As propriedades do solo cotidianamente podem não ser adequadas às características e às necessidades de projeto. É apresentada, como alternativa, a técnica de reforço com inclusão de elementos fibrosos à matriz de solo cimentado e não cimentado. Ainda, embora comuns, o comportamento do solo frente a solicitações cíclicas não é completamente conhecido. Nesse sentido, o estudo do comportamento de hidratação e da resposta cisalhante cíclica de um resíduo de mineração cimentado reforçado com fibras é objetivado. Para tanto, medidas de retração química, medidas de rigidez ao longo da hidratação e ensaios simple shear monotônicos e cíclicos foram realizados com resíduo de mineração cimentado e não cimentado, reforçado com fibras e não reforçado. O resíduo, oriundo da mineração de ouro, um silte arenoso com traços de argila, foi cimentado com diferentes teores de cimento Portland, entre 0% e 10% em relação à massa de solo seco, e reforçado com 0% e 0,5%, em relação à massa de sólidos secos, de fibras de polipropileno de 50mm de comprimento e 0,1mm de espessura, equivalentes a um índice aspecto de 500. Os resultados demonstraram que as fibras não afetaram o processo de hidratação das misturas de resíduo de mineração cimentadas, que apresentam tendência de atenuação logarítmica da retração química com o tempo. Quanto maiores as relações água/cimento, maior o nível de retração química. A inclusão de fibras a misturas de resíduo de mineração cimentadas, da mesma forma, não afetou a evolução dos valores de rigidez inicial, que crescem com tendência logarítmica em função do tempo e aumentam com o acréscimo do nível de cimentação. Sob condições monotônicas de cisalhamento, a adição de fibras conferiu ao material cimentado e não cimentado comportamento de endurecimento. Sob condições cíclicas de deformação cisalhante controlada, as fibras não afetaram a resposta cisalhante das amostras não cimentadas e provocaram aumento dos valores da tensão cisalhante das amostras cimentadas após sucessivos ciclos de esforços. Sob condições cíclicas de tensão cisalhante controlada, a adição de fibras às misturas não cimentadas proporcionou o aumento da resistência aos ciclos de esforços e às misturas cimentadas provocou aumento dos níveis de deformação cisalhante. A concordância das mesmas envoltórias de resistência tanto às trajetórias de tensões dos ensaios monotonônicos quanto às trajetórias dos ensaios cíclicos sob diferentes condições de carregamento possibilitou a obtenção dos mesmos parâmetros de resistência das misturas analisadas sob diferentes condições de carregamento. / The soil properties commonly may not suit the project characteristics and requirements. It is presented, as alternative, the improvement technique of fibrous elements inclusion to the cemented and uncemented soil matrix. Moreover, although common, the behaviour of soil under cyclic loads is not completely known. In this sense, the study of the hydration behaviour and the cyclic shear response of fibre reinforced cemented mine tailings is the main objective of this research. Therefore, chemical shrinkage measurements, stiffness measurements during hydration and monotonic and cyclic simple shear tests were conducted on fibre reinforced and unreinforced cemented and uncemented mine tailings. The tailings, produced from gold mining, are classified as a sandy silt with traces of clay and were cemented with different amounts of Portland cement, ranging from 0% to 10% by dry weigh of soil, and reinforced with 0% and 0.5% by dry weigh of solids of polypropylene fibers 50mm long and 0.1mm thick, equivalent to an aspect ratio of 500. The results showed fibres did not affect the hydration process of cemented mine tailings mixtures, which presents logarithmic attenuation of chemical shrinkage over time. The greater the water / cement ratio, the higher the level of chemical shrinkage. The inclusion of fibers to cemented mine tailings, likewise, did not affect the evolution of initial stiffness values, that raise logarithmic over time and increase with the increase of the cementation level. Under monotonic shear conditions, the addition of fibers confers hardening behaviour to the uncemented and cemented materials. Under shear strain controlled cyclic conditions, fibres did not affect the shear response of uncemented samples and increased shear stress values of cemented samples after successive load cycles. Under shear stress controlled cyclic conditions, the fibres addition to the uncemented mixtures increased the resistance to load cycles and to the cemented mixtures increased levels of shearing strain. The agreement of the same strength envelopes to both monotonic and cyclic stress paths, under different cyclic loading conditions, allows the use of the same strength parameters of mixtures analyzed under different loading conditions.

