In this thesis we numerically compute the scattering lengths and bound states for sodium-rubidium collisions at low energy. This work was motivated by experiments which aim to produce Bose-Einstein condensates (BEC) mixtures of sodium-rubidium. Elastic collision properties are important for the rethermalization of the atoms during the evaporative cooling process. Inelastic processes, which we also discuss to some extent, cause trap losses in those experiments. In order to reach the required temperature and density the elastic collision rates should be sufficiently large compared to the inelastic rates. The scattering lengths, which completely specify the elastic collision parameters at low energy, determine the miscibility and phase diagram of the sodium-rubidium condensate mixture. We calculate the scattering lengths approximately and find agreement with previous calculations indicating that miscible phases of sodium and rubidium condensates do not appear to be feasible in the absence of external fields.

Quantum memories are key components in photonics-based quantum information processing networks. Their ability to store and retrieve information on demand makes repeat-until-success strategies scalable. Warm alkali-metal vapours are interesting candidates for the implementation of such memories, thanks to their very long storage times as well as their experimental simplicity and versatility. Operation with the Raman memory protocol enables high time-bandwidth products, which denote the number of possible storage trials within the memory lifetime. Since large time-bandwidth products enable multiple synchronisation trials of probabilistically operating quantum gates via memory-based temporal multiplexing, the Raman memory is a promising tool for such tasks. Particularly, the broad spectral bandwidth allows for direct and technologically simple interfacing with other photonic primitives, such as heralded single photon sources. Here, this kind of light-matter interface is implemented using a warm caesium vapour Raman memory. Firstly, we study the storage of polarisation-encoded quantum information, a common standard in quantum information processing. High quality polarisation preservation for bright coherent state input signals can be achieved, when operating the Raman memory in a dual-rail configuration inside a polarisation interferometer. Secondly, heralded single photons are stored in the memory. To this end, the memory is operated on-demand by feed-forward of source heralding events, which constitutes a key technological capability for applications in temporal multiplexing. Prior to storage, single photons are produced in a waveguide-based spontaneous parametric down conversion source, whose bespoke design spectrally tailors the heralded photons to the memory acceptance bandwidth. The faithful retrieval of stored single photons is found to be currently limited by noise in the memory, with a signal-to-noise ratio of approximately 0.3 in the memory output. Nevertheless, a clear influence of the quantum nature of an input photon is observed in the retrieved light by measuring the read-out signal's photon statistics via the g⁽²⁾-autocorrelation function. Here, we find a drop in g⁽²⁾ by more than three standard deviations, from g⁽²⁾ ~ 1.69 to g⁽²⁾ ~ 1.59 upon changing the input signal from coherent states to heralded single photons. Finally, the memory noise processes and their scalings with the experimental parameters are examined in detail. Four-wave-mixing noise is determined as the sole important noise source for the Raman memory. These experimental results and their theoretical description point towards practical solutions for noise-free operation.

Les effondrements massifs de flancs sont des évènements destructeurs qui affectent tous les édifices volcaniques. Ces effondrements peuvent impliquer quelques dizaines, voire centaines de km3 de roche. Les volcans boucliers océaniques, bien que possédant de faibles pentes, sont également affectés par ces épisodes destructeurs, entraînant la formation de tsunamis. Dans le contexte de bouclier océanique, ces déstabilisations n’ont jamais été observées. Actuellement, seules des reliques sont présentes sur les îles volcaniques, avec la présence de cicatrices d’effondrements, de dépôts détritiques en mer ou de dépôts de tsunami sur les îles voisines. Les relations entre le magmatisme des volcans boucliers et les effondrements de flanc sont peu contraintes. Afin de mieux comprendre ces relations, deux effondrements de flanc de volcans boucliers océaniques ont été étudiés : l’effondrement de Monte Amarelo sur l’île de Fogo, dans l’archipel du Cap Vert, et l’effondrement de Güímar, situé sur la rift-zone Nord-Est de Tenerife, dans l’archipel des Canaries. Les deux archipels résultent de l’activité d’un panache mantellique sous la plaque africaine.Les produits volcaniques pré et post-effondrement de ces deux secteurs ont été étudiés d’un point de vue géochimique (majeurs, traces, isotopes Sr-Nd-Pb), pétrologique et géochronologique (K-Ar, Ar-Ar), de manière à identifier à la fois les sources et les processus magmatiques mis en jeu lors de leur formation. L’évolution temporelle des sources, ainsi que des processus magmatiques, a été reconstruite afin d’identifier d’éventuels liens avec l’effondrement de flanc étudié.Les résultats montrent que l’évolution du magmatisme de l’île de Fogo amène à la formation de zones superficielles de stockage, de complexes intrusifs et d’éruptions explosives conduisant à de nouvelles instabilités de l’édifice. Suite à l’effondrement, ces zones de stockage sont déstabilisées en quelques milliers d’années. Les processus magmatiques lithosphériques (assimilation, fusion partielle) sont également perturbés mais sur une période plus longue (plusieurs dizaines de milliers d’années). L’effondrement de Güímar ne montre aucun lien avec le magmatisme de l’île de Tenerife.La différence principale entre ces deux contextes est la localisation de la zone effondrée par rapport au système magmatique. En effet, l’effondrement de Güímar est situé en périphérie du système magmatique et ne montre aucun lien avec ce dernier ; à l’inverse l’effondrement du Monte Amarelo, situé à l’aplomb du système magmatique, se répercute rapidement sur ce système à faible profondeur, mais également à des profondeurs lithosphériques avec un délai plus long. / Massive flank collapses are destructive events that affect all volcanic edifices. They can take off huge volumes of rock, from tens to hundreds km3. Oceanic shield volcanoes are also affected by such events even if they have shallow slopes, thus, tsunamis could also be generated in this context. However, a shield volcano flank collapse has never been observed. Nowadays, only relics are visible, such as collapse scars, detritic deposit offshore or tsunami deposits on nearby islands. The relationships between collapse and magmatic history of oceanic shield volcanoes are poorly constrained. Two flank collapses are studied in this thesis, with the aim to better understand these relationships: the Monte Amarelo collapse, on Fogo Island (Cape Verde), and the Güímar collapse, located on North-East rift-zone of Tenerife (Canary Islands). Those archipelagos are the result of hot spot activity below the African plate. Geochemical (major and trace elements, and Sr-Nd-Pb isotopes), petrological and geochronological (K-Ar and Ar-Ar) analyses were carried out on volcanic samples as to identify the source and magmatic processes at stake during magma genesis. The temporal evolution of source and magmatic processes is reconstructed in order to track possible links with the flank collapse. The magmatic system of Fogo Island evolves through time, favouring the formation of superficial storage zones, intrusive complex and explosive eruptions prior to the collapse, which participate to the instability of the edifice. Following the Monte Amarelo collapse, shallow storage zones are destabilized within a few thousand years. Lithospheric magmatic processes (assimilation, partial melting) are also affected but on a longer timescale (tens of thousands years). The Güímar collapse shows no links with the magmatic evolution of Tenerife Island. The main difference between the two collapses is the location of the collapse area with respect to the plumbing system. Güímar collapse is located at the periphery of the plumbing system and show no link with the magmatic history. Contrariwise, the Monte Amarelo collapse is located directly above the plumbing system and influence rapidly the superficial plumbing system, and the deep plumbing system in the long term.

La corrosion des échangeurs de chaleur est un problème économique et technique majeur des Unités de Valorisation Energétique de Ordures Ménagères (UVEOM). Elle est causée par l’action combinée (i) des gaz de combustion contenant notamment HCl et SO2 et (ii) des cendres riches en chlorures et sulfates alcalins, et sels de métaux lourds. Les travaux présentés dans ce mémoire s’inscrivent dans le projet ANR SCAPAC (n°11-RMNP-0016) et portent sur l’influence des paramètres expérimentaux (température, teneur en chlorures dans les cendres, présence de gaz corrosifs et présence de chlorures de métaux lourds dans les cendres) sur la tenue à la corrosion de deux alliages utilisés en milieu UVEOM : l’acier 16Mo3 et l’alliage base nickel Inconel 625. Ces travaux ont permis de mettre en évidence que la présence de phases fondues, l’augmentation de la teneur en chlorures, la présence de 10% en masse de ZnCl2 dans les mélanges de cendres et la présence de gaz corrosifs (HCl, SO2) dans l’atmosphère sont trois facteurs qui ont induit une corrosion plus importante sur les matériaux, de manière plus prononcée sur l’alliage base fer. Une autre partie du travail s’est focalisée sur l’influence des éléments d’alliage Fe, Cr et Mo. Des alliages « modèles » dont les compositions oscillent autour de la composition de l’alliage Inconel 625 commercial ont été synthétisés par fusion haute fréquence et leur tenue à la corrosion a été évaluée sous air et