The number of people suffering from neurodegenerative diseases, such as Alzheimer`s disease, increased dramatically over the past centuries and is expected to increase even further within the next years. Based on predictions of the World Health Organization and Alzheimer`s Disease International, 115 million people will suffer from dementia by the year 2050. An additionally increase in other age related neurodegenerative diseases is also forecasted. Quite naturally, neurodegenerative diseases became a focus of attention of governments and health insurances, trying to control the uprising financial burden. Early detection and treatment of neurodegenerative diseases could be an important component in containing this problem. In particular, researchers focused on automatic methods to analyze patients’ imaging data. One way to detect structural changes in magnetic resonance images (MRI) is the voxel-based method approach. It was specifically implemented for various imaging modalities, e.g. T1-weighted images or diffusion tensor imaging (DTI). Voxel-based morphometry (VBM), a method specifically designed to analyze T1-weighted images, has become very popular over the last decade. Investigations using VBM revealed numerous structural brain changes related to, e.g. neurodegeneration, learning induced structural changes or aging. Although voxel-based methods are designed to be robust and reliable structural change detection methods, it is known that they can be influenced by physical and physiological factors. Dehydration, for example, can affect the volume of brain structures and possibly induce a confound in morphometric studies. Therefore, three-dimensional T1-weighted images were acquired of six young and healthy subjects during different states of hydration. Measurements during normal hydration, hyperhydration, and dehydration made it possible to assess consequential volume changes in gray matter (GM), white matter (WM), and cerebrospinal fluid (CSF). The datasets were analyzed using VBM, FreeSurfer and SIENA. A significant decrease of GM and WM volume, associated with dehydration, was found in various brain regions. The most prominent effects were found in temporal and parietal areas, in the left inferior orbito-frontal region, and in the extra-nuclear region. Moreover, we found consistent increases in CSF, an expansion around 6% of the ventricular system affecting both lateral ventricles, i.e. the third and fourth ventricle. Similar degrees of shrinkage in WM volume and increase of the ventricular system have been reported in studies of Alzheimer’s disease during disease progression and in its prestage mild cognitive impairment. Based on these findings, a potential confound in GM and WM or CSF studies due to the subjects’ hydration state cannot be excluded and should be appropriately addressed. These results underline the sensitivity of VBM and might also concern other voxel-based methods, such as Tract-Based Spatial Statistics (TBSS). TBSS was specifically designed for WM analyses and its sensitivity might be helpful for revealing the spatial relation of structural WM changes and related blood serum biomarkers. Two common brain related biomarkers are the glial protein S100B, a plasticity inducing neuro- and gliotrophin, and neuron-specific enolase (NSE), a marker for neuronal damage. However, the spatial specificity of these biomarkers for brain region has not been investigated in vivo until now. Therefore, we acquired two MRI parameters – T1- weighted and DTI - sensitive to changes in GM and WM, and obtained serum S100B and NSE levels of 41 healthy subjects. Additionally, the gene expression of S100B on the whole brain level in a male cohort of three subjects from the Allen Brain Database was analyzed. Furthermore, a female post mortal brain was investigated using double immunofluorescence labeling with oligodendrocyte markers. It could be shown that S100B is specifically related to white matter structures, namely the corpus callosum, anterior forceps and superior longitudinal fasciculus in female subjects. This effect was observed in fractional anisotropy and radial diffusivity – the latest an indicator of myelin changes. Histological data confirmed a co-localization of S100B with oligodendrocyte markers in the human corpus callosum. S100B was most abundantly expressed in the corpus callosum according to the whole genome Allen Human Brain Atlas. In addition, NSE was related to gray matter structures, namely the amygdala. This effect was detected across sexes. The data demonstrates a very high S100B expression in white matter tracts, in particular in human corpus callosum. This was the first in vivo study validating the specificity of the glial marker S100B for the human brain, and supporting the assumption that radial diffusivity represents a myelin marker. The results open a new perspective for future studies investigating major neuropsychiatric disorders. All above mentioned studies are mainly dependent on the sensitivity and accuracy of soft and hardware parameters. In particular, technical developments have improved acquisition accuracy in the field of MRI. Interestingly, very little is known about