Made available in DSpace on 2014-07-29T15:18:22Z (GMT). No. of bitstreams: 1 dissertacao sandra k de melo - parte 1.pdf: 1174678 bytes, checksum: 23084cd61c88de8cd244682ffbc84c82 (MD5) Previous issue date: 2010-07-05 / Delayed ettringite formation (DEF) is a special type of an internal sulfate attack with SO4 2- ions from cement. This process is distinguished by neoformation of ettringite in concrete thermally cured at high temperature levels and exposed to high moisture in service life. This phenomenon can promote expansion and cracking, leading to rupture and spalling, achieving severe deterioration. This research had an experimental approach with the purpose to investigate DEF in concretes with pozzolanic Portland cement containing fly ash. These concretes were undergone to temperature rise by heat of hydration. It was produced two types of pumped concrete with cement content of 350 kg/m3 and 450 kg/m3 containing basaltic aggregate. Two big specimens were cast containing 200 liters of concrete and were immediately submitted to adiabatic temperature rise tests. After that, several specimens were drilled from them in order to evaluate compressive strength and elasticity modulus, as well as microstructural investigations by scanning electron microscopy (SEM) and X Ray diffraction (XRD) along 270 days. In addition, it was cast several cylindrical and prismatic samples with concrete containing 350 kg/m3of cement. Some of them were stored at the same condition of those during the thermal cure and others were conditioned in a moist room as reference, for properties and microstructural investigation. Prismatic ones were submitted to mass variation study, ultrasonic wave tests and also expansion tests. In order to complement this experimental program, a specific study on cement pastes was performed. This involved casting three series of cylindrical samples submitted to different cure cycles followed by evaluation of mass variation, ultrasonic velocity and also microstructure investigation by SEM and XRD. Main results proved that rising internal temperature of concrete by hydration heat above 60ºC promote delayed ettringite formation by microstructural analyses, although this formation had not caused negative consequences on mechanic properties of concretes up to age of 270 days evaluated. The study on the cement pastes confirmed that high temperatures affects the microstructure of cement matrix and also the formed products, collaborating to the formation of hydrated alumina phases besides ettringite. The presence of suggestive thaumasite at advanced ages seems to indicate that this calcium silicate sulfo-carbonate hydrate can accompany DEF process. / A formação da etringita tardia - Delayed Ettringite Formation (DEF) é um tipo especial de ataque por sulfato interno, em que os íons SO4 2- são provenientes do cimento. O processo se distingue pela neoformação da etringita em concretos curados termicamente às elevadas temperaturas e expostos às altas umidades na etapa de serviço. Tal fenômeno pode promover expansão e consequente fissuração, culminando na ruptura e lascamento do material, levando-o à severa deterioração. Este trabalho, de caráter experimental, objetivou investigar a formação da etringita tardia em concretos de cimento Porltand pozolânico, contendo cinza volante, submetido à elevação da temperatura devido ao calor de hidratação do cimento. Para isso, foram produzidos dois concretos bombeados, contendo agregados basálticos, e com consumos de cimento de 350 kg/m3 e 450 kg/m3, com os quais foram moldados dois corpos-de-prova (CPs) de 200 litros, que foram, separadamente, submetidos aos ensaios de elevação adiabática de temperatura. Após o ciclo de cura térmica nestes ensaios, deles foram extraídos corpos-de-prova para a avaliação da resistência à compressão e módulo de elasticidade, além de investigações microestruturais por microscopia eletrônica de varredura (MEV) e difração de Raios X (DRX) durante 270 dias. Adicionalmente, foram moldadas duas séries de corpos-de-prova cilíndricos e prismáticos com o primeiro concreto, sendo que uma foi armazenada na câmara adiabática juntamente com o CP de 200 L e a outra curada continuamente em câmara úmida, servindo de referência para as análises do comportamento mecânico e investigações microestruturais dos CPs cilíndricos. Os CPs prismáticos foram utilizados para a avaliação da variação de massa, velocidade ultrassônica e expansão. Para complementar a pesquisa, realizou-se, também, um estudo específico em pastas de cimento, sendo moldadas três séries de CPs cilíndricos, que foram submetidas a três diferentes ciclos de cura seguidas por uma avaliação da variação de massa e velocidade ultrassônica, além de investigações microestruturais por MEV e DRX. Os principais resultados mostraram que o aumento da temperatura interna do concreto, acima de 60ºC, por calor de hidratação do cimento, propiciou a formação da etringita tardia, constatada pela presença de etringita neoformada durante as análises microestruturais, porém sem efeito negativo sobre as propriedades mecânicas avaliadas até a idade investigada de 270 dias. O estudo de pasta comprovou que as altas temperaturas influem na porosidade da microestrutura da matriz cimentícia e sobre o tipo de produto formado, favorecendo a formação de aluminatos hidratados ao final do ciclo térmico e da etringita durante a estocagem sob alta umidade. A sugestiva presença da taumasita, em idades mais avançadas, parece indicar que este sulfocarbonato de cálcio e sílica hidratado pode acompanhar o processo de DEF.