sous atmosphère corrosive. La bonne optimisation de l’alliage commercial a ainsi été démontrée sous air. Sous atmosphère gaz corrosifs, une teneur en chrome supérieure à 22% massique s’est montrée indispensable à la bonne tenue de l’alliage / Corrosion of heat exchangers is an economic and technical issue in Waste-to-energy plants. It is caused by the combined action of (i) flue gas containing HCl and SO2 and (ii) chlorides and alkali sulfates rich ash. This work is part of the ANR project SCAPAC (supported by the ANR-11-RMNP 0016) and focused on the influence of experimental parameters on the corrosion behavior of two commercial alloys used in Waste-to-Energy plants: the 16Mo3 steel and the nickel-based alloy Inconel 625. This study allowed to highlight that the presence of molten phase, the increase in the chloride content, the presence of 10% by weight of ZnCl2 in the ash mixtures and the presence of corrosive gases (HCl, SO2) in the atmosphere are three factors that have induced an higher corrosion of materials, more pronounced on the iron alloy base. Another part of the work has been focused on the influence of alloying elements Fe, Cr and Mo. Thus, model alloys with compositions oscillating around the composition of Inconel 625 commercial alloy were synthesized by high frequency induction and their corrosion resistance was evaluated in air and in corrosive atmosphere. Good optimization of the commercial alloy has been demonstrated in air. In corrosive atmosphere, a minimum chromium content was required to obtain a good corrosion resistance

Afin de répondre aux questions des propriétaires de structures atteintes de réaction alcali-silice (RAS), ce travail se concentre sur une partie d'une méthodologie globale, proposée initialement par le LMDC et EDF, et dont le but est l'étude du comportement mécanique des constructions endommagées par la RAS. Pour atteindre cet objectif, l'avancement chimique de la RAS des granulats récupérés dans les structures affectées doit être évalué. Ainsi, ce travail est consacré à la quantification de la silice potentiellement réactive des granulats, par l'utilisation de deux approches : une approche indirecte par un test d'expansion et une approche directe par des méthodes chimiques. La présentation du manuscrit s'articule autour des points suivants :• Un test d'expansion pertinent et rapide sur mortiers pour relier la quantité de silice réactive à l'expansion mesurée. Les conditions expérimentales suivantes ont été choisies pour tester différentes tailles et natures de granulats, ainsi que différentes tailles d'éprouvettes : solution de NaOH à 1 mol/l et température de conservation de 60°C.• Une méthode chimique rapide de dissolution sélective pour mesurer directement la quantité de silice réactive disponible pour la RAS. La méthode HF / HF+HCl a été trouvé comme étant la plus efficace.• Un modèle chemo-mécanique pour analyser les effets de la taille des granulats et des éprouvettes, et évaluer l'avancement chimique de la réaction.Finalement, une méthodologie est proposée pour calculer la constante cinétique de la réaction dans le cadre de la requalification des structures atteintes de RAS. / In order to answer the questions of the ASR-affected structures owners, this work focused on a part of a global methodology, which is proposed originally by the LMDC and EDF, aiming to reassess the mechanical behavior of ASR-damaged constructions. To achieve this purpose, the chemical advancement of ASR in the aggregates recovered from the structure should be evaluated. Thus, this work focuses on the assessment of the potentially reactive silica content with two main methods: indirectly by expansion test and directly by chemical methods. The presentation of this manuscript is around the following points: • A relevant and rapid expansion test on mortars to link the reactive silica content to measured expansion. The experimental condition: 1 mol/l NaOH solution conserved at 60°C is chosen to test different aggregate sizes, specimen sizes and natures of aggregate. • A fast chemical method of selective dissolution to measure directly the silica available for ASR. Acid/basic methods are tested and compared; HF / HF+HCl method is found to be the most effective. • A chemo-mechanical model to analyze the effect of aggregate size and specimen size, and evaluate the chemical advancement of ASR. Finally, a methodology is proposed to calculate the kinetics constant in the framework of structural requalification. Key words: alkali-silica reaction (ASR), chemical advancement, reactive silica, expansion test, chemical test, chemo-mechanical model, kinetic constant, selective dissolution