the confounding effects of variations due to hardware parameters and their possible impact on reliability and sensitivity of VBM. Recent studies have shown that different acquisition parameters may influence VBM results. Therefore age-related GM changes were investigated with VBM in 36 healthy volunteers grouped into 12 young, 12 middle-aged and 12 elderly subject. Six T1-weighted datasets were acquired per subject with a 12-channel matrix coil, as well as a 32-channel array, MP-RAGE and MP2RAGE, and with isotropic resolutions of 0.8 and 1 mm. DARTEL-VBM was applied on all images and GM, WM and CSF segments were statistically analyzed.. Paired t-tests and statistical interaction tests revealed significant effects of acquisition parameters on the estimated gray-matter-density (GMD) in various cortical and subcortical brain regions. MP2RAGE seemed slightly less prone to false positive results when comparing data acquired with different RF coils and yielded superior segmentation of deep GM structures. With the 12-channel coil, MP-RAGE was superior in detecting age-related changes, especially in cortical structures. Most differences between both sequences became insignificant with the 32-channel coil, indicating that the MP2RAGE images benefited more from the improved signal-to-noise ratio and improved parallel-imaging reconstruction). A possible explanation might be an overestimation of the GM compartment on the MP-RAGE images. In view of substantial effects obtained for all parameters, careful standardization of the acquisition protocol is advocated. While the current investigation focused on aging effects, similar results are expected for other VBM studies, like on plasticity or neurodegenerative diseases. This work has shown that voxel-based methods are sensitive to subtle structural brain changes, independent of imaging modality and scanning parameters. In particular, the studies investigated and discussed the analysis of T1- and diffusion weighted images with VBM and TBSS in the context of dehydration, blood serum sensitive biomarkers and aging were discussed. The major goal of these studies was the investigation of the sensitivity of voxel-based methods. In conclusion, sensitivity and accuracy of voxelbased methods is already high, but it can be increased significantly, using optimal hardand software parameters. It is of note, though, that these optimizations and the concomitant increase of detection sensitivity could also introduce additional confounding factors in the imaging data and interfere with the latter preprocessing and statistical computations. To avoid an interference e.g. originating from physiological parameters, a very careful selection and monitoring of biological parameters of each volunteer throughout the whole study is recommended. A potential impact of scanning parameters can be minimized by strict adherence to the imaging protocol for each study subjectwithin a study. A general increase in detection sensitivity due to optimized parameters selection in hard- and/or can not be concluded by the above mentioned studies. Although the present work addressed some of those issues, the topic of optimal selection of parameters for morphometric studies is still very complex and controversial and has to be individually decided. Further investigations are needed to define more general scanning and preprocessing standards to increase detection sensitivity without the concomitant amplification of confounding factors.

L'objectif de ce travail est de contribuer à la valorisation du métakaolin en substitution du ciment dans les matrices cimentaires en levant certains verrous scientifiques. En effet l'utilisation d'additions minérales modifie les propriétés des bétons, que cela soit à l'état frais, à l'état durcissant ou à l'état durci. A l'état frais, la rhéologie a été étudiée avec l'adaptation et l'application d'une méthode de formulation pour béton auto-plaçant. Cette application a été développée jusqu'à l'échelle industrielle. A l'état durcissant, la phase d'hydratation a été étudiée en s'attardant particulièrement sur l'effet de la nature du ciment substitué sur la réactivité du métakaolin. Enfin à l'état durci deux caractéristiques de durabilité ont été explorées, à savoir l'effet du métakaolin sur la carbonatation dans une première partie, puis sur la diffusion des chlorures dans une deuxième partie. / The objective of the present thesis was to promote the use of metakaolin as substitute for cement in cementitious matrix by unlocking several scientific challenges. The use of mineral additions modifies the properties of concrete in the fresh state, the hardening state and the durability state. In the fresh state, rheology was studied by adapting a formulation method for self-compacting concretes. This application was then further developed to be used at an industrial scale. In the hardening state, the hydration phases were analysed with a focus on the effect of the cement nature on the metakaolin reactivity. Finally in the durability state, two particular features were studied:1) the metakaolin effect on the carbonation kinetic and 2) the effect of the metakaolin on the chloride diffusion.

