Chronic conditions such as obesity, inflammatory bowel disease (IBD), and colitis are associated with gastrointestinal (GI) inflammation and compromised GI barrier integrity. Cocoa may be a potential dietary strategy to mitigate gut-related conditions and been shown to elicit anti-inflammatory, antioxidant, and prebiotic effects. Alkali treatment of cocoa was once thought to reduce its bioactivity, but new evidence suggests it may enhance cocoa's health properties, through the formation of new, potentially bioactive high molecular weight compounds. Inulin, a fructose-containing plant polymer, exerts prebiotic effects and has also been investigated in the mitigation of IBD. This study aims to 1) investigate effects of alkali processing on gut health related bioactivity and phytochemical composition of cocoa and 2) evaluate potential additive benefits of combining cocoa and inulin. Polyphenolic and flavanol compounds in natural cocoa, alkalized cocoa, and inulin powders were characterized using Folin-Ciocalteu (total polyphenols) and 4-dimethylaminocinnamaldehyde (total flavanols) assays, thiolysis , and HILIC UPLC-MS/MS. Treatments of cocoa and inulin were made in 1:2 cocoa:inulin and 1:4 cocoa:inulin mixtures for both natural and alkalized cocoas. Cocoa mixtures, in addition to both cocoa powders and inulin alone, were subjected to an in-vitro digestion to generate material for an in-vitro fecal fermentation. Samples collected from the fermentation at 0, 6, 12, and 24 hours were analyzed via HPLC-MS for microbial metabolites, applied to HT-29 colon cancer cells to assess anti-inflammatory activity, and applied to a florescence assay measuring PLA2 inhibitory activity. The alkalized cocoa powder was found to have a significantly lower concentration of total polyphenols and total flavanols, as well as a lower mDP, suggesting that alkalization may affect larger procyanidins more than smaller flavanol compounds. Inulin enhanced the inhibition of the PLA2 enzyme and enhanced the IL-8 anti-inflammatory properties of cocoa, although the trends were weak. Overall, we did not see any clear, significant effects of alkalization or the addition of inulin to cocoa's colonic metabolite formation or its gut bioactivity in vitro. However, we have demonstrated that colonic fermentation of cocoa may have a negative effect on its bioactivity in vitro. Future research should further explore flavanol DP and bioactivity, fiber's interaction with polyphenols, colonic metabolism of cocoa, and cocoa's gut health effects in vivo. / Master of Science in Life Sciences / Gut conditions like obesity-associated inflammation and inflammatory bowel disease are highly prevalent, debilitating, and currently have no cure. Cocoa has been investigated as a possible dietary strategy for the mitigation and prevention of chronic inflammatory gut conditions due to its anti-inflammatory and enzyme inhibiting properties. Most attribute these effects of cocoa to its abundance of compounds called polyphenols. It is widely thought that the ability of cocoa to promote health is lost when cocoa beans are processed, because of the loss of polyphenols. Alkalization, or "Dutching", is an optional step in cocoa processing that some manufacturers perform to enhance flavor and color formation. Dutching cocoa can promote the polymerization of many smaller, flavanol, protein, and other compounds into larger, indigestible compounds. These indigestible compounds will not be absorbed in the small intestine and may be broken down in the large intestine by colonic bacteria, forming new metabolites. We obtained cocoa powders, one natural (not alkalized) and one alkalized and compared them in terms of content of polyphenols, bioactivities, and anti-inflammatory abilities. Additionally, we added a known prebiotic, inulin, to our cocoa formulations to determine if there are additive benefits of cocoa and inulin together. Ultimately, we found that alkalized cocoa contained lower concentrations of all polyphenolic compounds, even the larger compounds. Inulin enhanced the inhibition of digestive enzymes and the anti-inflammatory properties of cocoa, though not significantly. Inulin also reduced the pH (i.e. increased the acidity) of a simulated gut environment, which may be beneficial. Alkalization did not significantly affect cocoa's enzyme inhibitory activity or anti-inflammatory activity. Overall, the addition of inulin to cocoa does not seem to be effective in increasing cocoa's ability to treat and prevent gut diseases, but more information is needed.