Les réactions de gonflements internes (RGI) sont des pathologies qui dégradent le béton de certains ouvrages tels que des barrages en étant à l'origine de gonflements. Electricité De France (EDF) doit assurer la sûreté des personnes et des biens situés à l'aval de ses structures. Ce travail a pour but d'améliorer la modélisation des phénomènes physiques liés à ces dégradations notamment l'interaction entre le produit gonflant et le squelette solide. La contrainte intraporeuse générée par la pression du produit peut créer un endommagement. Dans le modèle proposé, la fissuration peut avoir lieu à deux échelles : - Au niveau microscopique c'est le produit gonflant qui comble le volume libre autour du site de réaction avant de mettre en traction le matériau jusqu'à fissuration, ce qui provoque une baisse des caractéristiques du matériau (résistances en traction et en compression, module d'Young). Un critère de plasticité anisotrope et une loi d'écrouissage positif sont proposés pour modéliser ce phénomène. - Au niveau macroscopique, des gradients de gonflements peuvent se développer à l'intérieur d'ouvrages dont les états de contraintes et les conditions d'humidité et de température ne sont pas homogènes. Une fissuration localisée peut alors s'initier. Elle est la source de risques de dislocations des structures pouvant mener à leur ruine, de concentrations de contraintes dans les aciers structuraux, de chemins facilités pour les agents agressifs extérieurs et pour l'eau, composé essentiel au développement rapide de ces pathologies. La prise en compte des couplages hydro-poro-mécaniques est nécessaire à la simulation de ces phénomènes. Cette fissuration est modélisée par un critère plastique de Rankine anisotrope dont l'énergie dissipée par la fissuration est régularisée par la méthode d'Hillerborg. Après avoir présenté ce modèle, il est validé et appliqué à différentes échelles pour des états de contraintes et des conditions environnementales diverses, sur : - des éprouvettes soumises à des contraintes et des blocages multi-axiaux, - des poutres de laboratoire plus ou moins armées subissant des gradients d'humidité importants, - des barrages dans des conditions réelles construits dans les années 1950. Les résultats obtenus avec le modèle permettent de retrouver les déplacements, les contraintes et les résistances de ces structures après vieillissement. Pour les poutres atteintes de réaction alcali-silice, les résultats numériques obtenus montrent notamment une prise en compte réaliste des contraintes induites par la présence d'armatures, ce qui est confirmé par la validation du comportement à rupture. Néanmoins, des difficultés de calage subsistent pour les poutres subissant la réaction sulfatique interne. Elles sont issues des grandes amplitudes d'expansion et des couplages diffusion-fissuration qui rendent spécifique le comportement de ces structures par rapport à des structures subissant des expansions moins importantes. Ce modèle est un outil pour la requalification des ouvrages dans le but d'assurer leur sûreté. Il peut également servir de base de calcul à la simulation de diverses réhabilitations et travaux de confortements. / Internal swelling reactions (ISR) damage the concrete of structures such as dams. Electricité De France (EDF) must ensure the safety of the people and goods located below the dam. This work aims to improve the modeling of the physical phenomena related to these damages, especially the interaction between the swelling product and the solid skeleton. The intraporous stress generated by the product pressure can create cracking, which, in the proposed model, can occur at two scales: - At a microscopic scale, the swelling product fills the gaps around the reaction site, which induces cracking and a decrease of the materials' characteristics (tensile and compression strengths, Young's modulus). Numerically, an anisotropic plastic criteria and a hardening law allow modelling this phenomenon. - At a macroscopic level, swelling gradients can develop inside concrete structures whose stress states and climatic conditions (humidity and temperature) are not homogeneous. A localized cracking can begin. It is a source of structure dislocation risks and stress concentrations in structural reinforcement. It may ease the way in for outside aggressive agents and water, an essential component for these reactions. Hydro-poro-mechanical couplings need to be taken into account when simulating these phenomena. The cracking is modelled by a Rankine plastic criterion whose dissipated energy is regularized by the Hillerborg's method. After presenting the model, several stress states and environmental conditions are applied to the model in order to validate it on: - samples under multi-axial stresses and restraints, - plain and reinforced beams submitted to moisture gradients in laboratory, - 1950s dams in real conditions. The results of the model make it possible to reproduce the displacements, the stresses and residual strength of these structures after aging. For the beams submitted to alkali aggregate reaction, the numerical results show a relevant prediction of the stress induced by reinforcement, confirmed by the failure behaviour. Nevertheless, the model encounters calibration difficulties for beams affected by delayed ettringite formation. They come from large swelling amplitude and diffusion-cracking coupling which are inherent to these structure behaviours. This model is a tool for concrete structure requalification in order to ensure their safety. It can also be a basis for diverse rehabilitations and reinforcement works simulation.