L'électrodialyse peut être utilisée pour traiter des effluents salins contenant de la matière organique. La compréhension des mécanismes de transfert (eau, ions, espèces organiques) à travers les membranes échangeuses d'ions et particulièrement l'influence de la composition ionique est un point clé vis-à-vis des performances du procédé. L'objectif de cette thèse est l'étude du transfert et la relation avec les performances de dessalement. Les nombres d'hydratation des ions sont tout d'abord calculés à partir des mesures du transfert des ions et de l'eau. Ils sont indépendants du courant et de la composition saline. La comparaison avec des valeurs de la littérature montre que les membranes ont peu d'effet sur l'hydratation des ions. Le transfert d'espèces organiques est ensuite étudié pour différentes compositions salines. Outre la diffusion, une contribution additionnelle est mise en évidence (convection pour les espèces neutres, migration pour les espèces chargées). Pour les espèces neutres, diffusion et convection sont du même ordre de grandeur et fixées par l'effet stérique. Des tendances inverses sont obtenues concernant l'hydratation des ions, la diffusion étant limitée par les modifications des membranes, la convection étant limitée par l'hydratation des espèces organiques en solution. Pour les espèces chargées, la migration domine la diffusion, les deux contributions étant influencées par la présence de sel. Les performances de dessalement sont enfin discutées sur la base d'un modèle phénoménologique à 4 paramètres liés au transfert de l'eau, des ions et des espèces organiques. La robustesse du modèle est validée pour différentes conditions. Ce travail montre que l'électrodialyse est une technologie très prometteuse pour le dessalement d'effluents contenant de la matière organique. / Electrodialysis can be used to treat saline water containing organic solute, separating organic solutes from salt. The understanding of salt, water and organic solute transfer through ion- exchange membranes and especially the influence of salt composition is a key factor regarding the process performances. The aim of the Thesis is to investigate the mass transfer and the relationship with the desalination performance. Firstly, hydration numbers of individual ion transferring through the membranes are computed based on experimental measurements of ion- water flux. They are independent from the salt compositions and current. Comparison with literatures values shows that the membranes have a weak influence on the ion hydration. Secondly, the transfer of different organic solutes is investigated with different salt compositions. Two contributions are pointed out, diffusion and additional one (convection for neutral solute, migration for charged one). For neutral solutes, diffusion and convection are comparable and both fixed by steric effect. Ion hydration leads to reversed trend for diffusion due to membrane swelling and convection due to solute dehydration. For charged solute, migration is more important than diffusion, both being influenced by the presence of salt. Then, desalination performance is discussed based on a phenomenological model, consisting of 4 parameters, related to ion, water and organic solute transfer respectively. The robustness of the model is demonstrated for different conditions. This work shows that electrodialysis can be a very promising process for the desalination of saline water containing organic solutes.

Le béton est le matériau le plus utilisé dans le monde. Son succès vient de son accessibilité et ses performances mécaniques, surtout lorsqu'il est renforcé par de l'acier. Dans le béton, l'acier doux est naturellement protégé par la formation d'une couche d'oxyde protectrice. Ceci est possible avec l'alcalinité du béton résultant de l'hydratation du ciment Portland.Cependant, la fabrication du ciment Portland est responsable de 5 à 7% des émissions anthropiques mondiales de CO2. Le développement du ciment Belite-Ye'elimite-Ferrite (BYF) comme liant alternatif est une solution prometteuse avec une diminution de 20 à 30% des émissions de CO2 par rapport à la production de ciment Portland. Les propriétés sont en cours d'évaluation et la possibilité d'utiliser l’acier doux en renfort sans corroder en fait partie.Cette thèse traite de la corrosion de l'acier incorporé dans des matériaux à base de ciment BYF sous différents angles. Tout d'abord, une étude d'hydratation détaillée a été effectuée pour comprendre l'évolution de l'électrolyte, c'est-à-dire de la solution interstitielle et de l'assemblage de phases. Ensuite, la passivation des barres d'armature d'acier ordinaire intégrées dans des mortiers renforcés a été étudiée. De plus, des analyses ont été effectuées avec des échantillons d'acier immergés dans des extraits aqueux de pâtes de ciment équivalentes pour caractériser la structure et l'épaisseur du film passif. Enfin, l'impact des chlorures initiaux sur la corrosion des mortiers renforcés a été évalué.L'hydratation a été caractérisée par plusieurs techniques, au jeune âge et pendant un an, avec des techniques telles que la calorimétrie