Résumé : La connaissance de la fiabilité d’une structure dans sa durée de vie est d’une importance stratégique. Plusieurs méthodes non destructives ont ainsi été développées pour évaluer l’état des ouvrages en béton. Parmi ces techniques, les méthodes basées sur l’acoustique non linéaire ont démontré une performance satisfaisante en laboratoire pour détecter les microfissures de façon précoce. L’objectif de cette thèse consiste à apporter de nouvelles idées contribuant au développement de la méthode du saut temporel ultrasonore (en tant que méthode acoustique non linéaire) pour l’évaluation in situ des structures en béton. Ce travail porte plus particulièrement sur la caractérisation du béton atteint de réaction alcalis-silice (RAS). L’originalité de ce travail réside principalement dans l’utilisation des sollicitations naturelles auxquelles les ouvrages d’art sont soumis comme source d’excitation du milieu pendant l’application du saut temporel (ST). La sollicitation fournie par le passage d’un véhicule sur un tablier d’un pont est l’un des exemples de ces sources naturelles. Un programme expérimental a donc été mis sur pied, qui consiste en une phase d’étude au laboratoire et à une phase d’étude sur site. Deux dalles de béton réactif et une dalle de béton non réactif (1,40×0,75×0,3 m[indice supérieur 3]) ont été fabriquées en laboratoire afin d’évaluer l’idée générale de cette thèse. Pour générer les ondes d’excitation de basses fréquences requises pour les essais ST, un vérin hydraulique a été utilisé comme sources d’impact simulant le passage d’un véhicule. Avec ce protocole d’essais, la progression de la RAS a été caractérisée dans les dalles réactives. Il a été démontré que le ST peut détecter sans équivoque la RAS à partir d’une expansion de 0,03%. Les résultats montrent également que la perturbation des éléments structuraux par le passage d’un véhicule serait exploitable pour les investigations in situ. L’effet de la température sur le comportement acoustique non linéaire du béton a également été étudié : les mesures acoustiques non linéaires sont plus fiables dans une plage de température entre 10[degré]C et 30[degré]C. Des essais préliminaires ont été effectués sur le tablier d’un petit pont en béton. Les perturbations requises ont été fournies par le passage d’un camion dans une plage de vitesses variant de 20 km/h à 50 km/h; en utilisant deux types d’excitation (naturelle et amplifiée en utilisant des obstacles). Les résultats ont démontré qu’on peut appliquer la méthode ST sur site en utilisant l’excitation naturelle générée par un camion. Les expériences faites dans cette thèse révèlent la faisabilité de la méthode du ST pour évaluer l’état des structures en béton, notamment celles qui sont dégradées par la RAS. // Abstract : Reliability of a structure during its service life is strategically important. Several non-destructive methods have been developed to evaluate the condition of concrete structures. Among these techniques, the methods based on nonlinear acoustic have shown an excellent performance in laboratory for detecting micro-cracks at early ages. The objective of the thesis is to work on new ideas, which may contribute to develop the method of Ultrasonic Time Shift (as a nonlinear acoustic method) for evaluating concrete structures. This thesis focused was on concrete elements suffering from Alkali-Silica Reaction (ASR). The originality of the work is related to the idea that the natural vibrations, which exist in structures, can be used for perturbing structural elements during a Time Shift test. For instance, the vibration generated by a vehicle passing on a bridge is one of the examples of the natural resources of vibration. To reach the objective of this thesis, a research program was conducted in two phases: 1) experiments in laboratory; 2) field experiments. Two concrete slabs with reactive coarse aggregates and one with nonreactive aggregate were fabricated in the lab in order to assess the main idea of the thesis. A hydraulic actuator with an impact form loading pattern was used to generate low frequency waves (used to perturb the test-media) for tests of Time Shift (TS). Such loading pattern is similar to the loading imposed by a vehicle passing on a bridge deck. The progression of ASR-damage in the concrete slabs was successfully tracked using the developed methodology. It was shown that the TS can detect ASR from an expansion level about 0.03%.The results also show that the new methodology used for exciting structural elements can be used for field investigations. The effect of the temperature on nonlinear acoustic behavior of the concrete was also assessed. This investigation revealed that measurements in temperatures ranged from 10oC to 30oC can lead to better results. Some filed tests were carried out on a concrete slab of a small-size bridge. The required perturbations for the tests were provided by a truck. The velocity of the truck ranged from 20 km/h to 50 km/h.; using two types of perturbation (natural and exaggerated using some obstacles on surface). The results showed that the TS is an applicable method for field investigations, where the required perturbations are provided by a truck. The performed experimental program revealed the feasibility of the method of Time Shift for evaluating concrete structures, specifically those damaged by ASR.