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Natural rice husk ash (RHA) used in concrete contributes to civil construction sustainability. In fact, RHA is considered a residual pollutant and then it is necessary to destine this material correctly. However, it is necessary to investigate the consequences of replacing part of cement by natural RHA to produce concrete for structural purposes. In this context, the aim of this study was to evaluate the concrete durability produced with 15 % of blinder partial replacement by natural RHA in the expansion due to alkali-silica reaction (ASR) and penetration of chloride ion, as well as to suggest preventive measures with the use of mineral additions. In the present study, natural RHA was used as partially replacement of Portland cement. This natural RHA has been obtained without temperature control burning and placed directly into the mixer to suffer self-grinding with aggregates. We investigated the RAS neutralization of natural RHA by the use of cement with mineral additions (CPIIZ, CPIII e CPIV), as well as, we performed additional replacements of part from CPIIZ cement by fly ash (10, 15, 20, 30 and 40 %). We employed accelerated expansion method at 80°C in mortar bars followed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), and long term at 38 °C and accelerated at 60 °C methods in concrete prisms. To investigate concrete resistance in the chloride ion penetration, we used chloride ions penetration method by immersion in saline solution (CPT) of concrete produced with natural RHA and CPIIZ cement added of fly ash (0, 12.75 or 17 %) and water-binder ratios of 0.45, 0.55 and 0.65 were adopted. Analyses of results were based in slope (K ) obtained from the average depths of penetration. In this study, we verified that in mortar bars assay the natural RHA generated expansion above of results allowed by norm in mixtures with standard cement, while CPIIZ cement with addition from 20 % of fly ash showed to mitigate the ASR. These results demonstrated that effect of mitigation of RAS proportionally increased with fly ash addition. Moreover, CPIV cement demonstrated excellence in mitigate the expansive reaction. The SEM analysis identified the characteristic products of ASR in the samples containing natural RHA. XRD analysis showed that the samples of mixtures with higher content of mineral addition showed peaks of calcium hydroxide (CH) with less intensity and mixtures with natural RHA presented greater calcium carbonate content. In relation to concrete prisms molded at 60°C, results showed an increase in expansion for mixture of CPIIZ with natural RHA, but these results remained below of maximum expansion predicted by test. Mixtures of CPII-Z with natural RHA added of 10 and 15% fly ash demonstrated better efficiency in expansion mitigation. In relation to concrete prisms molded at 38°C, the results are not conclusive to 12 months, but mixtures that presented a great expansion were of CPII-Z with natural RHA and 15% fly ash, the CPII-Z with RHA natural and CPII-Z with natural RHA and 10% fly ash, respectively. However, all mixtures had expansion below the maximum limit suggested by the Brazilian standard at 24 months. Through of results CPT, we can conclude that mineral additions provided improvements to the concrete with higher ages due to pozzolanic effect. Moreover, the best results obtained were in trace with lowest water-binder ratios, probably due to increased consumption of cement, which increases the CH amount to interact with the RHA and the fly ash. Therefore, mixtures of Portland cement with fly ash and natural RHA meet the durability of concrete, and also the use of natural RHA would be an important contribution to sustainability and preservation of environment by civil construction. / O emprego de cinza de casca de arroz (CCA) natural no concreto visa contribuir para a sustentabilidade da construção civil, destinando de maneira adequada, esse material que antes seria considerado um resíduo poluente. Porém, é necessária a investigação das consequências em substituir parte do cimento por CCA natural para produzir concreto com finalidade estrutural. Neste sentido, o objetivo deste trabalho foi avaliar a durabilidade de concretos produzidos com teor de 15 % de substituição parcial do aglomerante por CCA natural, frente à expansão devido à reação álcali-sílica (RAS) e à penetração de íons cloretos, assim como, sugerir medidas preventivas através do uso de adições minerais. No presente estudo, a CCA natural foi utilizada em substituição parcial ao cimento Portland no estado em que se encontra ao sair dos fornos de queima (sem controle de temperatura), diretamente na betoneira para sofrer auto-moagem com os agregados. Foi investigada a neutralização das RAS da CCA natural pelo emprego de cimentos com adições minerais (CPIIZ, CPIII e CPIV), assim como foram realizadas as substituições adicionais de parte do cimento CPIIZ por cinza volante (10, 15, 20, 30 e 40 %). Na investigação da RAS foram empregados os métodos de expansão acelerado a 80 °C em barras de argamassa acompanhado pela microscopia eletrônica de varredura (MEV) e difração de raios-X (DRX), e os métodos de longa duração a 38 °C e acelerado a 60 °C em prismas de concreto. Na investigação da resistência a penetração de íons cloretos foi empregado o método de penetração de íons cloretos por imersão em solução salina (EPCI) dos concretos produzidos com CCA natural e cimento CPIIZ adicionados de cinza volante (0; 12,75 ou 17 %) e nas relações água/aglomerante(a/ag) de 0,45; 0,55 e 0,65. A análise dos resultados do EPCI foi realizada com base no coeficiente angular da equação da reta (K ) obtido a partir das profundidades médias de penetração dos períodos investigados. Neste trabalho verificou-se que, no ensaio em barras de argamassa a CCA natural gerou expansão acima do permitido por norma nas misturas com cimento padrão, enquanto o cimento CPIIZ com adição a partir de 20 % de cinza volante se mostrou mitigador da RAS. Através desses resultados pode-se verificar que o efeito mitigador da RAS aumentou proporcionalmente com a adição de cinza volante. Além disso, o cimento CPIV mostrou excelência em mitigar a reação expansiva. A análise de MEV identificou os produtos característicos da RAS nas amostras contendo CCA natural e a DRX verificou que as amostras retiradas das misturas com maior teor de adição mineral apresentaram picos de hidróxido de cálcio (CH) com menor intensidade e ainda, que as misturas com CCA natural apresentaram maior quantidade de carbonato de cálcio. Em relação aos prismas de concreto moldados a 60 °C, os resultados mostraram maior expansão na mistura de CPIIZ com CCA natural, mas ela se manteve abaixo do limite máximo de expansão preconizado pelo ensaio. As misturas de CPII-Z com CCA natural adicionadas de 10 e 15 % de cinza volante mostraram melhor eficiência em mitigar a expansão. Em relação aos prismas de concreto moldados a 38 °C os resultados ainda não são conclusivos aos 12 meses, porém as misturas que apresentaram maior expansão em 12 meses foram as de CPII-Z com CCA natural e 15 % de cinza volante, de CPII-Z com CCA natural e CPII-Z com CCA natural e 10 % de cinza volante, respectivamente, entretanto, todas abaixo do limite máximo de expansão aos 24 meses, preconizado pela norma brasileira. Através das análises dos resultados do EPCI concluiu-se que as adições minerais proporcionaram melhorias ao concreto com maiores idades devido ao efeito pozolânico. Além disso, os melhores resultados obtidos foram nos traços com menor relação a/ag, provavelmente devido ao maior consumo de cimento que aumenta a quantidade de CH para interagir com a CCA e a cinza volante. Portanto, as misturas de cimento Portland com CCA natural e cinza volante atendem aos parâmetros de durabilidade do concreto, e com isso o uso da CCA natural seria um importante contribuinte na sustentabilidade e preservação do meio ambiente pela construção civil.

Muitas estruturas e elementos estruturais de concreto vêm sofrendo nas últimas décadas reações químicas deletérias do tipo álcali-agregado (RAA) no Brasil e no mundo. Essas reações geram expansões que podem comprometer a capacidade portante da estrutura, assim como o seu desempenho em serviço e sua durabilidade. Diagnosticar uma estrutura deteriorada pela RAA in loco é um assunto ainda pouco estudado, mas perfeitamente possível. Propor uma solução em termos de recuperação e/ou reforço é difícil e geralmente tem custo muito elevado, correndo-se o risco de que a solução, na maioria das vezes, seja ineficiente ou parcial. Até os dias atuais, não existe um consenso no meio técnico-científico no que tange a recuperação de estruturas afetadas por tal manifestação deletéria, devendo ser cada caso analisado de maneira única. No entanto, é consenso no meio técnico-científico que o ideal para combater a RAA é a prevenção. Para isto, torna-se necessário o desenvolvimento e a utilização de métodos experimentais, que possam de maneira antecipada detectar o risco da eventual futura reação deletéria. Este trabalho estuda os principais e mais utilizados métodos de ensaio para a análise de agregados e de combinações cimento/agregados em laboratório, fazendo ao seu final, uma análise crítica no que tange a eficiência e confiabilidade de cada um deles. Para o presente estudo, são utilizados seis agregados encontrados no Brasil, com quatro litologias diferentes (dois granitos, dois basaltos, um milonito e um quartzito). Entre os ensaios estudados, podem ser citados os métodos AMBT, (método acelerado de barras de argamassa), CPT (método dos prismas de concreto), ACPT (método acelerado de prismas de concreto) e ACPST (método acelerado de prismas de concreto imerso em solução), além de análises petrográficas através do microscópio ótico. Além da análise comparativa entre métodos de ensaio existentes, esta