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-04-27T15:25:17Z No. of bitstreams: 3 Dissertação - Sandra Kurotusch de Melo - 2010 - (1).pdf: 4813708 bytes, checksum: 1d9f47d43918bba38729e74a5014833d (MD5) Dissertação - Sandra Kurotusch de Melo - 2010 - (2).pdf: 12360828 bytes, checksum: 0c969028600897645eaa255c2ea06346 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-04-27T15:28:35Z (GMT) No. of bitstreams: 3 Dissertação - Sandra Kurotusch de Melo - 2010 - (1).pdf: 4813708 bytes, checksum: 1d9f47d43918bba38729e74a5014833d (MD5) Dissertação - Sandra Kurotusch de Melo - 2010 - (2).pdf: 12360828 bytes, checksum: 0c969028600897645eaa255c2ea06346 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-04-27T15:28:35Z (GMT). No. of bitstreams: 3 Dissertação - Sandra Kurotusch de Melo - 2010 - (1).pdf: 4813708 bytes, checksum: 1d9f47d43918bba38729e74a5014833d (MD5) Dissertação - Sandra Kurotusch de Melo - 2010 - (2).pdf: 12360828 bytes, checksum: 0c969028600897645eaa255c2ea06346 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2010-07-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Delayed ettringite formation (DEF) is a special type of an internal sulfate attack with SO42- ions from cement. This process is distinguished by neoformation of ettringite in concrete thermally cured at high temperature levels and exposed to high moisture in service life. This phenomenon can promote expansion and cracking, leading to rupture and spalling, achieving severe deterioration. This research had an experimental approach with the purpose to investigate DEF in concretes with pozzolanic Portland cement containing fly ash. These concretes were undergone to temperature rise by heat of hydration. It was produced two types of pumped concrete with cement content of 350 kg/m3 and 450 kg/m3 containing basaltic aggregate. Two big specimens were cast containing 200 liters of concrete and were immediately submitted to adiabatic temperature rise tests. After that, several specimens were drilled from them in order to evaluate compressive strength and elasticity modulus, as well as microstructural investigations by scanning electron microscopy (SEM) and X Ray diffraction (XRD) along 270 days. In addition, it was cast several cylindrical and prismatic samples with concrete containing 350 kg/m3of cement. Some of them were stored at the same condition of those during the thermal cure and others were conditioned in a moist room as reference, for properties and microstructural investigation. Prismatic ones were submitted to mass variation study, ultrasonic wave tests and also expansion tests. In order to complement this experimental program, a specific study on cement pastes was performed. This involved casting three series of cylindrical samples submitted to different cure cycles followed by evaluation of mass variation, ultrasonic velocity and also microstructure investigation by SEM and XRD. Main results proved that rising internal temperature of concrete by hydration heat above 60ºC promote delayed ettringite formation by microstructural analyses, although this formation had not caused negative consequences on mechanic properties of concretes up to age of 270 days evaluated. The study on the cement pastes confirmed that high temperatures affects the microstructure of cement matrix and also the formed products, collaborating to the formation of hydrated alumina phases besides ettringite. The presence of suggestive thaumasite at advanced ages seems to indicate that this calcium silicate sulfo-carbonate hydrate can accompany DEF process. / A formação da etringita tardia - Delayed Ettringite Formation (DEF) é um tipo especial de ataque por sulfato interno, em que os íons SO42- são provenientes do cimento. O processo se distingue pela neoformação da etringita em concretos curados termicamente às elevadas temperaturas e expostos às altas umidades na etapa de serviço. Tal fenômeno pode promover expansão e consequente fissuração, culminando na ruptura e lascamento do material, levando-o à severa deterioração. Este trabalho, de caráter experimental, objetivou investigar a formação da etringita tardia em concretos de cimento Porltand pozolânico, contendo cinza volante, submetido à elevação da temperatura devido ao calor de hidratação do cimento. Para isso, foram produzidos dois concretos bombeados, contendo agregados basálticos, e com consumos de cimento de 350 kg/m3 e 450 kg/m3, com os quais foram moldados dois corpos-de-prova (CPs) de 200 litros, que foram, separadamente, submetidos aos ensaios de elevação adiabática de temperatura. Após o ciclo de cura térmica nestes ensaios, deles foram extraídos corpos-de-prova para a avaliação da resistência à compressão e módulo de elasticidade, além de investigações microestruturais por microscopia eletrônica de varredura (MEV) e difração de Raios X (DRX) durante 270 dias. Adicionalmente, foram moldadas duas séries de corpos-de-prova cilíndricos e prismáticos com o primeiro concreto, sendo que uma foi armazenada na câmara adiabática juntamente com o CP de 200 L e a outra curada continuamente em câmara úmida, servindo de referência para as análises do comportamento mecânico e investigações microestruturais dos CPs cilíndricos. Os CPs prismáticos foram utilizados para a avaliação da variação de massa, velocidade ultrassônica e expansão. Para complementar a pesquisa, realizou-se, também, um estudo específico em pastas de cimento, sendo moldadas três séries de CPs cilíndricos, que foram submetidas a três diferentes ciclos de cura seguidas por uma avaliação da variação de massa e velocidade ultrassônica, além de investigações microestruturais por MEV e DRX. Os principais resultados mostraram que o aumento da temperatura interna do concreto, acima de 60ºC, por calor de hidratação do cimento, propiciou a formação da etringita tardia, constatada pela presença de etringita neoformada durante as análises microestruturais, porém sem efeito negativo sobre as propriedades mecânicas avaliadas até a idade investigada de 270 dias. O estudo de pasta comprovou que as altas temperaturas influem na porosidade da microestrutura da matriz cimentícia e sobre o tipo de produto formado, favorecendo a formação de aluminatos hidratados ao final do ciclo térmico e da etringita durante a estocagem sob alta umidade. A sugestiva presença da taumasita, em idades mais avançadas, parece indicar que este sulfocarbonato de cálcio e sílica hidratado pode acompanhar o processo de DEF.