For repairing concrete transportation infrastructure, such as pavements and bridges, much importance is placed on early-age strength gain as this has a major impact on scheduling and opening to traffic. However, the long-term performance and durability of such repair materials are often not satisfactory, thus resulting in future repairs. This research project focuses on the evaluation of the durability of various rapid-setting cementitious materials. The binders studied in this project include calcium aluminate cement (CAC), calcium sulfoaluminate cement (CSA), Type III portland cement, alkali-activated fly ash (AAFA) , and various prepackaged concrete materials. In addition, selected CAC and CSA mixtures were further modified with the use of a styrene-butadiene latex. The durability aspects studied include freezing-and-thawing damage and the implications of air entrainment in these systems, alkali-silica reaction, sulfate attack, and permeability of the concrete matrix and potential corrosion. / text

Clusters/nanoparticles are aggregates of a “small” number of building blocks, atoms or molecules, ranging from two up to millions of atoms. Two main groups of clusters have been studied using photoelectron spectroscopy based on synchrotron radiation. They are dry/wet alkali-halide clusters, including pure water clusters, and metal-based nanoparticles. For the dry alkali halide clusters, analysis of the data and theoretical modeling has allowed us insights into the local electronic properties at nanoscale: a change of polarizability of ions in the alkali-halide clusters due to the varying environment has been suggested. The study of the wet salt clusters shows that the alkali-halides are already solvated at the nanoscale reached by water clusters doped with salt vapor. The photoelectron angular distribution of water cluster shows lower anisotropy parameters as compared to the separate monomers. A model based on intracluster scattering has been built to partly explain the reduction. In the last part of the thesis, metal-based multi-component nanoparticles have been produced by self-assembly processes using reactive magnetron sputtering. Depending on the specific metal element, oxidation processes have been applied before or after the aggregation. Clearly radial distributions such as core-shell and “sandwich-like” structures have unambiguously determined by photoelectron spectroscopy.

This paper reports the development of an Alkali Activated Binder (AAB) with an emphasis on the performance and the durability of the AAB-matrix. For the development of the matrix, the reactive components granulated slag and coal fly ash were used, which were alkali activated with a mixture of sodium hydroxide (2 - 10 mol/l) and aqueous sodium silicate solution (SiO2/Na2O molar ratio: 2.1) at ambient temperature. A sodium hydroxide concentration of 5.5 mol/l revealed the best compromise between setting time and mechanical strengths of the AAB. With this sodium hydroxide concentration, the compressive and the 3-point bending tensile strength of the hardened AAB were 53.4 and 5.5 MPa respectively after 14 days. As a result of the investigation of the acid resistance, the AAB-matrix showed a very high acid resistance in comparison to ordinary Portland cement concrete. In addition, the AAB had a high frost resistance, which had been validated by the capillary suction, internal damage and freeze thaw test with a relative dynamic E-Modulus of 93% and a total amount of scaled material of 30 g/m2 after 28 freeze-thaw cycles (exposure class: XF3).