isotherme, la spectroscopie d'émission optique par plasma à couplage inductif, la thermogravimétrie, la diffraction des rayons X et la porosimétrie par intrusion au mercure. L'évolution de l'acier dans les mortiers a été évaluée avec des techniques électrochimiques. L'applicabilité des techniques non destructives courantes (potentiel de demi-cellule, résistance à la polarisation linéaire, et l'impédance électrochimique) a été validée par des mesures de polarisation potentiodynamique large et une inspection visuelle. Le film passif formé dans des extraits aqueux des mortiers a été caractérisé par des techniques électrochimiques couplées aux mesures de spectroscopie de photoélectrons aux rayons X. Une fois que la passivation établi, l'impact des chlorures initiaux sur les mortiers renforcés a été évalué.Pour le BYF, le processus d'hydratation et les assemblages de phases hydratées sont différents du ciment Portland, mais la solution interstitielle est finalement très basique après un jour (pH de 13). La principale différence est le pH qui est inférieur (10.6) avant la prise. Les mesures ont montré que l'acier se passive avec le même niveau de protection qu’avec le ciment Portland. La différence est le temps nécessaire pour atteindre le meilleur niveau de protection (28 jours avec le ciment BYF au lieu de 7 jours avec le ciment Portland). Les échantillons d’acier immergés dans des extraits aqueux de ciment Portland et BYF après 28 jours d’hydratation ont présenté une épaisseur et une composition similaires, indiquant que le milieu BYF est aussi protecteur que celui de Portland. L'acier passive dans les mortiers BYF (E/C = 0.5) contenant 0.4% de chlorures par masse de ciment, ce qui ne remet pas en question, pour ce nouveau ciment, la limite imposée par la norme européenne EN-206 aux bétons armés. / Concrete is the most widely used material in the world. The success lies on its affordability and mechanical performance, especially when reinforced with steel. Once embedded in the concrete, mild steel is naturally protected by the formation of a protecting oxide layer. This is possible thanks to the alkalinity of the concrete which results from the hydration of the Portland cement.However, Portland cement manufacturing is responsible of about 5 to 7% of the global anthropogenic CO2 emissions. The development of Belite-Ye’elimite-Ferrite (BYF) cement as alternative binder is a promising solution with a decrease of 20 to 30% in CO2 emissions compared to Portland production. The properties are being evaluated and the possibility of using mild steel reinforcement without corroding is part of it.This thesis approaches the corrosion of steel embedded in BYF cement based materials from various angles. First, a detailed hydration study was performed to understand the evolution of the “electrolyte”, i.e. of the pore solution and of the phase assemblage. Second, the passivation of ordinary steel rebar embedded in reinforced mortars was investigated. In addition, analyzes were carried out with steel samples immersed in aqueous extracts of equivalent cement pastes to characterize the structure and the thickness of the passive film. Finally, the impact of the initial chlorides on corrosion of reinforced mortars was evaluated.The hydration was characterized by several techniques, at early-age and then over one year, with techniques such as isothermal calorimetry, inductively coupled plasma optical emission spectroscopy, thermogravimetry, X-ray diffraction and mercury intrusion porosimetry. The evolution of steel embedded in mortars was evaluated with several electrochemical techniques. The applicability of current non-destructive techniques (half-cell potential readings, linear polarization resistance and electrochemical impedance spectroscopy) has been validated by large potentiodynamic polarizations and visual inspection. The passive film formed in aqueous extracts of the mortars was characterized with electrochemical techniques coupled to X-ray photoelectron spectroscopy measurements. Once the passivation understood, the impact of the initial chlorides on the reinforced mortars was evaluated.For the BYF, the hydration process and the hydrated phase assemblages are different from Portland cement, but the interstitial solution is finally very basic after one day (pH of 13). The main difference is the pH that is lower (10.6) before setting. The measurements showed that steel was effectively passivated in BYF mortars with the same level of protection as with Portland cement. The difference between the BYF and Portland cement is the time required that to reach the greatest level of protection (28 days instead of 7 days), probably because of initial lower pH value. The steel immersed in Portland and BYF aqueous extracts obtained after 28 days of hydration exhibited similar thickness and composition of protective layer, indicating that BYF media was as protective as Portland ones. Steel passivates in BYF mortars (W/C = 0.5) containing 0.4% chlorides by cement mass which is in agreement with the limit imposed by the European Standard EN-206 to reinforced Portland concretes.