Submitted by Cássia Santos (cassia.bcufg@gmail.com) on 2017-06-21T12:08:58Z No. of bitstreams: 2 Tese - Leonardo Martins de Abreu - 2017.pdf: 3441219 bytes, checksum: 28d75017e1ff1cdccf27de35d71771ea (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-07-10T13:08:28Z (GMT) No. of bitstreams: 2 Tese - Leonardo Martins de Abreu - 2017.pdf: 3441219 bytes, checksum: 28d75017e1ff1cdccf27de35d71771ea (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-07-10T13:08:28Z (GMT). No. of bitstreams: 2 Tese - Leonardo Martins de Abreu - 2017.pdf: 3441219 bytes, checksum: 28d75017e1ff1cdccf27de35d71771ea (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-05-12 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Using continuum and discrete solvent description models, we have investigated the chain length dependence of hydration free energy of polyol, glycine and ANK peptides. In this work this property values were calculated using thermodynamics integration with classical molecular dynamics simulation of one solute molecule to around 1000 solvent molecules. In addition, hydration free energy of polyol, glycine and ANK peptides were also calculated using polarizable continuum model in combination with the universal solvation model. Dipole moment and linear polarizability of the three systems had been also calculate using the PCM method. Our MD results show that ΔG exhibit a linear pattern with the size of glycine and ANK chain as well as observed for organic compounds in literature. In opposition, polyol’s ΔG shows a nonlinear behavior with increasing chain length and for this group of molecules it were found that water solvating effects have an important role over the polyol’s electric properties. These results suggest that in the case of polyols not only variation of polarizability but also variations of dipole moment in going from vacuum to water can influence the behavior of the free energy of hydration. All DM and PCM calculations were performed using the GROMACS 4.5 and the GAUSSIAN09 programs, respectively. / Utilizando modelos contínuo e discreto de descrição de solventes investigamos o comportamento da variação da energia livre na hidratação de series homólogas de poliol, glicina e peptídeos ANK. Neste trabalho os valores da energia de hidratação foram obtidos por integração termodinâmica utilizando simulações de dinâmica molecular clássica em sistemas com uma molécula de soluto para aproximadamente 1000 moléculas de solvente. Adicionalmente, o s resultados de ΔG foram obtidos utilizando o modelo contínuo polarizável combinado com o modelo de solvatação universal. Com o modelo PCM estudamos ainda o momento de dipolo e a polarizabilidade linear destes sistemas em questão e analisamos as contribuições que estas propriedades tem sobre a energia livre de hidratação e sua evolução com o crescimento de sistemas. Os resultados obtidos mostram que a variação da energia livre em função do número de resíduos cresce em valor absoluto para os três sistemas estudados. Para as moléculas de glicina e de peptídeos ANK observa-se um comportamento linear de ΔG com o número N de subunidades do sistema, semelhante ao observado para sistemas moleculares apresentados na literatura. Diferentemente, para as moléculas de poliol, os resultamos de ΔG exibem um comportamento não linear com o crescimento do sistema. Para esse grupo de moléculas inclusão do solvente tem grande impacto sobre o momento de dipolo e sobre a polarizabilidade linear. Este resultado mostra que para as moléculas de poliol não apenas a polarizabilidade, mas também variações no momento de dipolo podem influenciar o comportamento da energia livre de hidratação. Todos os cálculos foram realizados utilizando o programa GROMACS 4.5.4 e GAUSSIAN09.