Des nouveaux procédés éco-efficients basés sur une meilleure utilisation des ressources renouvelables sont nécessaires pour assurer la continuité du développement énergétique. La thèse étudie le procédé de gazéification en eau supercritique (T>374°C et P>22,1 MPa) de la biomasse très humide pour l’obtention de l’hydrogène, molécule ayant un potentiel énergétique très intéressant à valoriser avec un impact environnemental très favorable. L’étude porte sur l’application du procédé à la biomasse modèle (solutions de glucose, glycérol et leur mélange) ainsi qu’au bioglycérol, résidu de la fabrication du biodiesel. Les propriétés du solvant et les mécanismes prépondérants développés par l’eau en phase souset supercritique peuvent être contrôlés par les paramètres opératoires imposés au processus : température, pression, concentration en molécules organiques et catalyseur alcalin, temps de réaction... Les études paramétriques des systèmes réactionnels ont été menées dans des réacteurs batch à deux échelles différentes, les phases résultantes étant caractérisées par des protocoles analytiques élaborés et validés dans le cadre de l’étude. Le suivi du milieu réactionnel en batch lors de son déplacement vers l’état supercritique a mis en évidence une conversion avancée des molécules organiques et une identification de certains intermédiaires générés. Parmi les paramètres étudiés, la température et le temps de réaction influent le plus le rendement à l’obtention d’hydrogène en présence de catalyseur (K2CO3) dans les réacteurs batch, rendements de 1,5 et 2 mol d’H2 respectivement par mol de glycérol et de glucose introduites. Les gaz obtenus contiennent des proportions variables d’hydrocarbures légers et du CO2. Environ 75% du carbone est converti en phase gaz et liquide (sous forme de carbone organique et inorganique), le restant étant déposé sous forme solide ou huileuse. L’analyse du solide généré (plus de 90% de C) laisse apparaître différentes phases, y compris la formation de nanoparticules sphériques. Enfin, la gazéification en réacteur continu du glycérol préchauffé a montré de meilleurs rendements en hydrogène que le procédé batch, pendant que celle du bioglycérol demande une évolution du procédé à cause de la précipitation en phase supercritique des sels contenus dans le réactant. En conclusion, la gazéification en eau supercritique de la biomasse peut être considérée comme une alternative intéressante à d’autres procédés physico-chimiques de production de l’hydrogène. L’amélioration du procédé sera possible par son intensification menée en parallèle avec l’utilisation de matériaux plus performants et le contrôle de la salinité de la phase réactante. / Supercritical water (T > 374 ° C and P > 22.1 MPa) gasification of wet biomass for hydrogen production is investigated. This process converts a renewable resource into a gas, which is mainly composed of hydrogen and hydrocarbons with interesting energy potential, and which can be separated at high pressure. In addition, the greenhouse gas effect of the process is zero or negative. Model biomasses (glucose, glycerol and their mixture) and bio-glycerol, residue from bio-diesel production, have been gasified by different processes: two-scale batch reactors (5 mL and 500 mL) and a continuous gasification system. Supercritical water acts as a reactive solvent, its properties can be adjusted by the choice of the experimental (P, T) couple. The operating parameters, e.g. temperature, pressure, concentration of biomass and alkaline catalysts, reaction time… allow favoring certain reaction mechanisms. In order to characterize the processes, specific analytical protocols have been developed and validated. The intermediates, formed during the heating time in the batch reactors, have been identified. Among the investigated operating parameters, temperature and reaction time have the greatest influence on the hydrogen production in batch reactors. In the presence of catalyst (K2CO3), H2 yields of 1.5 mol/mol glucose and 2 mol/mol glycerol have been respectively observed. The obtained gas contains different proportions of light hydrocarbons and CO2. About 75% of the carbon is converted into gas and liquid (in form of organic and inorganic carbon). The conversion leads also to a solid or oily residue. In the generated solid phase (composed over 90% of C), spherical nanoparticles are observed via electronic microscopy. The hydrogen production from glycerol is improved in the continuous process compared to batch reactors, however, bio-glycerol supercritical water gasification requests process improvement due to the precipitation of the salt contained in the reactant. In conclusion, supercritical water gasification of biomass can be considered as an promising alternative process for hydrogen production. The process should be improved by more performing equipments and by the control of the salinity content of the crude biomass.