dissertação propõe ao meio técnico um novo método de ensaio, denominado ABCPT (método acelerado brasileiro de prismas de concreto). Este método foi desenvolvido com o intuito de possuir a confiabilidade de resposta do método CPT e a agilidade do ensaio ACPST. Os resultados demonstram que todos os métodos de ensaio realizados em concreto (CPT, ACPT, ACPST e ABCPT) possuem grande correlação entre si, podendo ser utilizado qualquer um deles para classificação da reatividade potencial de agregados em laboratório. Já o ensaio de barras de argamassa (AMBT) apresenta incongruências na análise e classificação de agregados quando comparado com os métodos realizados em concreto e a análise petrográfica. Portanto, os parâmetros que envolvem o ensaio como suas condições. / Many concrete structures have been suffering from alkali-aggregate reactions (AAR) since the last decades in Brazil and around the world. The reactions generate expansions that could compromise the strength of a concrete structure as well as its performance in service and its durability. Nowadays, it is completely possible to detect AAR in the field, but repair and reinforce a damaged structure is difficult, very expensive and in most cases inefficient or partial. There is no consensus in the market on how to repair and reinforce damaged structures. However, there is a consensus that the best way to face the problem is the prevention. This work studies the main test methods used to analyze aggregates and the combinations cement/aggregates in the laboratory and finally comparing them. In this work six Brazilian aggregates with four different lithologies (two granites, two basalts, one granite-gneiss and one quartzite) were used. Among the test methods studied were AMBT (accelerated mortar bar test), CPT (concrete prism test), ACPT (accelerated concrete prism test), ACPST (accelerated concrete prism soaked test) and petrographic analysis. Beyond the comparison among used tests, this work presents the attempt to develop a new accelerated test method. The test was called ABCPT (accelerated Brazilian concrete prism test), and it was developed with the aim of being as reliable as CPT and as fast as the ACPST. The results show that all concrete test methods (CPT, ACPT, ACPST and ABCPT) have good correlation among them, and anyone can be used to classify and analyze aggregates in the laboratory. On the other hand, the AMBT test method has showed different classifications for the same aggregates when compared to the concrete test methods and petrographic analysis. Therefore, its parameters need to be rethought and improved.

A presente dissertação trata da implementação e otimização de um sistema de detecção condutométrica sem contato capacitivamente acoplada (C4D) para Eletroforese Capilar (CE). O sistema é caracterizado pela compactação do sistema de detecção, versatilidade e flexibilidade de instalação em diferentes equipamentos comerciais de eletroforese capilar e home made. Desde a década de 80, a eletroforese capilar vem se consolidando como uma das técnicas de separação mais relevantes. Normalmente, os instrumentos comerciais são disponibilizados com detectores ópticos e detectores eletroquímicos. A C4D é utilizada em eletroforese capilar posicionando-se dois eletrodos tubulares envoltos ao capilar. A aplicação de sinais de alta frequência entre os eletrodos permite monitorar variações de condutividade da solução dentro do capilar. Assim, a resposta do detector depende de diversos fatores como mobilidade do analito, do co-íon do eletrólito, da frequência e amplitude do sinal aplicado entre os eletrodos e da geometria dos mesmos. A ausência de componentes móveis torna o presente detector compacto (6,5 cm3) e robusto. O presente C4D é constituído de um oscilador local funcionando a 1,1 MHz, um circuito capaz de converter corrente em tensão, retificar e filtrar os sinais analógcos, além de apresentar um conversor de sinais analógicos em digitais (Conversor A/D) de alta resolução (21 bits efetivos). Outra vantagem é a possibilidade de determinar o diâmetro interno do capilar através da leitura do conversor A/D quando se faz passar um fluxo de ar e, posteriormente água através do capilar. A diferença de leitura de conversor A/D pode ser convertida em diâmetro interno mediante uma curva de calibração. Em uma aplicação típica, os limites de detecção baseado no critério 3s (sem filtragem inicial) foi de 0,6, 0,4, 0,3, 0,5, 0,6 e 0,8 µmol L-1 para K+, Ba2+, Ca2+, Na+, Mg2+ e Li+, respectivamente, é comparável a outras implementações de alta qualidade de um detector condutométrico sem contato capacitivamente acoplado. / This dissertation deals with the implementation and optimization of a Capacitively Coupled Contactless Conductivity Detector (C4D) applied to capillary electrophoresis (CE). The system is characterized by compaction of the detection system, installation flexibility and versatility in different commercial capillary electrophoresis equipment and home-made. Since the 80s, capillary electrophoresis has been consolidated