Emulsões são sistemas dispersos constituídos de pelo menos duas fases líquidas imiscíveis e um agente emulsificante para estabilização das mesmas. a fase dispersa destesw sistemas é conhecida como fase interna e o meio dispersante como fase externa, porém, são sistemas termodinamicamente instáveis. A presença de cirstais líquidos aumenta a estabilidade destas dispersões e além de alterar a viscosidade. São capazes de promover o encapsulamento de ativos, permitindo liberação sustentada, bem como a proteção dos fármacos foto- e termosensíveis. O óleo de girassol é uma interessante fase oleosa em uma emulsão, pois possui proprie3dades cicatrizantes devido à alta concentração de ácido linoléico e propriedades antioxidantes devido à presença de polifenóis e vitamina E Possuemaplicações em diferentes áreas como: cosméticos, alimentos, veículos de medicamentos e outros. Assim, os objetivos deste estudo foram desenvolver emulsões estáveis contendo cristais líquidos a partir da mistura de óleo de girassol (Helianthus annus L.) e mineral (vaselina líquida), caracterizá-las e avaliar a influência de diferentes ésteres graxos na formação dos cristais líquidos. As formulações foram desenvolvidas utilizando o método de diagrama e pseudo-diagrama ternário, a partir dos quais foram selecionadas duas formulações que demonstraram se estáveis e apresentaram cristais líquidos durante todo o teste de estabilidade acelerada. As mesmas foram aditivadas com extrato glicólico de polifenois e ésteres graxos e permaneceram estáveis com cristal líquido. A caracterização reológica observou-se fluxo pseudo-plástico e tixotrópico, ideal para produtos farmacêuticos e cosméticos. O óleo de girassol apresentou atividade antioxidante mesmo quando aquecidos para o processo de emulsificação pelo método do radical DPPH·. As cadeias carbônicas dos ésteres graxos utilizados em produtos cosméticos podem influenciar na formação e manutenção dos cristais líquidos. Por meio dos testes in vivo observou-se que as formulações desenvolvidas promoveram aumento prolongado da hidratação da pele e não foram observados sinais de irritação cutânea. / Emulsions are dispersed systems consisting of at least two immiscible liquid phases and an emulsifying agent to stabilize them. The dispersed phase of these systems is known as the internal phase and the dispersing environ is the external phase, which are, however, thermodynamically unstable systems. The presence of liquid crystals increases the stability of these dispersions and also change the viscosity. They are able to promote the encapsulation of active, allowing sustained release as well as the protection of photo-and thermo-sensitive drugs. Sunflower oil is an interesting phase in an oily emulsion, because it has healing properties due to the high concentration of linoleic acid, and antioxidant properties due to the presence of polyphenols and vitamin E. They have applications in different areas such as cosmetics, food, medicines and other vehicles. The objectives of this study were to develop stable emulsions containing liquid crystals from a mixture of sunflower oil (Helianthus annus L.) and mineral (mineral oil), characterize them and evaluate the influence of different fatty esters in the formation of liquid crystals. The formulations were developed using the method of diagram and ternary pseudo-diagram, from which we selected two formulations that have been demonstrated stable and presented as liquid crystals throughout the accelerated stability test. They were doped with polyphenols glycolic extracts and acid esters, and have been kept stable with liquid crystal. At the rheological characterization was observed pseudo-plastic flow and thixotropic, ideal for pharmaceuticals and cosmetics. Sunflower oil showed antioxidant activity even when heated to the emulsification process by the radical DPPHo method. The carbon chains of fatty esters used in cosmetics can influence the formation and maintenance of liquid crystals. In vivo tests showed that the formulations developed promoted prolonged increase in skin hydration and were not seen signs of skin irritation.