Ce travail de thèse propose une méthodologie multi-échelle basée sur l'utilisation de modèles de substitution fonction de variables aléatoires, pour évaluer la fiabilité résiduelle d'ouvrages en béton atteints de réaction alcali-granulat (RAG), dans l'optique d'une meilleure maintenance. Les modèles de substitution, basés sur des développements en chaos de polynômes des paramètres d'une fonction de forme (sigmoïde dans les cas traités), ont été constitués à plusieurs échelles, afin notamment de réduire les temps de calculs des modèles physiques sous-jacents. A l'échelle microscopique, le modèle de RAG employé est celui développé par Multon, Sellier et Cyr en 2009, comprenant initialement une vingtaine de variables aléatoires potentielles. A l'issue d'une analyse de sensibilité de Morris, le modèle de substitution permet de reproduire la courbe de gonflement dans le temps du volume élémentaire représentatif en fonction de neuf variables aléatoires. L'utilisation du modèle de substitution construit, pour la prédiction des effets mécaniques du gonflement dû à la RAG sur une éprouvette, a nécessité de prendre en compte l'anisotropie de ces effets en améliorant les fonctions poids proposées par Saouma et Perotti en 2006. L'échelle de l'éprouvette étant validée par la confrontation des prédictions aux données expérimentales des travaux de thèse de Multon, une application à l'échelle du barrage de Song Loulou a été entreprise. Le calcul du comportement thermo-chemo-mécanique d'une pile d'évacuateur de crues, dont les résultats en déplacements ont pu être confrontés aux données d'auscultation fournies par l'entreprise AES-SONEL (devenue ENEO), a été réalisé. Des modèles de substitution ont été construits ensuite à l'échelle de la structure afin d'obtenir les déplacements aux points d'intérêt, liés aux états limites de fonctionnement des évacuateurs, et procéder ainsi à l'estimation de la fiabilité résiduelle du barrage. Les calculs d'analyse de sensibilité et la construction des modèles de substitution ont été implémentés en Fortran, Java et OpenTURNS Les calculs sur éprouvette et pile de barrage ont été effectués sous Cast3M. / This work proposes a multi-scale methodology based on the use of surrogate models function of random variables, to evaluate the residual reliability of concrete structures suffering from alkali-aggregate reaction (AAR), for a better maintenance purpose. Surrogate models, based on polynomial chaos expansion of the parameters of a shape function (sigmoid in the studied cases), have been constituted at several scales, in particular in order to reduce computation time of the underlying physical models. At the microscopic scale, the AAR model employed is that developed by Multon, Sellier and Cyr in 2009, initially comprising about twenty potential random variables. At the end of a Morris sensitivity analysis, the surrogate model enables to reproduce the expansion curve over time of the representative elementary volume as a function of nine random variables. The use of the built-in surrogate model in predicting the mechanical effects of AAR expansion on a concrete core required to take into account the anisotropy of these effects by improving the weight functions proposed by Saouma and Perotti in 2006. The core's scale being validated by the comparison of the predictions with the experimental data of Multon's thesis work, an application at the scale of the Song Loulou dam was undertaken. The computation of the thermo-chemo-mechanical behavior of a spillway stack, whose results in displacement could be compared with the auscultation data provided by the company AES-SONEL (now ENEO), was realized. Surrogate models were then constructed at the scale of the structure to obtain displacements at the points of interest, related to the operating limit states of the spillways, and thus to estimate the residual reliability of the dam. The sensitivity analysis computations as well as the construction of the surrogate models were implemented in Fortran, Java and OpenTURNS. Computations on concrete cores and Song Loulou dam spillway were performed under Cast3M.

