com as cinéticas pseudo-primeira ordem e pseudo-segunda ordem. Para o corante VR-120, os dados de equilíbrio (298-323 K) foram ajustados para o modelo de isoterma de Liu. A capacidade máxima de adsorção do corante ocorreu a 323 K, atingindo valores de 40,94 e 65,63 mg g-1 para o PN e PP, respectivamente. Os resultados dos estudos de adsorção/dessorção mostraram que a maior porcentagem de remoção de PN e PP foram alcançadas quando a mistura de solventes (acetona a 50% + 50% de 0,050 mol L-1 de NaCl (v/v)) foi utilizada. Os efluentes simulados foram utilizados para verificar a aplicabilidade dos biossorventes propostos. A remoção ocorreu de 68,2 e 94,6%, para PN e PP, respectivamente, em meio com elevada concentração salina. Já para NTCPM e CA os tempos de contato foram fixados em 3 horas e 4 horas, respectivamente. O modelo da cinética de ordem geral forneceu o melhor ajuste aos dados experimentais, se comparado aos modelos de adsorção cinéticos de pseudoprimeira ordem e pseudo-segunda ordem. Para o corante AD-53, os dados no equilíbrio (298-323 K) foram ajustados pelo modelo de isoterma de Sips. A capacidade máxima de adsorção do corante ocorreu a 323 K, com os valores de 409,4 e 135,2 mg g-1 para NTCPM e CA, respectivamente. Os resultados dos estudos de adsorção/dessorção mostraram que os NTCPM carregados com AD-53 podem ser regenerados (97,85%) utilizando uma solução de acetona aquosa (50% de acetona + 50% NaOH 3 mol L-1 (v/v)). Em experimentos de simulação de efluentes têxteis para aplicação dos adsorventes no tratamento de efluentes industriais, foram obtidas as remoções de 99,87% e 97,00% para NTCPM e CA, respectivamente, num meio com alta salinidade e diversos corantes. / Jatropha curcas shell an abundant residue of the biocombustible industry, was used in its natural form (JN) and treated by non-thermal plasma (JP) as biosorbents for the removal of Reactive Red 120 (RR-120) dye from aqueous solutions. Multi-walled carbon nanotubes (MWCNT) and powder activated carbon (PAC) were used as adsorbents for adsorption of Direct Blue 53 dye (DB-53) from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, infrared spectroscopy, N2 adsorption/desorption isotherms, and scanning and transmission electron microscopy. The best conditions to adsorption of the dye by adsorbent were achieved at pH 2.0. The contact time to obtain equilibrium isotherms at 298–323 K was fixed at 10 h for both biosorbents. The general order kinetic model provided the best fit to the experimental data compared with pseudo-first order and pseudo-second order kinetic adsorption models. For RR-120 dye, the equilibrium data (298–323 K) were best fitted to the Liu isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, attaining values of 40.94 and 65.63 mg g−1 for JN and JP, respectively. The results of adsorption/desorption studies showed that the highest percentage of removal of JN and JP were obtained when the mixture of solvents (acetone 50% + 50% 0.050 mol L-1 NaCl (v/v)) was used. Simulated dyehouse effluents were used to check the applicability of the proposed biosorbents for effluent treatment. The removal was 68.2 and 94.6% for JP and JN, respectively, in media with high salinity. As for NTCPM and CA the contact times were set at 3 h and 4 h, respectively. The general order kinetic model provided the best fit of the experimental data compared to pseudo-first order and pseudo-second order kinetic adsorption models. For DB- 53 dye, the equilibrium data (298 to 323 K) were best fitted to the Sips isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, with the values of 409.4 and 135.2 mg g-1 for MWCNT and PAC, respectively. The results of adsorption/desorption studies showed that MWCNT loaded DB-53 could be regenerated (97.85%) using mixture 50% acetone + 50% of 3 mol L-1 NaOH (v/v). Simulated dye house effluents were used to evaluate the application of the adsorbents for effluent treatment, with removal of 99.87% and 97.00% for MWCNT and PAC, respectively.
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