Ce travail porte sur le conditionnement de déchets radioactifs dans une matrice cimentaire. Il vise plus particulièrement à évaluer la compatibilité chimique entre un mortier à base de ciment phospho-magnésien et l’aluminium métallique. Dans un premier temps, les processus physico-chimiques responsables de la prise et du durcissement du ciment phospho-magnésien sont étudiés : la diffraction des rayons X (DRX), la thermogravimétrie (ATG) et la résonance magnétique nucléaire (RMN-MAS du 31P et 11B) permettent d’identifier les phases solides précipitant au cours de l’hydratation du ciment ; la spectroscopie à plasma à couplage inductif (ICP-AES), la conductimétrie et la pH-métrie apportent des informations sur la composition de la solution porale. Dans un second temps, la corrosion de l’aluminium dans des mortiers phospho-magnésiens est étudiée par suivi du potentiel d’équilibre (OCP) et par spectroscopie d’impédance électrochimique (SIE).Le ciment phospho-magnésien est préparé à partir d’oxyde de magnésium (MgO) et de dihydrogénophosphate de potassium (KH2PO4). En présence d’eau, il s’hydrate selon un processus de dissolution / précipitation. La dissolution des réactifs conduit principalement à la formation de K-struvite (MgKPO4.6H2O), précédée par celle de deux hydrates intermédiaires : la phosphorrösslerite (MgHPO4.7H2O) et la phase Mg2KH(PO4)2.15H2O. L’acide borique retarde l’hydratation du ciment en ralentissant la formation des hydrates. La précipitation initiale d’un ou plusieurs composés boratés et phosphatés amorphes ou très mal cristallisés ainsi que la stabilisation des cations en solution (magnésium, potassium) pourraient en être la cause. Par comparaison avec une matrice à base de ciment Portland, la corrosion de l’aluminium dans le mortier phospho-magnésien est fortement limitée.Le pH de la solution interstitielle, proche de la neutralité, est en effet situé dans le domaine de passivation de l’aluminium. La corrosion dépend de plusieurs paramètres : elle est favorisée pour un rapport massique eau/ciment (e/c) très supérieur à la demande chimique en eau du liant (e/c = 0.51) ainsi que par la présence d’acide borique. Au contraire, le nitrate de lithium ajouté à l’eau de gâchage agit comme un inhibiteur de corrosion. Un mécanisme de corrosion en 4 étapes permet de modéliser les diagrammes d’impédance. L’évolution de la vitesse de corrosion et de la production de dihydrogène qui lui est associée peut alors être calculée au cours du temps. Les résultats obtenus sont en bon accord avec les mesures expérimentales du dihydrogène relâché par des plaques d’aluminium enrobées dans un mortier phospho-magnésien. / This work deals with the stabilization / solidification of radioactive waste using cement.More particularly, it aims at assessing the chemical compatibility between metallic aluminum and mortars based on magnesium phosphate cement. The physical and chemical processes leading to setting and hardening of the cement are first investigated. X-ray diffraction (XRD), thermogravimetry (TGA) and nuclear magnetic resonance spectroscopy (31P and11B MAS-NMR) arefirst used to characterize the solid phases formed during hydration, while inductively coupled plasma atomic emission spectroscopy analysis (ICP-AES), electrical conductimetry and pH measurementsprovide information on the pore solution composition. Then,the corrosion of metallic aluminum in magnesium phosphate mortars is studied by monitoring the equilibrium potential and by electrochemical impedance spectroscopy (EIS).Magnesium phosphate cement is prepared from a mix of magnesium oxide (MgO) and potassium dihydrogen orthophosphate (KH2PO4). In the presence of water, hydration occurs according to a dissolution – precipitation process. The main hydrate is K-struvite (MgKPO4.6H2O). Its precipitation is preceded by that of two transient phases: phosphorrösslerite (MgHPO4.7H2O) and Mg2KH(PO4)2.15H2O. Boric acid retards cement hydration by delaying theformation of cement hydrates. Two processes may be involved in this retardation: the initial precipitation of amorphous or poorly crystallized minerals containing boron and phosphorus atoms, and/or the stabilization of cations (Mg2+, K+) in solution.As compared with a Portland cement-based matrix, corrosion of aluminum is strongly limited in magnesium phosphate mortar. The pore solution pH is close to neutrality and falls within the passivation domain of aluminum. Corrosion depends on several parameters: it is promoted by a water-to-cement ratio (w/c) significantly higher than the chemical water demand of cement (w/c = 0.51), and by the addition of boric acid. On the contrary, lithium nitrate, dissolved in the mixing solution, acts as a corrosion inhibitor.A 4-step mechanism makes it possible to model the impedance diagrams. The evolution of the corrosion rate and of the amount of dihydrogen released with ongoing hydration is then calculated The results are in good agreement with the experimental determination of the H2 production by aluminum sheets embedded in magnesium phosphate mortar.