As deformações derivadas da retração e da fluência estão entre os principais fatores que afetam a integridade e facilidade de manutenção das estruturas de concreto a longo prazo. Outro fator que corrobora para a deterioração do concreto é a Reação Álcali-Agregado (RAA), que devido à sua característica expansiva é considerada uma manifestação patológica de difícil tratamento, sendo necessário medidas mitigadoras para evitar sua ocorrência. A retração, a fluência e a RAA são deformações expressivas em estruturas com grandes volumes de concreto, em que as deformações devido à retração e à fluência potencializam o efeito da RAA, criando um ciclo de degradação do concreto de difícil controle. Deste modo, este trabalho tem como objetivo a análise numérica que possibilite a previsão do comportamento da retração e da fluência quando associadas à RAA. O código computacional é baseado no Método de Elementos Finitos Posicional considerando o elemento de chapa com elementos triangulares de ordem cúbica e utilizando a lei constitutiva de Saint-Venant-Kirchhoff. Para a modelagem da RAA utiliza-se o estudo desenvolvido por Carrazedo & Lacerda (2008). A fluência e a retração são modeladas implementando-se os modelos FIB, JSCE e B4. Os resultados deste trabalho demonstram a eficiência da modelagem e da análise numérica para a previsão do comportamento das deformações do concreto sujeito à RAA, considerando os efeitos de retração e fluência. / Shrinkage and creep strains are among the main factors that affect the integrity and serviceability of concrete structures in long term. Another corroborating factor for the concrete deterioration is the Alkali-Aggregate Reaction (AAR), which due to its expansive characteristic is considered a pathological manifestation of difficult treatment, and mitigating measures are necessary to avoid its occurrence. Shrinkage, creep and AAR are expressive strains in structures with large volumes of concrete, in which strains due shrinkage and creep enhance the effect of AAR, creating a concrete degradation cycle that is difficult to control. Thus, this work has the aim of numerical analysis that allows the prediction of the shrinkage and creep behavior when associated with AAR. The computational code is based on the Positional Finite Elements Method considering the element of plate with triangular elements of cubic order and using the constitutive law of Saint-Venant-Kirchhoff. For the modeling of AAR is used the study developed by Carrazedo & Lacerda (2008). The creep and shrinkage are modeled by implementing the FIB, JSCE and B4 models. The results of this work demonstrate the efficiency of modeling and numerical analysis for the prediction of the strains behavior of concrete subject to AAR, considering the effects of shrinkage and creep.

O presente trabalho se insere no Programa de Biomassa - Energia - Materiais - PROBEM?, cuja Refinaria de Biomassa desenvolve tecnologias para o aproveitamento integral de biomassas lignocelulósicas e oleosas, objetivando sua exploração autossustentada. Os principais produtos obtidos são combustíveis para geração de energia termoelétrica, produtos químicos, materiais inorgânicos e reciclagem de fertilizantes. Neste trabalho explorou-se a celulignina, que é um combustível obtido pela pré-hidrólise ácida da biomassa, visando à obtenção de gás de síntese (singás) da celulignina para geração de energia termoelétrica com turbinas a gás, como substituto do gás natural. Para essa aplicação, e também para aplicações em síntese de produtos químicos e combustíveis pelo processo Fischer Tropsch, teores de metais alcalinos, enxofre e cloretos são críticos. A biomassa considerada foi a madeira de Eucalyptus grandis. O trabalho propõe a lixiviação aquosa daqueles contaminantes por pré-hidrólise ácida da biomassa, seguida da moagem a úmido da celulignina para razões líquido/sólido (L/S) otimizadas em relação ao consumo de água e aos teores finais dos contaminantes na biomassa tratada. A eficiência da sequência de tratamentos foi verificada medindo os teores de potássio, sódio, cloreto e enxofre total após cada etapa de lixiviação