L’optimisation des performances énergétiques du bâtiment et la réduction des émissions de CO2 générées par le secteur de la construction sont devenus des enjeux majeurs. Il s’agit non seulement de réduire considérablement les consommations d’énergie liées au chauffage et à la climatisation durant la période de fonctionnement des bâtiments mais aussi de choisir des matériaux à faible impact carbone en privilégiant l’utilisation de ressources renouvelables et locales. Ces dernières années ont vu naître un intérêt croissant pour les bétons de chanvre. Ces agromatériaux associent un granulat végétal issu de la tige du chanvre avec un liant minéral. Il en résulte un matériau isolant qui présente une certaine efficacité à réguler les variations de température et d’humidité. Considérés comme multifonctionnels, les bétons de chanvre constituent une alternative écologique aux enveloppes traditionnelles. Face aux matériaux à isolation répartie comme le béton cellulaire ou la brique dont l’impact carbone est élevé, les bétons de chanvre présentent l’inconvénient d’être peu résistants mécaniquement et sont de ce fait associés à une structure porteuse. Ce travail de thèse s’inscrit dans une démarche visant d’une part à diversifier la ressource végétale utilisée pour la confection des agromatériaux de construction en développant un béton innovant incorporant les balles de riz de Camargue et d’autre part à étudier certains procédés dans l’optique d’améliorer les performances mécaniques de ces matériaux après les premiers mois de cure. Le premier objectif a consisté à caractériser la balle de riz naturelle préalablement à son association avec un liant à base de chaux. Les caractéristiques propres au granulat de balles de riz se sont traduites par la fabrication d’un agrobéton moins dosé en eau et de densité apparente plus élevée que celle du béton de chanvre (en restant inférieure à 800 kg.m-3). La conductivité thermique du béton à base de balles de riz s’est montrée similaire à celle du béton de chanvre pour un ratio massique « liant/granulat (L/G) » identique. En revanche, les performances mécaniques en compression se sont révélées plus faibles pour le béton à base de balles de riz après 1 mois de cure à 20°C et 50%HR.Le second axe de travail s’est porté sur le suivi temporel des caractéristiques mécaniques et du durcissement du liant jusqu’à 10 mois de conservation soit à 20°C et 50%HR soit en conditions extérieures. Les bétons de chanvre se sont caractérisés par un gain de résistance en compression plus favorable que celui observé sur les bétons de balles de riz malgré une cinétique de durcissement du liant équivalente. Cette conservation naturelle a été comparée à une cure en carbonatation accélérée (CO2). Les résultats ont montré que ce procédé a permis d’obtenir une résistance en compression 2 mois après la fabrication des éprouvettes équivalente à celle obtenue après 10 mois de conservation à l’extérieur. Considérant que la résistance mécanique du béton à base de balles de riz est limitée par la liaison mécanique liant/particule, ce travail s’est porté également sur l’effet d’un traitement des particules à l’eau de chaux saturée. S’il s’est montré inefficace pour le béton de chanvre, il a permis d’améliorer la résistance en compression des bétons à base de balles de riz.Enfin, cette étude a traité de l’effet d’une cure humide (95%HR) et d’une élévation de température (50°C) sur le durcissement du liant et l’acquisition des résistances mécaniques à court terme. L’étude a été préalablement menée sur des mortiers de chaux. Les résultats ont montré que ce type de cure permet une très forte augmentation de la résistance mécanique du liant après 28 jours par un effet cinétique sur les réactions d’hydratation. Toutefois, ces conditions de cure ont entrainé une perturbation de la zone de transition entre le liant et la particule et par conséquent une dégradation des propriétés mécaniques des agrobétons. / The improvement of building energy efficiency and the reduction of CO2 emissions from the construction industry have become a major issue over the last years. We need to cut the energy consumption linked to heating and cooling of buildings during their operating period but also to choose materials with low carbon footprint using renewable and local resources.Hemp concretes are more and more used in green construction. These bio-based building materials consist of hemp-derived aggregates mixed with mineral binders and water. These concretes have attractive insulating properties and present some effectiveness in buffering variations of temperature and humidity in buildings. Considered as a multifunctional material, hemp concrete can offer an eco-friendly alternative to traditional building envelopes but have the disadvantage of being very low strength. Unlike cellular concrete or clay bricks, hemp concretes cannot be used