La baisse de la performance aérobie en climat tropical a été décrite dans de multiples activités d’endurance mais les processus responsables de cette altération restent assez méconnus. Nous nous proposons donc au travers d’études de laboratoire et de terrain, de tenter d'explorer les mécanismes responsables de cette baisse de performance aérobie en climat tropical. Si l'atteinte d'une température plafond est plutôt observée dans les protocoles de laboratoire, particulièrement à des intensités élevées, il semble que les mécanismes d'anticipation par réduction de l'intensité de l'exercice soient plus prégnants dans un environnement thermique qui exacerbe le stockage de chaleur. En effet, le climat tropical qui provoque l'augmentation du stockage de chaleur et les pertes hydriques, est un environnement susceptible de faire émerger l'un ou l'autre de ces processus. L'incapacité à opérer une thermorégulation optimale en raison de l'inefficacité des processus d'évaporation, mène théoriquement à une augmentation inéluctable de la température corporelle, catalysée par la déshydratation. Aussi, l'atteinte d'une température plafond pourrait être l'origine de l'arrêt de l'exercice. L'hyperthermie, en relation avec les contraintes d'humidité de l'air ambiant, est également susceptible d'accentuer le processus d'anticipation par une baisse d'intensité précoce, et donc la fatigue centrale. Ainsi, nous avons étudié sur 2 épreuves de compétition, un trail de 27 km et un half-Ironman, les relations entre les stratégies d’hydratation, l’évolution de la température gastro-intestinale et la performance des athlètes. Nous avons également testé en situations standardisées les différents paramètres pouvant être responsables de l’arrêt ou de la baisse d’intensité (i.e) en climat tropical : les paramètres cardio-respiratoires, les paramètres psychologiques, d'hydratation et de température corporelle, la fatigue musculaire et centrale. / The decrease in aerobic performance in tropical climate has been widely described in many endurance activities, but the processes responsible for this alteration remain relatively undetermined. We therefore propose through laboratory and field studies, to explore the mechanisms responsible for this diminution in aerobic performance in tropical climate. If reaching a 40 °C core temperature is rather observed in laboratory procedures, especially with high levels of exercise intensity, it seems that the mechanisms of anticipation by reducing the intensity of exercise are more proliferious in a thermal environment intensifying heat storage and dehydration. Indeed, the tropical climate elicits a rise in heat storage and water loss even if sweating is ineffective in releasing heat. The attainment of a critically high level of core temperature has been proposed as the main limiting factor of aerobic performance in the heat. In opposition with this hypothesis, the inability to control optimal thermoregulation in uncompensable environments could lead to central fatigue, with a reduction in power output subconsciously selected by the subjects in order to prevent core temperature from reaching dangerous levels.Thus, we studied on 2 competition events, a 27 km-trail and a half-Ironman, relations between hydration strategies, changes in gastrointestinal temperatures and athletes' performance. We also tested in standardized conditions different factors that may be responsible for exhaustion or decreasing intensity in tropical climate: cardio-respiratory parameters, psychological parameters, hydration and body temperature, and central and muscle fatigue.

The aim of this thesis is to summarize the knowledge regarding reduction of negative impact of high volumes of fly ash in HVFA concretes using nanotechnology and experimentally verify the findings. To compensate the inferior early-age properties, it is possible to use active nanoparticles, such as nanosilica or nanolimestone. The first step of the experiment was the production of stable nanoparticle’s dispersions using ultrasonic homogenization and UV/Vis spectroscopy. In subsequent steps the influence of nanoparticle’s presence on cementitious materials’ properties was verified on cement pastes and mortars with 40 a 60 % of fly ash. The best variant was then used to produce nano-modified HVFA concretes. Even at a minimum dose, the positive effect on early-age properties indicates the usefulness of nanoparticles in technology of concrete. An important contribution of this thesis is also the acquired knowledge related to the nanoparticle’s behavior and handling.

Dans les réacteurs nucléaires à eau pressurisée, une solution d'acide borique de pH contrôlé par ajout de lithine est injectée dans le circuit primaire. Le bore joue le rôle de neutrophage et participe au contrôle des réactions de fission. La solution du circuit primaire est épurée par passage sur colonnes de résines échangeuses d'ions. Ces résines sont périodiquement renouvelées et constituent un déchet de faible activité. Outre des radionucléides, elles contiennent majoritairement des ions borate et lithium. Elles sont actuellement conditionnées dans une matrice organique avant stockage en site de surface. Une évolution du procédé est envisagée, avec remplacement de la matrice organique par une matrice minérale. Cette thèse évalue les potentialités des ciments sulfo-alumineux pour le conditionnement de résines boratées en présence de lithium. Ces liants présentent en effet l'avantage de former des hydrates capables d'insérer les ions borate dans leur structure, et leur hydratation est moins retardée que celle des ciments silico-calciques conventionnels. Une démarche analytique, procédant par complexification progressive des systèmes étudiés, est mise en œuvre. Ainsi, l'hydratation de ciments sulfo-alumineux à forte teneur en ye'elimite est-elle successivement étudiée en présence (i) de sels de lithium, (ii) d'hydroxyde de lithium et de borate de sodium, et (iii) d'hydroxyde de lithium et de résines boratées. L'approche expérimentale est complétée par des simulations thermodynamiques s'appuyant sur une base de données développée pour les besoins de l'étude. Il apparaît que les ions lithium accélèrent l'hydratation du ciment sulfo-alumineux en diminuant la durée de la période d'inertie thermique. Le mécanisme mis en jeu implique