da celulignina. A pré-hidrólise ácida do E. grandis foi realizada na presença de ácido sulfúrico como catalisador, com produção de cerca de 67% de celulignina e 34% de solução de açúcares, em relação à quantidade de biomassa seca inicial. Os resultados desta etapa do processamento mostraram uma redução no teor de potássio de 3,3 vezes e no teor de sódio de 1,9 vez na celulignina em relação ao E. grandis in natura. A celulignina assim obtida foi submetida a uma sequência de moagem a úmido em moinho de martelos. Resultados apontaram a razão L/S = 12 como mais eficiente. O singás obtido da celulignina apresentou teores estimados de K+ + Na+= 600 ppb, Cl-=1,4 mg/Nm³ e enxofre total = 4 mg/Nm³. Isso significa uma redução de 1000 vezes em K+ + Na+ em relação à biomassa bruta. Nessas condições, o gás de síntese obtido já seria similar ao singás do gás natural, podendo ser usado em turbinas a gás. As aplicações com o gás de síntese no processo Fischer Tropsch não estão descartadas já que as especificações do gás natural para essa mesma aplicação permitem um máximo de enxofre de 70 mg/Nm³. Melhoramentos nos procedimentos de análise química em todas as etapas do processo são necessários para levar a resultados mais acurados. Melhoramentos nos equipamentos de controle das emissões gasosas na geração do singás tendem a diminuir os teores de enxofre para os níveis previstos em norma (< 1mg/Nm³). / This work is part of the Program Biomass - Energy - Materials - PROBEM?, whose Biomass Refinery develops technologies for a self-sustaining exploration of lignocellulosic and oily biomass. The main products are fuels for thermal and electricity energy generation, chemicals, materials and recycled inorganic fertilizers. This work explores the cellulignin, which is a fuel obtained by acidic prehydrolysis of biomass aiming to produce synthesis gas (syngas) as a substitute for natural gas for themoelectrical energy generation with gas turbines. This application, and also for the Fischer Tropsch process, of alkali metals, sulfur and chlorine concentrations in the syngas must be very low. The selected biomass is Eucalyptus grandis. The main objectives are to promote the aqueous leaching of those contaminants from cellulignin by a sequence of treatments, and to obtain the syngas by gasification of the cleaned cellulignin. The aqueous leaching of contaminants is carried out by acidic prehydrolysis of the wood, followed by the wet grinding of cellulignin at different liquid / solid (L/S) rations optimized with respect to water consumption and the final concentration of contaminants in the treated biomass. The efficiency of the sequence of treatments was checked by measuring potassium, sodium, chloride and sulfur contents in the cellulignin after each leaching step. Prehydrolysis of E. grandis was carried out using sulfuric acid as a catalyst, producing 67% of cellulignin and 34% of hydrolysate in relation to the initial dry biomass mass. Results after prehydrolysis showed a reduction of 3.3 times in the potassium content and of 1.6 times for sodium in the unwashed cellulignin in relation to the E. grandis \'in natura\'. The cellulignin so obtained was wet-ground in hammer mill. Results showed the L/S = 12 as the more efficient ratio in the grinding step. After gasification of the cellulignin the estimated values of the contaminants in the syngas were K++Na+ = 600 ppb, Cl- =1,4 mg/Nm³, and total S = 4 mg/Nm³, similar to the syngas from natural gas specifications for those elements. This means that the syngas from the cellulignin can be used as a fuel in gas turbines, replacing the syngas obtained from natural gas. Yet, its application in the Fischer Tropsch process is not discarded because maximum sulfur content allowed in the natural gas for that application is 70 mg/Nm³. Improvements have to made on the analytical procedures to ensure more accurate results, and is also necessary to improve the efficiency of the equipments for gas emission control in the syngas generation process. The last improvement should lower the S content to the specification values for the syngas (< 1mg/Nm³).