as load-bearing materials but for infilling walls with a wood timber frame. The aim of this thesis work is, on the one hand, to diversify plant aggregates used for the manufacturing of bio-based concretes by developing an innovative material based on local rice husk from the Camargue area and on the other hand to investigate some processes in order to increase mechanical strength of these materials after the first months of curing. The first objective of this work was to characterize rice husks prior to incorporating them in a lime-based mix. Intrinsic features of rice husks led to the manufacturing of a new bio-based concrete designed with a lower water content and a higher apparent density than hemp concrete (by remaining below 800 kg.m-3). Thermal conductivity of rice husk concrete was comparable to that of hemp concrete for a given « binder on aggregates (B/A) » mass ratio. Nevertheless, mechanical performances in compression have proved lower for the rice husk concrete after one month of hardening at 20°C and 50%RH. The second line of the work dealt with the evolution of mechanical properties and binder hardening over time. Specimens were cured during 10 months either at 20°C and 50%RH or exposed outdoors. Hemp concrete exhibited a higher compressive strength gain over time than that achieved for rice husk concrete despite a same hardening kinetics. This curing under natural carbonation was compared to an accelerated one (CO2 curing). Accelerated carbonation provided the opportunity to obtain the same compressive after 2 months than that reached after the outdoor exposure during 10 months. Considering that compressive strength of rice husk concrete is restricted by the bonding strength between the binder and the aggregates, this work also focused on the effect of a lime-water treatment of plant aggregates. This latter was not efficient for hemp concrete but increased compressive strength of rice husk concrete. Finally, the effect of a moist curing (95%RH) and elevated temperature (50°C) on binder hardening and strength development of bio-based concretes was investigated. This aspect was also studied on lime-based mortars. The results showed that this type of curing led to a strong increase of mechanical strength for the binder after 28 days due to kinetic effects on hydration reactions. Nevertheless, these curing conditions were detrimental to the transition zone between the binder and the plant aggregates and consequently counterproductive for the mechanical performances of bio-based concretes.

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No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Tese - Fernanda Vieira Castejon - 2017.pdf: 1633636 bytes, checksum: 5ac5b85abaf8273f5b10ebe5577fb0e0 (MD5) Previous issue date: 2018-12-15 / Two experiments aimed to evaluate the association between a nutritive gel and synbiotic, offered on different days and pharmaceutical formulations in face of the situations of pre-allotment fasting and sanitary challenge. At the first trial, the synbiotic supplementation associated to the nutritive gel were evaluated at the performance of broilers, nutrient metabolizability, intestinal histomorphometry, blood biochemistry, organ morphometry and carcass traits in chicks submitted to fasting. The treatments were: CN - negative control; G - nutritive gel in the hatchery; GS - synbiotic dissolved in the nutritive gel; GSS - synbiotic dissolved in the nutritive gel+synbiotic offered in drinking water on specific days and S - only synbiotic, on specific days, in the water. Significant differences were observed on 7, 21, 28 and 35 days of age, with higher values for the G, GS and GSS treatments, as well as higher metabolizable values for the ether extract. There were no differences of total intestinal length or segments, but the relative weight of some organs differed between treatments. Carcass yield were not influenced by the treatments. In the second experiment, the objective was to evaluate the synbiotic supplementation associated with nutritional gel in mortality, lesion scores, oocyst excretion, litter quality, zootechnical performance and organ morphometry in chickens challenged with E. acervulina, E tenella and E. maxima. The treatments were: CP - positive control; GSA - synbiotic dissolved in the nutritive gel in the hatchery and supply, of synbiotic in the water on specific days; GSR - synbiotic dissolved in the nutritive gel in the hatchery+ continuous use of synbiotic in the diet and SAL - anticoccidial salinomycin added in the diet. Higher absolute mortality in all treatments was observed in the third experimental week and higher total mortality was found in the CP group. No differences were found for intestinal lesions, oocyst excretion, pH and dry matter of the bed between treatments. Some differences were found between relative weight of organs at the ages