la précipitation d'un hydroxyde mixte d'aluminium et de lithium. Au contraire, le borate de sodium ralentit l'hydratation du ciment sulfo-alumineux en augmentant la durée de la période d'inertie thermique. Une espèce riche en bore et sodium, l'ulexite, précipite transitoirement dès le début de l'hydratation. En sa présence, la dissolution de la ye'elimite reste lente. Lors de l'ajout simultané d'hydroxyde de lithium et de borate de sodium dans la solution de gâchage, les mécanismes observés pour chacune des espèces considérées séparément se superposent. Un troisième processus vient s'ajouter dans le cas d'un ciment non gypsé : le lithium favorise la formation initiale d'une phase AFm boratée qui disparaît au profit d'une phase AFt boratée lorsque l'hydratation s'accélère. Les résultats obtenus permettent in fine de proposer une première formulation d'enrobage de résines boratées dont les propriétés sont compatibles avec les exigences requises pour une matrice de conditionnement sur la durée de l'étude. / In pressurized water reactors, a solution of boric acid, the pH of which is controlled by the addition of lithium hydroxide, is injected in the primary circuit. Boron acts as a neutron moderator and helps controlling the fission reactions. The primary coolant is purified by flowing through columns of ion exchange resins. These resins are periodically renewed and constitute a low-level radioactive waste. In addition to radionuclides, they mainly contain borate and lithium ions. They are currently encapsulated in an organic matrix before being stored in a near-surface repository. An evolution of the process is considered, involving the replacement of the organic matrix by a mineral one.In this PhD study, the potential of calcium sulfoaluminate cements (CSAC) to solidify / stabilize borated resins in the presence of lithium is investigated. These binders have the advantage to form hydrates which can incorporate borate ions in their structure, and their hydration is less retarded than that of Portland cement.An analytical approach is adopted, based on a progressive increase in the complexity of the investigated systems. Hydration of ye'elimite-rich CSAC is thus successively investigated in the presence of (i) lithium salts, (ii) lithium hydroxide and sodium borate, and (iii) lithium hydroxide and borated ion exchange resins. The experimental investigation is supplemented by thermodynamic modelling using a database specially developed for the needs of the study.Lithium ions are shown to accelerate CSAC hydration by decreasing the duration of the period of low thermal activity. The postulated mechanism involves the precipitation of lithium-containing aluminum hydroxide. On the contrary, sodium borate retards CSAC hydration by increasing the duration of the period of low thermal activity. Ulexite, a poorly crystallized mineral containing sodium and borates, transiently precipitates at early age. As long as ulexite is present, dissolution of ye'elimite is strongly slowed down. When sodium borate and lithium hydroxide are simultaneously introduced in the mixing solution, these two mechanisms are superimposed. With a gypsum-free cement, a third process is additionally observed: lithium promotes the initial precipitation of a borated AFm phase which is later converted into a borated AFt phase when hydration accelerates.Finally, based on the achieved results, a cement-based formulation is designed for the encapsulation of borated resins. Its properties fulfill the requirements for a conditioning matrix over the duration of the study.

Previous studies have found vocal fold hydration to be crucial for healthy function of the vocal mechanism. Surface tissue hydration facilitates efficient vocal fold oscillation. The composition of vocal fold surface fluid includes protective water and mucus layers, similar to the fluid that covers the mucosa and epithelia of the upper airway. Laryngeal dehydration has been linked to several factors such as mouth breathing, obstructive sleep apnea, dry air exposure, upper airway hypersensitivity, and certain diseases or behavioral voice use factors. Laryngeal dehydration affects phonation threshold pressure (PTP) and phonation threshold flow (PTF), defined as the pressure and flow observed at the onset of phonation, respectively. The application of topical nebulized isotonic saline (0.9% Na+Cl-) has been shown in previous work to decrease PTP. However, there are no studies examining the effects of aerosolized saline, administered supraglottally, on dehydrated excised porcine larynges. Examining the effects of aerosolized saline in an excised model is essential to determine any independent effects of this treatment in the absence of other physiologic mechanisms such as mucus secretion. This study sought to investigate the effects of aerosolized saline on dehydrated animal vocal folds to determine if the administration of supraglottic aerosolized saline, via a nebulizer, could reverse the adverse effects of laryngeal dehydration. The study included a prospective, mixed experimental design with two groups, one desiccation/aerosolization (A/B) group and a control (A) group, each comprised of five bench-mounted porcine larynges. Larynges in both groups received desiccated air (<1% relative humidity) supraglottally via custom tubing for 1-min doses until the vocal folds ceased audible phonation. Following the desiccation challenge, the A/B group received 2-min doses of aerosolized isotonic saline until phonation began again. The PTP and PTF were measured during phonation trials following each dose of the desiccation or aerosolization treatment. Significant changes in PTP and PTF were observed following both the dehydration and aerosolization treatment. The PTP increased significantly following the dehydration challenge and returned near baseline following the aerosolization treatment. The results of this investigation supported the hypothesis that the administration of aerosolized saline may reverse the adverse effects of vocal fold dehydration. Moreover, in a more physiologically realistic excised model, applying the mechanics of respiration, this study advanced the development of innovative theories related to the reversal of the adverse effects of dehydration, which may prevent the development of voice disorders.