Les horloges atomiques miniatures présentent des stabilités de fréquence inégalées avec des volumes de quelquescentimètres cubes et des consommations inférieures à 100mW.Dans cette thèse, les paramètres optimaux concernant la conception et la fabrication des cellules à vapeur decésium, un des composant clés de ce type d’horloges, sont définis. Ainsi, les performances de plusieurs cellulesont été caractérisées en condition d’horloge à court et long terme. En parallèle, des solutions sont proposéespour pallier à certaines limitations telles que la plage de température opérationnelle, le coût de fabrication dudispositif et la facilité d’assemblage du module physique.Un nouveau mélange de gaz tampon composé de néon et d’hélium peut étendre la plage de fonctionnementau-dessus de 80 C, en adéquation avec les besoins industriels. A l’inverse des gaz tampon usuels, ce mélangeest compatible avec les dispensers de césium solides, dont la fiabilité est établie.Outre les gaz tampon, les revêtements permettent également de limiter la relaxation induite par les parois dela cellule. Ici, des revêtements d’octadécyltrichlorosilane sont étudiés. Un effet anti-relaxant a été observé dansdes cellules centimétriques et un procédé a été développé pour revêtir des cellules micro-fabriquées.D’autres sources de césium sont présentées pour s’affranchir des inconvénients propres aux dispensers solides.Un dispenser sous forme de pâte, qui peut être déposée collectivement, a été étudié et montre des densitésatomiques stables jusqu’à présent. Un concept de vannes hermétiques micro-fabriquées a été proposé poursceller hermétiquement et séparer des cellules d’un réservoir de césium commun.Les premières étapes vers un module physique micro-fabriqué sont ensuite présentées. En particulier, un designoriginal de cellule combinant des réseaux de diffraction à une cavité en silicium formée par gravure anisotropea été caractérisé et a montré des contrastes CPT remarquables malgré un volume de cavité réduit, ce qui permettraitde réaliser un module physique particulièrement compact. Enfin, des cellules intégrant des résistanceschauffantes et thermométriques ont été fabriquées et leur compatibilité vis-à-vis du champ magnétique généréa été caractérisée dans un prototype de module physique compact. / Chip-scale atomic clocks (CSACs) provide unprecedented frequency stability within volumes down to a fewcubic centimeters and power consumptions as low as 100mW.In this work, we determine the optimal parameters regarding the design and the fabrication of cesium vaporcells, one of the key components of a CSAC. For this purpose, cells were characterized on both short and longtermperformances in clock setups. In addition, we propose solutions to overcome present limitations includingthe operating temperature range, the device microfabrication cost and the ease of integration of the physicspackage.A novel mixture of buffer-gas composed of neon and helium was found to potentially extend the operating rangeof the device above 80 C, meeting the industrial requirements. Unlike the well-known buffer gas compositions,this mixture is compatible with solid cesium dispensers whose reliability is established. As an alternativeto buffer gases, wall coatings are known to limit the relaxation induced by sidewalls. Here, we investigatedoctadecyltrichlorosilane (OTS) coatings. An anti-relaxation effect has been observed in centimeter-scale cellsand a process was developed to coat microfabricated cells.Other cesium sources have been investigated to overcome the drawbacks imposed by solid cesium dispensers. Apaste-like dispenser, which can be deposited collectively, was explored and has shown stable atomic densities sofar. Single-use zero-leak micro valves were also proposed to hermetically seal and detach cells from a commoncesium reservoir.Eventually, the first steps toward a microfabricated physics package were made. In particular, an originalcell design combining diffraction gratings with an anisotropically etched single-crystalline silicon sidewalls wascharacterized and exhibited remarkable CPT contrasts despite a reduced cavity volume, which could lead to amore compact physics package. Finally, cells with integrated heating and temperature sensing resistors werefabricated and their magnetic field compliance was characterized in a compact physics package prototype.