evaluated. Better overall performance was observed in the SAL group. It is concluded that in the pre-accommodation fasting situation, the early supplementation of nutritive gel associated or not to the synbiotic can stimulate or contribute to the functional development of the gastrointestinal tract, which was reflected in better performance and metabolizability. Under the conditions of the second experiment, the same observed benefits of the use of the gel associated or not to the synbiotic were not observed, since no improvement could be verified in the evaluated parameters, so the use of anticoccidial in the diet should still be recommended. / Dois experimentos foram realizados com o objetivo de verificar os efeitos da associação entre um gel nutritivo fornecido no incubatório associado a um produto simbiótico frente às situações de desafios de manejo e sanitário. No primeiro experimento, avaliou-se a a suplementação de simbiótico associado ao gel nutritivo no desempenho de frangos de corte, metabolizabilidade, histomorfometria intestinal, bioquímica sanguínea, morfometria de órgãos e características de carcaça em pintos submetidos à jejum hídrico e alimentar no período pré-alojamento. Os tratamentos foram: CN – controle negativo; G – somente gel nutritivo no incubatório; GS – somente simbiótico dissolvido no gel nutritivo no incubatório; GSS - simbiótico dissolvido no gel nutritivo no incubatório e simbiótico ofertado na água de bebida, em dias específicos, e S – somente simbiótico, em dias específicos, na água dos animais. Diferenças significativas foram observadas no desempenho aos 7, 21, 28 e 35 dias de idade, em geral, com valores superiores para os tratamentos G, GS e GSS, assim como maiores valores de metabolizabilidade do extrato etéreo encontradas para os mesmos grupos. Não ocorreram diferenças no comprimento intestinal total ou segmentos, mas o peso relativo de alguns órgãos diferiram entre os tratamentos. As características de carcaça não foram influenciadas pelos tratamentos. No segundo experimento, objetivou-se avaliar a suplementação de simbiótico associado ao gel nutritivo comparados à salinomicina na mortalidade, escores de lesões, excreção de oocistos de Eimeria, qualidade da cama, desempenho zootécnico, histomorfometria intestinal e morfometria de órgãos em frangos desafiados com E. acervulina, E. tenella e E. maxima. Os tratamentos foram: CP - controle positivo; GSA – simbiótico dissolvido no gel nutritivo no incubatório e fornecimento, em dias específicos, de simbiótico na água; GSR – simbiótico dissolvido no gel nutritivo no incubatório associado ao uso contínuo de simbiótico na ração e SAL – anticoccidiano salinomicina adicionado na ração. Foi observado um aumento na mortalidade absoluta em todos os tratamentos na terceira semana experimental e maior mortalidade durante todo o período experimental no grupo CP. Não foram verificadas diferenças para lesões intestinais, excreção de oocistos, pH e matéria-seca da cama entre os tratamentos. Algumas diferenças foram encontradas entre peso relativo de órgãos nas idades avaliadas. Melhor desempenho zootécnico, de forma geral, foi observado no grupo SAL. Conclui-se que na situação de jejum pré-alojamento, a suplementação precoce de gel nutritivo associado ou não ao simbiótico pode estimular e/ou contribuir para o desenvolvimento funcional do trato-gastrintestinal, o que se refletiu em melhor desempenho e metabolizabilidade. Já nas condições do segundo experimento, os mesmos benefícios observados do uso do gel associado ou não ao simbiótico não foram observados, uma vez que não pôde ser verificado melhoria nos parâmetros avaliados, de forma que o uso de anticoccidiano na ração ainda deve ser recomendado.

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.

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.

This masters thesis deals with influence of cement bypass kiln dust on physico-mechanical properties of alkali activated slag and influence of chosen compounds of cement bypass kiln dust on alkali activated slag. Using alkali activated slag is limited by its shrinkage. The setting time with different amount of cement bypass kiln dust and its chosen compounds (CaO, KCl and K2SO4) were measured by isotermal and isoperibolic calorimetry too. The strength and length changes of the mixtures with different amount of cement bypass kiln dust were measured. Samples were analysed by X-Ray diffraction analysis and scanning electron microscopy. It has been found that the increasing addition of dust reduce setting time, flexural and compresive strength and shrinkage. Presence of free CaO was found being one of the reasons for accelerated setting. KCl and K2SO4 have retarding effect but influece of free CaO prevails even for its lower contents. Long-term properties evolution is strongly dependent on curing regime due to potential volume expansion.