as one of the most important separation techniques. Typically, commercial instruments are available to optical detectors and electrochemical detectors. The C4D is used in capillary electrophoresis positioning two electrodes encased in tubular capillary. The application of high frequency signals between the electrodes allows monitoring changes in conductivity of the solution within the capillary. Thus, the detector response depends on several factors such as mobility of the analyte, the co-ion electrolyte, the frequency and amplitude of the signal applied between the electrodes and the geometry of the same. The absence of moving parts makes this compact detector (6.5 cm3) and robust. This C4D is composed of a local oscillator, working at 1.1 MHz, a circuit capable of converting current into voltage, rectify and filter the analogs signals, besides presenting a high-resolution analog-to-digital converter (ADC) (21 bits effective). Another advantage is the possibility of determining the internal diameter of the capillary by reading the ADC when it is passed a stream of air and then water through the capillary. A readings different ADC can be converted into inner diameter through a curve a calibration curve. In a typical application, the detection limits based on the 3s criterion (without baseline filtering) was 0.6, 0.4, 0.3, 0.5, 0.6 and 0.8 µmol L-1 for K+, Ba2 +, Ca2 +, Na+, Mg2+ and Li+, respectively, is comparable to other high-quality implementations of a capacitively coupled contactless conductivity detector.

A reação álcali-agregado (RAA) é uma reação química complexa envolvendo os álcalis presentes no cimento Portland e minerais silicosos presentes em alguns tipos de agregados reativos. O produto dessa reação expande quando em contato com a água, causando fissuração e deformação, o que afeta a durabilidade e importantes propriedades mecânicas das estruturas de concreto. Entretanto, estruturas que estejam sob tensão de compressão, aplicada por carregamentos ou induzida pela presença de armadura, apresentam expansão reduzida na direção comprimida. Uma das ferramentas que se utiliza para a previsão da vida útil de estruturas afetadas pela RAA é a modelagem numérica da expansão do concreto, possibilitando a previsão e projeto de reparos necessários. Nesse contexto, modelos paramétricos combinam os principais fatores que influenciam a reação (reatividade dos constituintes, porosidade, temperatura, umidade e estado de tensões), possibilitando a determinação da distribuição e da taxa de expansão na estrutura. Nessa pesquisa foi desenvolvido um modelo paramétrico cujo principal interesse foi o estudo das tensões induzidas pela presença de fibras e armadura na expansão do concreto afetado pela RAA. O modelo implementado em elementos finitos tem como parâmetros nodais as posições, uma formulação alternativa ao método dos elementos finitos baseado em deslocamentos; a medida de deformação utilizada é a de Green e a lei constitutiva dos materiais é a de Saint-Venant-Kirchhoff. O material composto é discretizado por meio de uma matriz elástica bi-dimensional reforçado por fibras lineares perfeitamente aderidas à matriz. Comparações entre os resultados obtidos por meio do modelo desenvolvido e resultados de trabalhos experimentais comprovam a aplicabilidade e potencialidade do modelo numérico apresentado. / The alkali-aggregate reaction (AAR) is a complex chemical reaction involving alkalis present in the Portland cement paste and siliceous minerals present in some types of reactive aggregates. The product of this reaction expands in contact with water, causing cracking and deformation that affects durability and important mechanical properties of the concrete structures. However, structures under compressive stress, applied or induced by the presence of rebars, the expansion is reduced in the compressed direction. One of the tools used to predict the service life of structures affected by AAR is the numerical modeling of the concrete expansion, allowing prevision and projecting repairs needed. In this context, parametric models combine the main factors that influence the reaction (reactivity of the constituents, porosity, temperature, humidity and stress state), enabling the determination of distribution and rate of expansion in the structure. In this research was developed a parametric model whose main interest was the study of stresses induced by the presence of fibers and rebars in the expansion of concrete affected by AAR. The model implemented in finite element has as nodal parameters positions, an alternative formulation to the finite element method based on displacement; the deformation measurement used is Green and the material constitutive law is the Saint-Venant-Kirchhoff. The composite material is discretized by a two-dimensional elastic matrix reinforced by perfectly adherent linear fibers. Comparisons between the results obtained from the developed model and results of experimental studies demonstrate the applicability and potential of the numerical model presented.